JPH04195136A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material ensuring satisfactory color reproducibility, shelf stability of an image, color developing property and a fine white ground by regulating the amts. of a UV absorber, a dye image stabilizer and a stain inhibitor. CONSTITUTION:A silver halide emulsion layer contg. a cyan coupler represented by formula I and further contg. at least one of compds. represented by formulae II-IV by 10-60mol% of the amt. of the coupler and a compd. represented by formula V by 0.3-3mol% is formed. In the formula I, R1 is a ballast group, R2 is >=2C alkyl and Z1 is H, etc. In the formula II, each of R10-R12 is alkyl, etc., and m is an integer of 0-3. In the formula III, R13 is H, hydroxyl, etc., each of R14-R''14 is alkyl, each of R15 and R16 is H, etc., and n is an integer of 0-4. In the formula IV, each of R21-R23 is H, halogen, etc. In the formula V, each of R1-R4 is H, halogen, etc. Superior color reproducibility, shelf stability of a cyan dye image, satisfactory color developing property and a fine white ground and ensured.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material that has excellent color reproducibility, image storage stability and color development.

[Background of the invention]

In silver halide color photographic materials, silver halide is spectrally sensitized using a sensitizing dye by a commonly used subtractive method, and the spectrally sensitized silver halide emulsion layer contains a coupler. After imagewise exposure, development is performed using an aromatic primary amine color developing agent, followed by bleach-fixing to form a dye image. Normally, such couplers reproduce colors by subtractive color method, so
3 forms three pigments: yellow, magenta, and cyan
species couplers are used.

In recent years, silver halide color photographic light-sensitive materials are required to have high standards in terms of color reproducibility and image storage stability. Therefore, the basic properties required of each coupler are as follows: Forms clear dye images with excellent spectral absorption characteristics, good color tone, and wide color reproduction gamut;
The image storage stability is good, that is, the obtained dye image does not change color even if it is exposed to light for a long period of time or is stored under high temperature and high humidity, and the color photographic light-sensitive material has good stability. One of the reasons for this is that stains caused by so-called fogging, which occur when unexposed areas of colored areas (hereinafter referred to as white backgrounds) are developed with silver, are less likely to occur. Among these, dyes formed from phenolic cyan couplers with a methyl group at the 5-position, which have been widely used as cyan couplers in particular, have excellent color tone and fastness to light (hereinafter referred to as light storage stability). Although it is good, there is a problem that its fastness under high temperature and high humidity (hereinafter referred to as dark storage stability) is poor. As a cyan coupler with improved dark storage stability, for example, a 2,5-diacylaminophenol cyan coupler is known.

The dye formed from the 2.5-diacylaminophenol cyan coupler is the commonly used 5
Compared to dyes formed from phenolic cyan couplers that do not have an acylamino group in the position, the maximum absorption wavelength is on the shorter wavelength side, and the secondary absorption near 550 nm is large, making it difficult to reproduce vivid green colors. There is a drawback.

On the other hand, when using a phenolic 2-acylaminocyan coupler having an alkyl group having 2 or more carbon atoms other than a methyl group at the 5-position,
Compared to acylamino cyan couplers, the color tone of the cyan dye formed is better and the dark storage stability is improved, but contrary to the aforementioned cyan couplers, the light storage stability may deteriorate. ,Understood.

In order to improve this bright storage stability, methods using ultraviolet absorbers and various dye image stabilizers are disclosed in Japanese Patent Publications No. 48-31256 and No. 48-31625, and U.S. Patent No. 3.069.26.
No. 2, No. 3.432.300, No. 3.574.6
No. 27 is stated in each specification.

Furthermore, it has conventionally been known to use hydroquinone derivatives and the like as anti-staining agents in order to prevent staining caused by fogging in non-colored areas.

Given the above background, phenolic 2-acylaminocyan couplers having an alkyl group with a carbon number of 2 or more other than a methyl group at the 5-position have good color tone and good dark storage stability, although they have poor light storage stability. Because of its excellent properties, it is often used, and further improvements are desired.

Therefore, in order to improve the light storage stability, we used this phenolic 2-acylaminocyan coupler in combination with the above-mentioned ultraviolet absorber, various dye image stabilizers, and stain inhibitors, and found that the spectral absorption properties A clear dye image with excellent color tone and a wide color reproduction gamut was formed, and a white background with almost no staining was obtained. However, even with the above combination, it was found that not only the light storage stability was still insufficient, but also a new problem was that the color development was poor.

Therefore, from the above combination, it was not possible to obtain a silver halide color photographic light-sensitive material that satisfied all the conditions of color reproducibility, image storage stability, good white background, and sufficient color development.

Therefore, the present inventors further investigated various aspects of this combination, and found that by specifying the amounts of the ultraviolet absorber, dye image stabilizer, and anti-stain agent within a certain range, all of the above-mentioned conditions could be satisfied. It was discovered that this could be obtained, and the present invention was hereby accomplished.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide color photographic material that provides excellent color reproducibility, excellent storage stability of cyan dye images, and provides a good white background and sufficient color development. It is in.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material having a cyan coupler-containing silver halide emulsion layer on a support, in which the cyan coupler-containing silver halide emulsion layer is represented by the general formula [C] as the cyan coupler. containing at least one cyan coupler, and having the general formula [work],
At least one of the compounds represented by the general formula (II) and the general formula (III) is added to the cyan coupler for 10
It contains 0.3 mol% to 3 mol% of at least one compound represented by the general formula [IV] based on the cyan coupler. This is achieved by silver halide color photographic light-sensitive materials.

