JPS5959656A - Phenolic compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula (X is O or S; R1 is halogen, alkyl, etc.; R2 is 1-20C straight or branched chain alkylene; the position of -CN is o- or m- to the ureido group; R3 is halogen, alkyl, etc.; Z is H or a group eliminable in the coupling reaction with the oxidation product of a color developing agent; n is 0-3; m is 0-4; l is 0 or 1). EXAMPLE:2- (o-Cyanophenyl)ureido-4-chloro-5-[alpha- (2,4-di-tert-pentylphenoxy)-hexanamido]phenol. USE:A cyan coupler for silver halide photosensitive material. PROCESS:The exemplified compound is prepared by reacting 2-amino-4-chloro-5- nitrophenol with o-cyanophenyl isocyanate, reducing the product, reacting with 2-(o-cyanophenyl) ureido-4-chloro-5-nitrophenol, catalytically reducing the reaction product, and adding 2-(2,4-di-tert-pentylphenoxy)hexanoyl chloride to the reduction product.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel phenolic compounds. The phenol compound of the present invention has a phenylureido group having at least one cyano group in the ortho or meta position at the 2-position, a hydrogen atom at the 4-position, or a phenol compound that can be eliminated during the coupling reaction of an oxidation product of a color developing agent. It is a phenolic compound having an acylamino group at the 5th position and is a new compound. Furthermore, the phenolic compound of the present invention is particularly advantageously used as a cyan dye-forming coupler for silver halide photographic materials.

The phenolic compound in the present invention is more preferably represented by the following general formula [I].

General formula [I] [In the formula, X is an oxygen atom or a sulfur atom, R2 is a linear or branched alkylene group having 1 to 20 carbon atoms,
N is at the O-1 or m-1 position with respect to the ureido group, and R3 is a halogen atom (particularly preferably chloro, prom, etc.) or a monovalent organic group, such as an alkyl group {preferably a straight carbon number of 1 to 4. Chain or branched alkyl group (especially preferably methyl, tert-butyl)}, aryl group {preferably substituted or unsubstituted phenyl group}, heterocyclic group {preferably nitrogen-containing heterocycle {particularly preferably , pyrrolidine, piperidine)}, hydroxy group, alkoxy group {preferably a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms (particularly preferably methoxy, tert-butyloxy, methoxycarbonylmethoxy group)}, aryloxy group { Preferably, substituted or unsubstituted phenoxy group}, acyloxy group {preferably, substituted or unsubstituted alkylcarbonyloxy group, arylcarbonyloxy group}, mercapto group, alkylthio group {preferably substituted or unsubstituted carbon number an alkylthio group having 1 to 8 carbon atoms (especially preferably a methylthio group)}, a nitro group, an acyl group {preferably an alkylcarbonyl group having 1 to 8 carbon atoms (especially preferably an acetyl group, a pivaloyl group)
}, amino group, alkylamino group {preferably a linear or branched alkylamino group having 1 to 4 carbon atoms (particularly preferably a methylamine group, ethylamino group, tert
-butylamino group)}, dialkylamino group (preferably dimethylamino group, diethylamino group), R1 is a halogen atom (preferably chloro, bromine), an alkyl group (preferably linear or branched carbon number 1) From 20
an alkyl group (preferably methyl, tert-butyl, tert-pentyl, tert-octyl, dodecyl, pentadecyl)}, an aryl group (preferably phenyl), a heterocyclic group (preferably a nitrogen-containing heterocyclic group) , aralkyl group (preferably benzyl, phenethyl), alkoxy group {preferably a linear or branched alkyloxy group having 1 to 20 carbon atoms (particularly preferably methoxy, ethoxy, tert-butyloxy, octyloxy, decyloxy, dodecyloxy)}, aryloxy group (preferably phenoxy), hydroxy group, acyloxy group {preferably substituted or unsubstituted alkylcarbonyloxy group, (particularly preferably acetoxy),
Arylcarbonyloxy group (especially preferably benzoyloxy)}, carbonyl group, alkoxycarbonyl group (preferably substituted or unsubstituted carbon number 1 to 20)
straight-chain or branched alkyloxycarbonyl), aryloxycarbonyl group (preferably substituted or unsubstituted phenoxycarbonyl), mercapto group, alkylthio group (preferably straight-chain or branched substituted with 1 to 20 carbon atoms) or unsubstituted alkylthio), arylthio groups (preferably substituted or unsubstituted phenylthio),
Alkylsulfonyl group (preferably 1 to 20 carbon atoms)
straight-chain or branched alkylsulfonyl), arylsulfonyl group (preferably substituted or unsubstituted benzenesulfonyl), acyl group (preferably carbon number 1 to 2)
0 straight chain or branched alkyl carbonyl, substituted or unsubstituted benzene carbonyl), acylamino group (preferably straight chain or branched alkyl carbonyl having 1 to 20 carbon atoms, substituted or unsubstituted benzene carbonyl), Sulfonamide group (preferably 1 to 2 carbon atoms)
0 straight chain or branched substituted or unsubstituted alkylsulfonamide group, substituted or unsubstituted benzenesulfonamide group), carbamoyl group (preferably straight chain or branched alkylaminocarbonyl having 1 to 20 carbon atoms, substituted or unsubstituted phenylaminocarbonyl), sulfamoyl group (preferably linear or branched alkylaminosulfonyl having 20 carbon atoms, substituted or unsubstituted phenylaminosulfonyl), Z is a hydrogen atom or a group that can be eliminated during the coupling reaction with the oxidation product of the color developing agent, a halogen atom (for example, each atom such as chlorine, bromine, or fluorine), or a position to which an oxygen atom or nitrogen atom is directly coupled. Examples thereof include an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamide group, a succinimide group, and more specific examples include U.S. Pat. No. 3,471,563. , Japanese Patent Publication No. 47-37425
No., Special Publication No. 48-36894, Japanese Patent Publication No. 1977-1013
No. 5, No. 50-117422, No. 50-130441
No. 51-108841, No. 50-120334, No. 52-18315, No. 53-52423, No. 5
3-105226 and the like, n represents an integer from 0 to 3, m represents an integer from 0 to 4, and l represents an integer of 0 or 1, respectively. ] Specific compound examples of the phenolic compound of the present invention are illustrated below, but the invention is not limited thereto.