[In the formula, R1 represents a ballast group, and R7 represents an alkyl group having 2 or more carbon atoms. Zl represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of a color developing agent.

] [In the formula, R1° and R11 each represent an alkyl group.

R+*(t7A kill group, -NHR', , -8R'
,.

(R'+* represents a monovalent organic group.) or -c.

OR' If (R"1. represents a hydrogen atom or a monovalent organic group). m represents an integer of 0 to 3.] [In the formula, R58 is a hydrogen atom, a hydroxyl group, an oxyradical group. , SOR'+m, -3O,R',.

(R'+s represents an alkyl group or an aryl group),
Alkyl group, alkenyl group, alkynyl group or COR
'1s (R'1. represents a hydrogen atom or a monovalent organic group). R14, R'14 and R' +4 each represent an alkyl group. R1 and R1° each represent a hydrogen atom or a monovalent organic group. 10COR"(R'" represents a -valent organic group). Also, R11 and R1 may jointly form a heterocycle. n represents an integer from θ to 4.] General formula (III) H [wherein R31, Ro and R1 are each a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an alkyl group,
Represents an aryl group, alkoxy group, aryloxy group or alkenyl group. [In the formula, R1, R7, R2 and R4 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group , alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, alkyl2. Sulfamoyl group, arylsulfamoyl group,
Represents an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a cyano group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group, or an arylacyloxy group. However, R5 and R2
At least one of them is a group having a total number of carbon atoms of 3 or more. ] [Specific Structure of the Invention] The cyan coupler represented by the above general formula [C] will be explained.

In the cyan coupler represented by the general formula [C],
The alkyl group represented by R2 may be linear or branched, and includes those having a substituent.

R2 is preferably an alkyl group having 2 to 6 carbon atoms.

The ballast group represented by R7 is an organic group having a size and shape that imparts sufficient bulk to the coupler molecule to substantially prevent diffusion of the coupler from the layer to which it is applied to other layers. be.

Preferable examples of the ballast group include the following general formula: include.

Next, specific examples of the coupler represented by the general formula [C] will be shown, but the coupler is not limited thereto.

Specific examples of cyan couplers that can be used in the present invention, including these, include JP-B No. 40-11572, JP-A-61-3142, JP-A-61-9652, and JP-A-61-9.
No. 653, No. 61-39045, No. 61-50136
No. 61-99141, No. 61-105545, etc.

The cyan dye-forming coupler of the present invention represented by the general formula [C] is usually 1X10-'' per mole of silver halide.
mole-1 mole, preferably lXl0-'' mole to 8X10
It can be used in the range of −' molar.

In the present invention, the cyan coupler represented by the general formula [C] is preferably used in combination with the cyan coupler represented by the following general formula (C-2).

General formula (C-2) [In the formula, R+ represents an alkyl group or an aryl group. R1
represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R8 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

Further, R8 may cooperate with R1 to form a ring. Z represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of an aromatic primary amine color forming agent. ] In the cyan coupler represented by the general formula (C-2), the alkyl group represented by R1 has 1 to 3 carbon atoms.
2 are preferred, and these may be linear or branched,
It also includes those with substituents.

The aryl group represented by R1 is preferably a phenyl group, including those having substituents.

The alkyl group represented by R2 preferably has 1 to 32 carbon atoms, and these alkyl groups may be linear or branched (and also include those having substituents).

The cycloalkyl group represented by R2 has 3 to 1 carbon atoms.
2 is preferred, and these cycloalkyl groups also include those having substituents.

The aryl group represented by R1 is preferably a phenyl group, including those having substituents.

The heterocyclic group represented by R8 is preferably a 5- to 7-membered one, including those having a substituent, and may be fused.

R represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, but Rs is preferably a hydrogen atom.

In addition, the ring formed jointly by R1 and R8 is preferably a 5- to 6-membered ring, for example, a ring that is separated by reaction with an oxidized product of the color developing agent represented by Z in the general formula (C-2). Possible atoms or groups include:
Examples include halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, sulfonyloxy groups, acylamino groups, sulfonylamino groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, and imide groups (including those with substituents). However, halogen atoms, aryloxy groups, and alkoxy are preferred.

Among the above-mentioned cyan couplers, those represented by the following general formula (C-2A) are particularly preferred.

In the formula, ROI represents a phenyl group substituted with at least one halogen atom, and these phenyl groups include those having a substituent other than a halogen atom. Rot has the same meaning as R in the general formula (C-2). Zo represents a halogen atom, an aryloxy group or an alkoxy group,
Including those with substituents.

Typical specific examples of the cyan coupler represented by general formula (C-2) are shown below.

Specific examples of the above-mentioned cyan couplers include Japanese Patent Application No. 61-21853, pages 26 to 35, and Japanese Patent Application Laid-Open No. 60-225155, page 7, lower left column to 10.
Described in the lower right column of the page, the upper left column of page 6 to the lower right column of page 8 of JP-A-60-222853, and the lower left column of page 6 to the upper left column of page 9 of JP-A-59-185335. 2,5
- diacylamino cyan couplers, and can be synthesized according to the methods described in these specifications and publications.

The cyan dye type coupler of the present invention represented by the general formula (C-2) is usually lXl0'' per mole of silver halide.
"~1 mole, preferably lXl0-" mole ~8X10-
' Can be used in the molar range.

In addition, in the cyan coupler used in the present invention, when the compound represented by the general formula [C] and the general formula (C-2) is used together, the compound represented by the general formula [C] and the general formula (C-2) are used together.
-2) The combination ratio of the compound shown is 5:5 to 9.5.
:0.5 ratio is preferred, particularly preferably 7:3~
The ratio is 9:1.

Next, the compound represented by the general formula CI) will be explained.

The alkyl group represented by R3° and R1+ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 3 to 8 carbon atoms and branched at the α position.

Particularly preferred for R1° and R11 is a t-butyl group or a t-pentyl group.

The alkyl group represented by R12 may be linear or branched, and includes, for example, a methyl group, ethyl group, propyl group, butyl group, octyl group, and octadecyl group. When this alkyl group has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, a nitro group, a cyano group, an aryl group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a heterocyclic group. Examples include groups.

R'1. and R#1. Examples of the monovalent substituent represented by include an alkyl group, an aryl group, a cycloalkyl group, and a heterocyclic group. When these organic groups have a substituent, examples of the substituent include a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, an alkyl group, an aryl group, an alkenyl group, and an acyloxy group.

In the present invention, compounds represented by the general formula (I) are preferably compounds represented by the following general formula [I'].

General formula [I'] In the formula, R'l. and R′1. each has 3 carbon atoms
~8 straight-chain or branched alkyl groups, especially t-
Butyl group, t-pentyl group, etc. are preferred.

Rk represents a divalent organic group. k represents an integer from 1 to 6.

Examples of divalent organic groups represented by Rk include alkyl groups, alkenyl groups, polyunsaturated hydrocarbon groups (ethylene,
trimethylene, propylene, hexamethylene, 2-chlorotrimethylene, etc.), unsaturated hydrocarbon groups (pentaerythrityl, dipentaerythrityl, etc.), alicyclic hydrocarbon groups (cyclopropyl, cyclohexyl, cyclohexenyl groups, etc.), aryl groups (phenyl group, etc.), arylene group (
1, 2-11, 3- or 1. 4-phenylene group, 3
, 5-dimethyl-1,4-phenylene group, 2-t-butyl-1,4-phenylene group, 2-chloro-1,4-phenylene group, naphthalene group, etc.), 1, 3. Examples include 5-trisubstituted benzene group.

In addition to the above-mentioned groups, Rk further includes divalent organic groups bonded to any of the above-mentioned groups via a 10-1-S-1-8O1- group.

Rk is more preferably 2,4-di-t-butylphenyl group, 2,4-di-t-pentylphenyl group, p-octylphenyl group, p-dodecylphenyl group, 3.5-t
-butyl-4-hydroxyphenyl group, 3,5-di-t
-pentyl-4-hydroxyphenyl group.

Preferably, k is an integer of 1 to 4.

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

I-9 Ni 10 ■-12 Next, the compound represented by the general formula (II) will be explained.

The alkyl group represented by Ro preferably has 1 to 1 carbon atoms.
12 alkyl groups, preferably alkenyl groups and alkynyl groups having 2 to 4 carbon atoms, and preferred groups for RIa include hydrogen atoms, alkyl groups, alkenyl groups, and alkynyl groups. and -COR',.

It is. R'1. The monovalent organic group represented by is, for example, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.

The alkyl groups represented by R14, R'14 and R', 4 are preferably linear or branched alkyl groups having 1 to 5 carbon atoms, and particularly preferably a methyl group.

In R4 and RIa, the monovalent organic group represented by R'' is, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylamino group, an arylamino group, etc. Examples of the heterocycle formed by this include (Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl group).

In the present invention, compounds represented by the general formula (II) are preferably represented by the following general formula [■'].

General formula [■'] Rb represents an alkyl group, an alkenyl group, an alkynyl group or an acyl group.

More preferable groups for Rb include methyl group, ethyl group,
They are vinyl group, allyl group, propynyl group, benzyl group, acetyl group, propionyl group, acryloyl group, methacryloyl group, and crotonoyl group.

Specific compounds represented by general formula (II) are listed below, but are not limited thereto.

II-1 II-2 F-5 F-6 II-7 l-8 I[-9 l-10 l-11 ■-12 Next, the compound represented by the general formula (III) will be explained.

As the halogen atom represented by R11, Rll and Ro, ° is particularly preferably a chlorine atom.

The alkyl group and alkoxy group represented by Rll, Rll and R12 preferably have 1 to 20 carbon atoms, and the alkenyl group preferably has 2 to 20 carbon atoms, and may be linear or branched.

These alkyl groups, alkenyl groups, and alkoxy groups include those having substituents, such as aryl groups, cyano groups, halogen atoms, heterocyclic groups, cycloalkyl groups, cycloalkenyl groups, and spiro compound residues. , bridged hydrocarbon compound residue, acyl group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, hydroxyl group, alkoxy group,
Aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, nitro group, amino group (including substituted amino group), sulfamoylamino group,
Examples include alkoxycarbonylamino group, aryloxycarbonylamino group, acylamino group, sulfonamide group, imide group, ureido group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, sulfamoyl group, phosphonyl group, etc. .

R11, R1! The aryl group represented by R21 is preferably, for example, a phenyl group, and the aryloxy group is preferably, for example, a phenyloxy group, and these groups also include those having a substituent (for example, an alkyl group, an alkoxy group, etc.).

Among the groups represented by R22 and Rx, hydrogen atoms, alkyl groups, alkoxy groups and aryl groups are preferable,
A hydrogen atom, an alkyl group, and an aryl group are particularly preferred, and a hydrogen atom and an alkyl group are particularly preferred.