Typical synthetic routes and synthetic examples of the phenolic compound of the present invention are shown below.

Synthesis Example 1 (Synthesis of Exemplary Phenolic Compound 7) 2-(
O-cyanophenyl)ureido-4-chloro-5-{α
Synthesis of -(2,4-di-tert-pentylphenoxy)hexanamide}phenol.

18.9 g of 2-amino-4-chloro-5-nitrophenol was dispersed in 200 mg of toluene, and a solution of 16 g of O-cyanophenyl isocyanate in 100 ml of toluene was added while stirring at room temperature. The resulting reaction mixture was boiled and reduced for 1 hour. Thereafter, the mixture was cooled to room temperature, and the crystals were filtered and washed with hot toluene. Further wash with cold methanol,
31 g of a reaction product with a mp of 251 to 255°C was obtained. 3
3 g of 2-(O-cyanophenyl)ureido-4-chloro-5-nitrophenol was added to T.I. H. F. The mixture was dispersed in 200 ml and catalytically reduced using a palladium-carbon catalyst. After consuming the theoretical amount of hydrogen, add 0.9 ml of pyridine,
An additional 3.7 g of 2-(2,4-di-tert-pentylphenoxy)hexanoyl chloride was added to T.I. H. F. 5
A solution dissolved in 0 ml was added while stirring at room temperature. After the addition was completed, the reaction was continued for an additional hour, and then filtered to remove the catalyst. The filtrate was added to ice water containing 10 ml of concentrated hydrochloric acid and extracted with ethyl acetate. After washing with water, the ethyl acetate layer was separated, dried over sodium sulfate, and concentrated under reduced pressure to obtain an oil. Further, the mixture was solidified into an oily substance using a mixed solvent of benzene and hexane to obtain the desired product. mp1.
2.6 g of a white solid with a temperature of 63-168°C was obtained.

Elemental analysis value (%) C H N Cl
Theoretical value 68.28 7.16 3.85 5.
60 Experimental value 67.95 6.88 9.03
5.82 Synthesis Example 2 (Synthesis of Exemplified Phenolic Compound 8)
2-(m-cyanophenyl)ureido-4-chloro-5
- Synthesis of {α-(2,4-di-tert-pentylphenoxy)tetradecanamide}phenol.

18.9 g of 2-amino-4-chloro-5-nitrophenol was dispersed in 200 ml of toluene, and a solution of 16 g of m-cyanophenyl isocyanate in 100 ml of toluene was added while stirring at room temperature. The resulting reaction mixture was boiled and refluxed for 1 hour. Thereafter, the mixture was cooled to room temperature, and the crystals were filtered and washed with hot toluene.