Among the groups represented by R2+, hydrogen atoms, norogen atoms, alkyl groups, and alkoxy groups are particularly preferred.

Specific compounds represented by the general formula [III] are listed below, but are not limited thereto.

In the present invention, the compounds represented by the general formula [I], the general formula [II] and the general formula (III) may be used alone, or
They may also be used in combination, and the amount of the compounds represented by general formula [I], general formula [II], and general formula [III] (if used together, the total amount) is the cyan coupler used in the present invention. C], it is preferably used in a content of 10 mol% to 60 mol%, particularly 20 mol% to 5 mol%.
More preferably, the content is 0 mol%.

According to the present invention, when the above content is less than 10 mol%, the dark storage stability is insufficient, and even when combined with any amount of the compound represented by the general formula [IV] of the present invention, the light storage stability is does not reach a sufficient level.

Next, the compound represented by the general formula [IV] will be explained.

In the general formula (IVI H tI), in the atoms or groups represented by R1, R2, R1, and R4, examples of the halogen atom include fluorine, chlorine, and bromine atoms, Examples of alkyl groups include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, amyl, i
Examples include various groups such as -amyl, octyl, dodecyl, and octadecyl, and particularly preferred are alkyl groups having 1 to 32 carbon atoms.

Examples of the alkenyl group include allyl, octenyl, and oleyl groups, with alkenyl groups having 2 to 32 carbon atoms being particularly preferred.

Examples of the aryl group include phenyl, naphthyl, and other groups.

Examples of the acyl group include acetyl, octanoyl, lauroyl, and other groups.

Examples of the cycloalkyl group include cyclohexyl and cyclopentyl groups.

Examples of the alkoxy group include methoxy, ethoxy, and dodecyloxy; examples of the aryloxy group include phenoxy; and examples of the alkylthio group include methylthio, butylthio, and dodecylthio. Examples of the arylthio group include a phenylthio group, and examples of the alkylacylamino group include an acetylamino group.
Examples of arylacylamino groups include benzoylamino groups, examples of alkylcarbamoyl groups include methylcarbamoyl groups, examples of arylcarbamoyl groups include phenylcarbamoyl groups, and alkylsulfonamide groups. as,
Examples of the arylsulfonamide group include a phenylsulfonamide group, examples of the alkylsulfamoyl group include a methylsulfamoyl group, and arylsulfonamide groups. Examples of the alkylsulfonyl group include a phenylsulfamoyl group, examples of the alkylsulfonyl group include a methylsulfonyl group, examples of the arylsulfonyl group include a phenylsulfonyl group, and examples of the alkyloxycarbonyl group include a phenylsulfonyl group. Examples of aryloxycarbonyl groups include phenyloxycarbonyl groups, examples of alkylacyloxy groups include acetyloxy groups, and examples of arylacyloxy groups include, for example, Examples include benzoyloxy group.

These groups include those having substituents, and these substituents include alkyl groups, aryl groups, aryloxy groups, alkylthio groups, cyano groups, acyloxy groups, alkoxycarbonyl groups, acyl groups, sulfamoyl groups, and hydroxy groups. , a nitro group, an amino group, a heterocyclic group, and the like.

And at least one group among R and R3 is
A group having a total number of carbon atoms of 3 or more including the substituents listed above.

Specific compounds represented by the general formula [IV] are listed below, but the present invention is not limited thereto.

H The compound represented by the general formula [IV] used in the present invention may be used alone or in combination, and the amount of the compound represented by the general formula [IV] may be 0.3 mol % to It is added in a proportion of 3 mol%, more preferably 0.5 mol% to 3.0 mol%. If it is less than 0.3 mol%, the stain will increase significantly, which is undesirable.
Moreover, if it exceeds 3 mol%, CI), [■], and CI[
No matter what amount (reason for limitation) of the compound shown in [] is combined, a configuration that achieves both color development and light storage stability cannot be found.

In addition to the cyan dye-forming coupler, a yellow dye-forming coupler and a magenta dye-forming coupler are used in the silver halide color light-sensitive material of the present invention.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable.

As the yellow dye-forming coupler, various acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloazole couplers, and open-chain acylacetonitrile couplers can be preferably used.

The compounds such as dye-forming couplers of the silver halide photographic light-sensitive material of the present invention are usually mixed with a high boiling point organic solvent having a boiling point of about 150° C. or higher or a water-insoluble polymer, and, if necessary, a low Buddha point and/or water-soluble organic solvent. They are dissolved together, emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and then added to the desired hydrophilic colloid layer. A step of removing the low-boiling organic solvent may be included simultaneously with the dispersion or dispersion.

The high boiling point organic solvent is preferably a compound having a dielectric constant of 665 or less, such as esters such as phthalates and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of 6.5 or less. More preferably, the dielectric constant is 6
．． 5 or less 1.9 or more, vapor pressure at 100℃ is 0.5
It is a high boiling point organic solvent of mmHg or less. Among these, phthalate esters and phosphoric esters are more preferred. Most preferred are dialkyl phthalates having an alkyl group having 9 or more carbon atoms. Furthermore, the high boiling point organic solvent may be a mixture of two or more kinds.

Note that the dielectric constant indicates the dielectric constant at 30°C.

These high-boiling organic solvents generally have a low
~400% by weight. Preferably, the amount is 10 to 100% by weight based on the coupler.