Furthermore, after washing with cold methanol, drying (mp255-2
33 g of a reaction product at 59°C was obtained. 3.3 g of 2-(m
-cyanophenyl)ureido-4-chloro-5-nitrophenol from T. H. F. The mixture was dispersed in 200 ml and subjected to catalytic reduction using a palladium-carbon catalyst. After consuming the theoretical amount of water, add 0.9 ml of pyridine and add 4.8 g of 2-(2,4-di-tert-pentylphenoxy).
T. detradecanoyl chloride. H. F. A solution dissolved in 50 ml was added at room temperature with stirring. After the addition was completed, the reaction was continued for an additional hour and then filtered to remove the catalyst. The filtrate was added to ice water containing 10 ml of concentrated hydrochloric acid and extracted with ethyl acetate. After washing with water, the ethyl acetate layer was separated, dried over sodium sulfate, and concentrated under reduced pressure to obtain an oil. The reaction composition was purified using silica gel and column chromatography, and solidified using hexane.

2.7 g of white solid with mp 185-188°C was obtained.

Elemental analysis value (%) C H N Cl theoretical value 70.89 8.25 7.52 4.76 Experimental value 69.91 7.86 7.72 5.02 Phenol according to the present invention synthesized in this way These compounds can be preferably used as cyan dye-forming couplers in silver halide photographic materials.

Phenolic compound of the present invention (hereinafter referred to as the compound of the present invention)
When used as a cyan coupler for silver halide photographic light-sensitive materials, the methods and techniques used for cyan dye-forming couplers for ordinary silver halide photographic light-sensitive materials can be applied in the same manner. Typically, the compounds of this invention are incorporated into a silver halide emulsion and the emulsion is coated onto a support to form a photographic element. Photographic elements can be single color or multicolor elements. In multicolor elements, when the compounds of this invention are used as cyan dye-forming couplers, they are usually included in red-sensitive emulsions, but in unsensitized emulsions or image-forming dyes sensitive to each of the three primary regions of the spectrum. It can also be contained in structural units. Each structural unit can consist of a single emulsion layer or multiple emulsion layers that are sensitive to a certain region of the spectrum. The layers of the element, including the amount of imaging units, can be arranged in various orders as is known in the art. A typical multicolor photographic element comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler (at least one of the cyan dye-forming couplers being a compound of the invention). a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler; at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler; It consists of a yellow image-forming structural unit supported on a base. The element can have additional layers such as filter layers, interlayer protective layers, subbing layers, and the like.

In order to incorporate the compound of the present invention into an emulsion, conventionally known methods may be followed. For example, tricresyl phosphate,
The compound of the present invention is used alone or in combination with a high boiling point organic solvent with a boiling point of 175° C. or higher such as dibutyl phthalate or a low boiling point solvent such as butyl acetate or butyl propionate, or in a mixture thereof as necessary. After dissolving it, it is mixed with an aqueous gelatin solution containing a surfactant, and then emulsified in a high-speed rotary mixer or colloid mill, and then added to silver halide to prepare the silver halide emulsion used in the present invention. You can. When the compound of the present invention is added to a silver halide emulsion, usually silver halide 1
About 0.07-0.7% mole per mole, preferably 0.1
The compound of the present invention is added in a range of mol to 0.4 mol.

Silver halide emulsions used in the silver halide emulsion include any silver halide emulsion commonly used in silver halide emulsions, such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. things are included.

Silver halide emulsion grains can be produced by various methods, including the usual method, such as the method described in Japanese Patent Publication No. 45-7772, i.e., by using at least a portion of silver halide emulsion grains whose solubility is greater than that of silver bromide. A method for producing a so-called conversion emulsion, such as forming an emulsion of silver salt grains made of silver salt, and then converting at least a part of the grains to silver bromide or silver iodobromide salt, or an average grain size of 0.1 μ or less It can be produced by any production method such as the production method of Lippmann emulsion consisting of fine grain silver halide having the following.

In addition, the silver halide emulsions may contain sulfur sensitizers, such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers, such as stannous salts, polyamines, etc., noble metals. sensitizers, such as gold sensitizers, in particular potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzthiazole methyl chloride, etc., or sensitizers of water-soluble salts such as ruthenium, rhodium, iridium, etc.; Specifically, chemical sensitization can be carried out using ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadide, etc. alone or in appropriate combinations.

Further, the silver halide emulsion can contain various known photographic additives. For example, ResearchDi
sclosure (Research Disclosure) 197
Photographic additives such as those described in December 8, Item 17643.

Silver halide is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity to the wavelength range required for red-sensitive emulsions. Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more. Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in the specifications of Patent No. 2,454,620 and Patent No. 2,776,280.