The silver halide photographic material used in the present invention can be, for example, color negative and positive films, particularly positive films using direct positive emulsions, and color photographic papers (including direct positive papers), but especially The effects of the present invention are effectively exhibited when color photographic paper intended for direct viewing is used.

The silver halide used in the silver halide photographic light-sensitive material of the present invention includes any silver halide commonly used in silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

The silver halide grains used in the present invention are preferably 9
It has a silver chloride content of 0 mol% or more, a silver bromide content of 10 mol% or less, and a silver iodide content of 0.5 mol%.
It is preferable that it is below. More preferred is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%.

The silver halide grains may be used alone or in combination with other silver halide grains having different compositions.

Further, it may be used in combination with silver halide grains having a silver chloride content of 90 mol % or less.

In addition, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more,
The ratio of silver halide grains having a silver chloride content of 90 mol% or more to all silver halide grains contained in the emulsion layer is 6.
It is 0% by weight or more, preferably 80% by weight or more.

The silver halide emulsion used in the present invention can be prepared by sulfur sensitization method,
Chemically sensitized by selenium sensitization, reduction sensitization, noble metal sensitization, etc.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.

As the binder used in the silver halide photographic material of the present invention, gelatin is preferably used.

Gelatin commonly used in the photographic industry includes alkali-treated gelatin, which is treated with limestone during the production process from collagen, and acid-treated gelatin, which is treated with hydrochloric acid, etc., and is generally made from cow bones, cow skin, and pig skin. Manufactured using nato as raw material.

The acid treatment in the acid-treated gelatin mentioned here is clearly distinguished from the I)H adjustment in the dispersion of the present invention.

For details on the manufacturing method, properties, etc. of these gelatins, see, for example, Arthur Veis' The Macro
Molecular Chemistry of Ge
1atin J, Academic Press.

pp. 187-217 (1964), T. H. James.
:The Theory of the Photog
rapic Process 4th, ed, 1
977, (Macmillan), page 55, Scientific Photography Handbook (Part 1), pages 72-75 (Maruzen), Fundamentals of Photographic Engineering - Silver Salt Photography Edition, pages 119-124 (Corona Publishing), etc.

The gelatin used in the silver halide photographic light-sensitive material of the present invention may be lime-treated gelatin or acid-treated gelatin, or may be gelatin manufactured from cow bone, cow skin, pig skin, etc. as a raw material. However, lime-processed gelatin produced using bovine bone as a raw material is preferable.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Ru. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

To prevent fogging caused by discharge caused by friction of the photosensitive material in the hydrophilic colloid layers such as the protective layer and intermediate layer of the silver halide photographic light-sensitive material of the present invention, and to prevent image deterioration due to ultraviolet light. may also contain an ultraviolet absorber.

The silver halide photographic material of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

A matting agent is added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photosensitive material of the present invention for the purpose of reducing the gloss of the photosensitive material, increasing the ease of writing, and preventing the photosensitive materials from sticking together. Can be added.

A lubricant can be added to the silver halide photographic material of the present invention in order to reduce sliding friction.

In the present invention, an antistatic agent can be added to the silver halide photographic light-sensitive material for the purpose of preventing static electricity. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in colloid layers.

The silver halide photographic light-sensitive material of the present invention has a photographic emulsion layer and/or
Alternatively, other hydrophilic colloid layers may contain various interfaces for the purpose of improving coating properties, preventing static electricity, improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.). An activator is used.

The photographic emulsion layer and other layers of the silver halide photographic light-sensitive material of the present invention are baryta paper or paper laminated with an α-olefin polymer or the like, a paper support from which the α-olefin layer can be easily separated from the paper support, or synthetic paper. Flexible reflective supports such as cellulose acetate, cellulose nitrate, polystyrene, etc.
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, reflective supports coated with white pigments, and rigid bodies such as glass, metal, and ceramics. Alternatively, a thin reflective support of 120 to 160 μm can also be used.

The support used in the present invention may be either a reflective support or a transparent support, and may contain a white pigment in the support in order to have reflective properties, or a hydrophilic support containing a white pigment on the support. A sex colloid layer may also be applied.

As the white pigment, inorganic and/or organic white pigments can be used, preferably inorganic white pigments, such as alkaline earth metal sulfates such as barium sulfate, calcium carbonate, etc. Examples include alkaline earth metal carbonates, finely divided silicic acid, synthetic silicates of silica, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

The silver halide light-sensitive material of the present invention can be prepared by subjecting the surface of the support to corrodischarge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or applying an undercoat layer (adhesiveness, antistatic property, dimensional stability, etc. of the support surface). degree stability, abrasion resistance, hardness, anti-halation properties,
1 for improving frictional properties and/or other properties
or two or more undercoat layers).

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes.

In the present invention, immediately after color development, it may be treated with a processing solution having a bleaching ability, but the processing solution having a bleaching ability may also be a processing solution having a fixing ability (a so-called bleach-fix solution). As the bleaching agent used in the bleaching step, a metal complex salt of an organic acid is used.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments are not limited thereto.

Example 1 On a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side, each layer having the structure shown below was coated on the side of the polyethylene layer containing titanium oxide. A multilayer silver halide color photographic material was prepared.

The painting solution was prepared as follows.

1st layer coating liquid Yellow coupler (Y-1) 26.7g, dye image stabilizer (ST-1) 10.0g, dye image stabilizer (ST
-2) 6.67 g, additive (IV-4) 0, 67
60 ml of ethyl acetate was added to 6.67 g of g and high boiling point organic solvent (DNP) and dissolved, and this solution was added to 220 ml of 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer. The mixture was emulsified and dispersed to prepare a yellow coupler dispersion. A blue-sensitive silver halide emulsion (
(containing 10 g of silver) to prepare a first layer coating solution.