The color developing solution that can be used when developing a silver halide photographic light-sensitive material using the compound of the present invention is preferably one containing an aromatic primary amine color developing agent as a main component. Typical examples of color developing agents include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and monomethyl-p-phenylenediamine hydrochloride.
-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, 2-amino-5 -(N-ethyl-N-β-methanesulfonamidoethyl)aminotoluene sulfate, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N-β- Examples include hydroxyethylamino)aniline, 2-amino-5-(N-ethyl-N-β-methoxyethyl)aminotoluene, and the like.

Bleaching to remove silver and silver halides after development;
Fixing or Bleaching - The usual steps of fixing, washing and drying are carried out.

The present invention will be specifically described below based on the implementation side, but the embodiments of the present invention are not limited thereto.

Reference Example (1) Take 0.03 mole each of the compounds of the present invention as shown in Table 1 and the following comparative compounds [A], [B], and [C], and add diptyl phthalate in an amount equal to their weight. It was added to a mixed solution with 3 times the amount of ethyl acetate and heated to 60°C to completely dissolve. This solution was added to an aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and gelatin, and emulsified using a colloid mill to prepare respective compound dispersions. Next, this compound dispersion was added to a silver chlorobromide emulsion containing 0.1 mol of silver (20 mol% silver bromide), and the mixture was coated on polyethylene laminated paper and dried to form a stable coating film. Various types of silver halide color photographic materials (sample numbers [1] to [6]) were obtained.

Comparative Compound [A] Comparative Compound [B] Comparative Compound [C] These samples were subjected to wedge exposure according to a conventional method and then subjected to the following processing. However, the color development process was carried out for two types of compositions: one with benzyl alcohol added (color development [1]) and one without (color development [2]).

〔process〕

Treatment process (30℃) Treatment time Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Wash with water 2 minutes The composition of each treatment is shown below.

[Color developer composition 1] 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate
5.0g benzyl alcohol
15.0ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.85g Sodium bromide
1.4g potassium bromide
0.5g borax
Add 39.1 g of water to make 1 liter, and adjust the pH to 10.30 using sodium hydroxide.

[Color developer composition 2] 4-Amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate
5.0g Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite
1.85g sodium bromide
1.4g potassium bromide
0.5g borax
Add 39.1g water to make 1l,
Adjust the pH to 10.30 using sodium hydroxide.

[Bleach-fix solution composition]

Ethylenediaminetetraacetic acid iron ammonium salt 50g
Ammonium sulfite (40% solution) 50m
l Ammonium thiosulfate (70% solution) 14
0ml ammonia water (28% solution)
20ml ethylenediaminetetraacetic acid
Add 4g water to make 1L.

Photographic properties were measured for each of the obtained samples.

The results are shown in Table 1. The relative sensitivity values in the table are expressed with the maximum sensitivity value when processed with color developer [1] being 100.

As is clear from Table 1 above, the samples using the compounds of the present invention are excellent in that they provide good sensitivity and maximum concentration regardless of the presence or absence of benzyl alcohol.

Furthermore, as a result of measuring the color spectrum, it was found that the cyan dye of the sample using the compound of the present invention has a maximum absorption maximum in a relatively long part of the red region, and exhibits excellent color purity with little absorption on the short wavelength side. It turns out.

Reference Example (2) Using a sample obtained in the same manner as in Reference Example (1) above, the light resistance, heat resistance, and moisture resistance of the dye image were examined.

The results obtained are shown in Table 2.

The light resistance in the table is expressed as the residual density after exposing each image obtained for 300 hours using a xenon fade meter, with the density before exposure being 100. Moisture resistance was expressed as the residual concentration after storage for 3 weeks at 60° C. and 70% relative humidity, with the concentration before the test being 100. Furthermore, the heat resistance is 7
The residual concentration after storage for 3 weeks at 7°C was expressed with the concentration before the test as 100. (However, the initial concentration was 1.0) As is clear from Table 2, Sample 10 using Comparative Compound A has excellent light resistance, but there is a problem with heat and humidity resistance. sample 11,1
2 has excellent heat and humidity resistance, but has a problem in light resistance in color development [2].

On the other hand, it can be seen that the samples using compounds [3], [4] and [8] of the present invention have excellent performance in all respects and are preferable as photographic couplers.

Reference Example (3) Compounds of the present invention as shown in Table 3, the comparative compounds [
A], [B] and the following comparative compound [D] at 0% each.
01 mole each was added to a mixture of tricresyl phosphate in an amount equal to its weight and 3 times the amount of ethyl acetate,
It was heated to 60°C to completely dissolve it.

This solution was added to an aqueous solution of Alkanol B and gelatin, and emulsified using a colloid mill to prepare respective compound dispersions.