The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution.

In addition, (H-1) was added to the second and fourth layers as a hardening agent.
(H-2) was added to the seventh layer. Coating aids include surfactant (SU-2), (SU-comparative cyan coupler cc-i T-1 I-2 Al-3 AI-4 CHaSOmNa Hibiki NaO,S -CHCOOCHICHC4H1CH*C
00CHzCHC4Hs 0*Hs U-3 NaO,S-CHCOOCH2(CF2CF2),HC
H,C00CH2(CF,CF2)2HC(CH2SO
2CH=CH2).

Na (Preparation method of blue-sensitive silver halide emulsion) The following (solution A) and (solution B) were added to a 2% gelatin aqueous solution of 10,100 O kept at 40°C while controlling pAg = 6.5 and pH = 3.0. They were added simultaneously over a period of 30 minutes, and the following (liquid C) and (liquid D) were added simultaneously over a period of 180 minutes while controlling pAg=7.3 and pH=5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

After the addition, desalination was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.85 μm.
, coefficient of variation (σ/r)=0.07, silver chloride content 99.
A 5 mol % monodisperse cubic emulsion EMP-1 was obtained.

The above emulsion EMP-1 was chemically ripened for 90 minutes at 50°C using the following compound, and a blue-sensitive silver halide emulsion (E
m-B) was obtained.

(Preparation method of green-sensitive silver halide emulsion) (Liquid A) and (B
The average particle size was 0.4 in the same manner as EMP-1 except that the addition time of liquid) and the addition time of (liquid C) and (liquid D) were changed.
A monodisperse cubic emulsion EMP-2 having a coefficient of variation (σ/F) of 3 μm1 of 0.08 and a silver chloride content of 99.5 mol % was obtained.

For EMP-2, the following compound was used at 120°C at 55°C.
A green-sensitive silver halide emulsion (Em-G
) was obtained.

Stabilizer S T A B -16xlO-'Moro 1 mol AgX sensitizing dye G S -14xlO-'
mol 1 mol AgX (Preparation method of red-sensitive silver halide emulsion) Addition time of (solution A) and (solution B) and (solution C) and (D
The procedure was the same as EMP-1 except that the addition time of liquid) was changed, and the average particle size was 0.50 μm and the coefficient of variation (σ/y) was 0.
08, a monodispersed cubic emulsion EMP-3 having a silver chloride content of 99.5 mol % was obtained.

EMP-1 was heated to 90°C at 60"C using the following compound.
A red-sensitive silver halide emulsion (Em-R
) was obtained.

S-1 (CH2)ssUs' and H2JUυHS-2 The second coating material was used as sample 1, and then the comparison cyan coupler (CC-1) in the fifth layer of sample 1 was changed as shown in Table 1. , Samples 2 to 2 were prepared in the same manner as Sample 1, except that the amounts of dye image stabilizer (1-13) and stain inhibitor (IV-4) were changed as shown in Table 1. 27 was produced.

For the amount of dye image stabilizer (1-13) and the amount of stain inhibitor (IV-4), the amount added (g/m') and the molar ratio (%) relative to the cyan coupler are listed at the same time.

However, when using two or more types of cyan couplers in combination, if only cyan couplers other than the present invention are used in combination, the molar ratio (%) to the cyan coupler that is added in the largest amount is stated, and the cyan coupler of the present invention [C] When using together with a cyan coupler other than the present invention, the molar ratio to only the cyan coupler [C] of the present invention is described, and when using only the cyan coupler [C] of the present invention together, the cyan coupler [C] ]
The molar ratio to the total mole is described.

Table 1 These samples were exposed according to a conventional method and then processed according to the following processing steps.

Processing process Temperature Time Color development
Bleach and fix at 35,0±0.3°C for 45 seconds 35
．． Stabilized at 0±0.5°C for 45 seconds 30~34
℃ 90 seconds drying 60-80℃
60 seconds color developer Pure water 800ml Triethanolamine 10g N,N-diethylhydroxylamine 5g Potassium bromide
0.02g potassium chloride
2g potassium sulfite
0.3g ethylenediaminetetraacetic acid 1.0g
4.5g Fluorescent brightener (4,4-diaminostilbenesulfonic acid derivative) 1.0g Potassium carbonate 27g Add water to bring the total amount to 1
1 and adjust the pH to 10.10.

Bleach fixer Ferric ammonium dihydrate ethylenediaminetetraacetic acid 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) 27.5ml Add water to bring the total volume to If, potassium carbonate or glacial acetic acid and pH=
Adjust to 5.7.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20 % aqueous solution) 3.0g optical brightener (4,
4'-Diaminostilbenesulfonic acid derivative) Add 1.5 g of water to bring the total amount to 11, and add sulfuric acid or hydroxide columnum to pH = 7.0.
Adjust to.

The following characteristic values were determined for the obtained sample.

(1) Color development properties Using a PDA-65@meter (manufactured by Konica Corporation) for each treated sample, determine the maximum density (Dmax), and
Evaluation was made using a relative value set to 00.

(2) Perform the above treatment on each white sample without exposing it to X-Light Co., Ltd.
Reflection density was measured by OTR, and the minimum density was defined as Dmim.

(3) Color reproducibility L☆U☆V☆ as described in JIS Z-8729-1980
According to the display method using the color system, u' when L☆=50,
A v' chromaticity diagram was created, and the green reproduction range formed by the yellow and cyan coloring pigments was evaluated based on the relative area with Sample 1 set as 100.

Visually evaluating the finished print, the level at which it can be perceived that the saturation of green color has clearly improved is 10% in the color reproduction gamut.
The goal is to improve.

(4) Photopreservability The obtained sample was stored outdoors under sunlight (on an exposure table) for one month, and evaluated by determining the residual rate (%) of the dye image at an initial density of 1.0.

(5) Storage in the dark The obtained sample was stored at 85°C and 160% RH for 20 days, and the residual rate (%) of the dye image at the initial density of 1.0
The evaluation was made by determining the

The above test results are shown in Table-2.

Margin Table 2 Below As is clear from the results in Table 2, when the cyan coupler represented by the general formula [C] according to the present invention is used, the green reproduction range is expanded, color reproducibility is improved, and color Image stabilizer C
If the additive amounts of I) and anti-stain agent (IV) are used in combinations other than those of the present invention, the color development, white background, and light storage stability will not be compatible; however, only with the configuration of the present invention, the color development,
It has been found that all the performances of white background and light storage stability are fully satisfied, and the combination of the present invention does not result in insufficient dark storage stability.

Color image stabilizer (I) for the cyan coupler of the present invention
It is a surprising new fact that a specific combination of the respective addition amounts of the stain inhibitor [■] has a remarkable synergistic effect on the deterioration of white backgrounds (color development and light storage stability).

Example-2 A sample exactly the same as sample 12 in Example-1 was prepared and designated as sample 2-1. Next, the cyan coupler in the fifth layer of sample 2-1 was changed as shown in Table-3. Alternatively, a dye image stabilizer (I-13) and a stain inhibitor (IIV
-4') was replaced as shown in Table-3, except for sample 2.
Samples 2-1 to 2-27 were prepared in the same manner as in -1.

The amounts of the dye image stabilizer and the stain inhibitor are expressed in molar ratio (%) to the cyan coupler.

However, when using two or more types of cyan couplers in combination, and when using only the cyan coupler CC) of the present invention, the molar ratio of the cyan coupler [C] to the total mole of the cyan coupler [C] and the cyan coupler [C] of the present invention should be stated. When a cyan coupler other than the present invention is used in combination, the molar ratio to only the cyan coupler [C] of the present invention is described.

Table-3 These samples were exposed and processed in the same manner as in Example-1,
Regarding the obtained sample, the same characteristic values as in Example-1 were determined.

The test results are shown in Table-3.

Margin Table 4 Below: As is clear from the results in Table 4, general formulas [I], (IF) and ( Compounds represented by the general formula [IV] according to the present invention other than the compound represented by II) and the stain inhibitor (IV-4) used in Example-1 are represented by the general formula [C] according to the present invention. It can be seen that even when used together with a cyan coupler, all of the performances of color development, white background, and light storage stability are fully satisfied only when the amounts added are within the ranges according to the present invention.

Further, the cyan coupler represented by the general formula [C] according to the present invention and the cyan coupler represented by the general formula [C-2] shown in this specification may be used together under the structure of the present invention. Samples 2-17 to 2-25 prepared by
It can be seen that an even higher level of overall performance can be obtained, including green reproducibility, storage stability in light and storage in darkness.

Example-3 Cyan coupler C-4 of sample 13 in Example-2 was converted into C-8, C-9, C-11, C-13, C-8, C-9, C-11, C-13, and C-4 in the same molar amount.
Among the cyan couplers of sample 20 in sample 13 and sample 20 in Example-2, which were prepared in the same manner as sample 13 except that C-15 and C-16 were substituted,
, C-2-9, C-2-12, C-2-14, C-2-
18, C-2-29, C-2-30, C-2-30: A sample prepared in exactly the same manner as Sample 2° was exposed and processed in the same manner as in Example-2, except for the following changes. When the obtained sample was evaluated in the same manner as in Example 2, the effects of the present invention were obtained.

Example 4 Each layer having the structure shown below was coated on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the first layer side of the other side, and a multilayer silver halide layer was formed. A color photographic material was produced. Kabu liquid was prepared as follows.

1st layer coating liquid Yellow coupler (Y-2) 26.5g, dye image stabilizer (I-13) 10.0g, stain inhibitor (■-4)
) and 10 g of a high boiling point organic solvent (DNP) were added and dissolved in 60 ml of ethyl acetate, and this solution was mixed with an ultrasonic homogenizer using a 10% aqueous gelatin solution containing 7 ml of a 20% surfactant (SU2). The mixture was emulsified and dispersed to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution.

In addition, (H-1) was added to the second and fourth layers as a hardening agent.
(H-2) was added to the seventh layer. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension.

Each color-sensitive emulsion was prepared as follows.

[Blue-sensitive silver chlorobromide emulsion]

A silver chlorobromide emulsion with an average grain size of 0.7 μm and a silver bromide content of 90 mol% was optimally sensitized at 57°C using sodium thiosulfate to form a sensitizing dye (S-1) and a stable Z- as an agent
1 was added.

[Green-sensitive silver chlorobromide emulsion]

A silver chlorobromide emulsion with an average grain size of 0.5 μm and a silver bromide content of 70 mol% was optimally sensitized at 59°C using sodium thiosulfate, and the sensitizing dye (S-2) and stabilizer were sensitized using sodium thiosulfate. As Z-1
was added.