Next, this compound limb solution was added to a silver iodobromide emulsion containing 0.1 mol of silver (6 mol% silver iodide), coated on a cellulose acetate film base, and dried to form a stable coating film. Six types of silver halide color photographic materials (sample numbers [13] to [18]) having the following properties were obtained.

Comparative Compound [D] These samples were subjected to wedge exposure according to a conventional method and then subjected to the following processing.

〔process〕

Processing step (33°C) Processing time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds [Color developer composition] 4-Amino- 3-Methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine 1/8 sulfate 1.98g Sulfuric acid
0.74mg anhydrous potassium carbonate 28.85
g Anhydrous potassium hydrogen carbonate 3.4
6g anhydrous potassium sulfite 5.
10g potassium bromide 1
．． 16g sodium chloride
0.14g 3-sodium nitriloacetate■
Add 1.20g water to make 1l
1.48g [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 1
00g ethylenediaminetetraacetic acid-2-ammonium salt 10g ammonium bromide
150g glacial acetic acid
Add 10 ml of water to make 1 liter, and adjust the pH to 6.0 using aqueous ammonia.

[Fixer composition]

Ammonium thiosulfate 175.
0g anhydrous sodium sulfite
8.6g sodium metasulfite
Add 2.3 g of water to make 1 liter and adjust to pH 6 using acetic acid.
．． Adjust to 0.

[Stabilizing liquid composition]

Formalin (37% aqueous solution) 1.5m
l Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5
The photographic properties of the obtained cyan colored image were measured. The results are shown in Table 3.

As is clear from Table 3, the samples using the compounds of the present invention were found to be excellent in sensitivity and color development.

In addition, as a result of measuring the spectroscopic spectrum, the dye image has a maximum absorption wavelength in the long wavelength region of the red region and a sharp cut in the short wavelength region, which is preferable in terms of color reproduction in the green region compared to samples using comparative compounds. It was found that it gives

Reference Example (4) Samples (1) to (6) obtained in Reference Example (1) were subjected to wedge exposure, and then developed using color developer composition 1 of Reference Example (1). On the other hand, development was carried out using a bleach-fix solution with the composition shown below, and the discoloration of the cyan dye by the fatigued bleach-fix solution was investigated.

[Bleach-fix solution composition]

Ammonium salt of ethylenediaminetetraacetate 50g Ammonium sulfite (40% solution) 50ml Ammonium thiosulfate (70% solution) 140ml
Ammonia water (28% solution) 20ml
Ethylenediaminetetraacetic acid 4g Hydrosulfite 5g Add water to make 1 liter.

The maximum reflection density of the cyan dye of the sample obtained after the development process was measured. The results are shown in Table 4.

The dye residual rate in the maximum density area was determined as follows.

Dye residual ratio = Tired bleach-fix solution treatment / Fresh bleach-fix solution treatment x 100 From Table 4, it is understood that the samples using the compounds of the present invention show less fading of the cyan dye when treated with fatigued bleach-fix solution.

Agent Yoshimi Kuwabara Procedural amendment (method) % formula % ) ) 2 Invention r, so-called phenolic compound ゛ (Supplement 116...+;:, 8 ・j; Leap R with A'1, Special 7'l'llll applicant II
Place +lj Q capital? ] lJ・i1me west 1'1
TYi'i I J' It 21i i1i'2'
Name (Ij, (+27) Konishi Roku Photo 1 ~ Industry Co., Ltd.?
1 I blasphemy 1 [V, tighten 1g Kawamoto I 1 Hiko 4th generation hitter 〒1 () 1 no 11:;su] 11 `` Old 1; 11111j Width
Sakurikawa 1' I ii:', 11! 'Konishi 7
°, ゛su゛continue viewing ('4, 1st procedure amendment 11t) sum 5RXl]fl 11.20th'Fat ￥1
Mr. Kazuo Wakasugi, Agency Official 1 Indication of Matter I J1 Patent Application No. 39529 1-2 Name of Invention Zej・Phenol Compound 3 Relationship with 11 Cases Special? '1Ill Yu1 person place°
1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (+27)
1 Kawamoto, Representative Director of Konishiroku η′ Shin Kogyo Co., Ltd.
A. 6, Object of amendment +1 (II 71+ "Detailed description of the invention" (Gate 7)
, Contents of Amendment 1

Claims (1)

[Claims] A phenylureido group having at least one cyano group in the ortho or meta position at the 2-position, a hydrogen atom at the 4-position or a group that can be removed during a coupling reaction with an oxidation product of a color developing agent, and an acylamino group at the 5-position. A phenolic compound with a group.