(Red-sensitive silver chlorobromide emulsion) Sodium thiosulfate, sensitizing dye (S-3) and phenol resin were added to a silver chlorobromide emulsion with an average grain size of 0.4 μm and a silver bromide content of 60 mol%. The sample was optimally sensitized at 60° C. and Z-1 was added as a stabilizer.

Cf T-4 CHI GH.

T-5 T-6 (Component A) (Component B) (Component C
) Component A: Component B: Component C = 50:46:4 (Mo/l
z ratio) O-1 song (CHrizsOsH(CHx)zsOs.

GH This coated sample is designated as Sample 4-1, and then the cyan coupler (CC-1) and (C-2-2) of the fifth layer of this Sample 4-1 are
) as shown in Table 5, and the amounts of dye image stabilizer (I-13) and stain inhibitor (IV-4) were changed as shown in Table 5. , Samples 4-2 to 4-28 were prepared in the same manner as Sample 4-1.

For the amount of dye image stabilizing compound agent (I-13) and the amount of stain inhibitor (IV-4), the amount added (g/m'') and the molar ratio (%) relative to the cyan coupler are listed at the same time.

However, when using two or more types of cyan couplers in combination, if only cyan couplers other than the present invention are used in combination, the molar ratio (%) to the cyan coupler that is added in the largest amount should be stated, and the cyan coupler of the present invention [c] If a cyan coupler other than the present invention is used in combination with the cyan coupler of the present invention, the molar ratio to only the cyan coupler of the present invention [C] should be described, and if only the cyan coupler of the present invention [C] is used in combination, the cyan coupler CC)
The molar ratio to the total mole is described.

Table 5 These samples were exposed to light according to a conventional method and then processed according to the following processing steps.

Processing process Temperature Time color development 33.0±0.3°C 3 minutes 30 seconds Bleach-fixing 33.0+0.5°C 1 minute 30 seconds Washing with water 30-34°C 3 minutes Drying 60-80°C 1 minute 3
0 second color developer Hydroxylamine sulfate 2.0g Potassium carbonate 25.0g Potassium bromide
0.6g anhydrous sodium sulfite
2.0g benzyl alcohol
13ml diethylenetriaminepentaacetic acid 3.0
g Triethanolamine 10.0 g Diethylene glycol io, 0 g Water was added to make 11, and the pH was adjusted to 10.0 with sodium hydroxide.

Bleach-fix solution Ethylenediaminetetraacetic acid iron (III) sodium salt 60g Ammonium thiosulfate 100g Sodium bisulfite 10g Sodium metabisulfite
Add 3g of water to make If, and adjust pH with ammonia water.
Adjust to 7.0.

Regarding the obtained sample, the same characteristic values as in Example-1 were determined. The test results are shown in Table-6.

The chromogenic green reproduction range was evaluated using a relative value with sample 4-1 set as 100.

Table 6 As is clear from the results in Table 6, only the configuration of the present invention provides excellent color reproducibility, excellent storage stability of cyan dye images, good white background, and sufficient color development of cyan dyes. A satisfactory photographic material was obtained.

Effects of the invention C] The present invention provides general formula [C], general formulas (I) to general formulas (IV
) in combination and in a specific ratio, it is possible to obtain excellent color reproducibility, excellent color development and cyan dye image storage stability, and also achieve the excellent effects of obtaining a good white background. .

Claims (1)

[Scope of Claims] In a silver halide photographic material having a cyan coupler-containing silver halide emulsion layer on a support, the cyan coupler-containing silver halide emulsion layer is represented by the general formula [C] as the cyan coupler. at least one cyan coupler
and contains at least one of the compounds represented by the general formula [I], the general formula [II], and the general formula [III] in an amount of 10 mol% to 60 mol% based on the cyan coupler, and further, A silver halide color photographic material containing at least one compound represented by the general formula [IV] in an amount of 0.3 mol % to 3 mol % based on the cyan coupler. General formula [C] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 represents a ballast group, and R_2 has 2 carbon atoms.
It represents the above alkyl group. Z_1 represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of a color developing agent. ] General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1_0 and R_1_1 each represent an alkyl group. R_1_2 is an alkyl group, -NHR'_1_2
, -SR'_1_2 (R'_1_2 represents a monovalent organic group) or -COOR''_1_2 (R''_1_2 represents a hydrogen atom or a monovalent organic group). m is 0~
Represents an integer of 3. ] General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1_3 is a hydrogen atom, hydroxyl group, oxy radical group, -SOR'_1_3, -SO_2R'_
1_3 (R′_1_3 represents an alkyl group or an aryl group), an alkyl group, an alkenyl group, an alkynyl group, or -COR″_1_3 (R″_1_3 represents a hydrogen atom or a monovalent organic group). R_1_4, R'_
1_4 and R″_1_4 each represent an alkyl group.R
_1_5 and R_1_6 are each a hydrogen atom or -O
COR'''(R''' represents a monovalent organic group). Further, R_1_5 and R_1_6 may jointly form a heterocycle. n represents an integer of 0 to 4. ] General formula [III] ▲ Contains mathematical formulas, chemical formulas, tables, etc. Represents an oxy group or an alkenyl group. ] General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3 and R_4 are each,
Hydrogen atom, halogen atom, alkyl group, alkenyl group,
Aryl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group,
Alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, cyano group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylacyloxy group, or Represents an arylacyloxy group. However, at least one of R_1 and R_3 has a total number of carbon atoms of 3.
These are the bases above. ]