JPH1067726A - New phenol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having a stable coloring property and a stable discoloring property and capable of corresponding to a wide range of use conditions and environmental conditions, when used as a color developer for reversible thermosensitive recording material. SOLUTION: A new phenol compound of the formula [X is NHCONH, NHCO, CONH, etc.; (n) is 2-11; (m) is 6-21], e.g. N-(4-hydroxyphenyl)-3-(n- octadecanoylamino)propanamide. The compound of the formula is snthesized by condensing a carboxylic acid of the formula: HOOC-(CH2 )m -X-(CH2 )m CH3 with p-aminophenol. The reaction is carried out by a general condensation reaction using a condensing agent (e.g. dicyclohexylcarbodiimide). A condensation auxiliary (e.g. N-hydroxyphthalic acid imide) is used together with the condensing agnet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phenolic compound, and more particularly, to a novel phenolic compound useful as a developer for a reversible thermosensitive recording material capable of forming and erasing a color image by controlling thermal energy. Related to phenolic compounds.

[0002]

2. Description of the Related Art A reversible thermosensitive recording medium using the phenolic compound of the present invention comprises an electron-donating color-forming compound (hereinafter also referred to as a color former or a leuco dye) and an electron-accepting compound (hereinafter referred to as a developer). ) As a main component. Conventionally, thermal recording media are widely known, such as facsimile, word processor,
Used for printers such as scientific measuring instruments. However, these conventional recording media that have been put into practical use all have irreversible color development, and once recorded images cannot be erased and used repeatedly.

However, according to the patent publication, a recording medium capable of reversibly developing and decoloring has also been proposed. For example, Japanese Patent Application Laid-Open No. Sho 60-1985 uses a combination of gallic acid and phloroglucinol as a color developer. JP-A-1936991, JP-A-61-237684 using a compound such as phenolphthalein or thymolphthalein as a developer, and a recording layer containing a homogeneous compatibilizer of a color former, a developer and a carboxylic acid ester. JP-A-62-138556, JP-A-62-1
38568 and JP-A-62-140881, and JP-A-63-63163 using an ascorbic acid derivative as a developer.
JP-A-173684, JP-A-2-188293 and JP-A-2-18893 using a salt of bis (hydroxyphenyl) acetic acid or gallic acid and a higher aliphatic amine as a developer.
No. 188294 is disclosed. However, the conventional reversible thermosensitive recording medium described above has a problem in terms of compatibility between color stability and decoloration, or stability in color density and repetition,
It is not satisfactory as a practical recording medium.

[0004] The present inventors have previously described Japanese Patent Application Laid-Open No. Hei 5-12436.
In Japanese Patent Publication No. 0, an organic phosphoric acid compound having a long-chain aliphatic hydrocarbon group, an aliphatic carboxylic acid compound or a phenol compound is used as a color developer, and a color is formed and erased by combining this with a leuco dye as a color former. Colors can be easily performed by heating and cooling conditions, and the color development and decoloration states can be stably maintained at room temperature, and furthermore, color development and decoloration can be repeated stably. A reversible thermosensitive coloring composition and a reversible thermosensitive recording medium using the same in a recording layer have been proposed. This has practical performance in terms of the balance between color stability and color erasure and color density, but it is also improved in terms of compatibility with a wider range of usage environments and the range of application of color erasure conditions. There was room to be. After that, use of a specific structure for a phenol compound having a long-chain aliphatic hydrocarbon group was proposed (Japanese Patent Laid-Open No. 6-210954), but this also had the same problem.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to maintain stable coloring and decoloring properties when used as a developer for reversible thermosensitive recording materials, and to meet a wide range of use conditions and environmental conditions. An object of the present invention is to provide a novel phenol compound that can be used.

[0006]

Means for Solving the Problems The present inventors have designed, synthesized, and studied various novel color developing agents which maintain stable coloring and decoloring properties and can cope with a wide range of use conditions and environmental conditions. As a result, they succeeded in obtaining a novel phenol compound useful as a developer.

That is, the present invention relates to a novel phenol compound represented by the following general formula (I).

Embedded image (Wherein X is -NHCONH-, -NHCO-, -NH
COCONH -, - CONHNHCO- or -SO ₂
Represents a group represented by-, n represents an integer of 2 to 11, and m represents an integer of 6 to 21. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The novel phenol compound of the present invention is represented by the general formula (I). This compound (I) can be synthesized, for example, from a condensation reaction between a carboxylic acid compound of the following general formula (II) and p-aminophenol.

Embedded image (Wherein X is -NHCONH-, -NHCO-, -CO
NH-, -NHCONH-, -CONHNHCO-
Or -SO ₂ - represents a group represented, n is 2 to 11,
m represents an integer of 6 to 21. )

This condensation reaction can utilize a generally known amide bond forming reaction. For example, a condensing agent such as dicyclohexylcarbodiimide and diisopropylcarbodiimide can be used. Further, together with these condensing agents, condensing assistants such as N-hydroxyphthalimide, N-hydroxysuccinimide, N-hydroxytartarimide, N-hydroxybenzotriazole and the like can be used. Further, the carboxylic acid compound of the general formula (II) is halogenated using thionyl chloride or the like, and
-It is also possible to synthesize by condensing with aminophenol. The phenol compound of the present invention is not limited to these synthesis methods.

The phenolic compound of the present invention is useful as a developer for a reversible thermosensitive recording material, and this reversible thermosensitive recording material is basically constituted by combining the developer of the present invention and a color former. Things. The reversible thermosensitive recording medium using the compound of the present invention is provided with a recording layer containing the developer and the color former of the present invention as main components on a support. The support is paper, resin film, synthetic paper, metal foil, glass or a composite thereof, and may be any as long as it can hold the recording layer.

The color former used together with the compound of the present invention has an electron donating property and is itself a colorless or pale color dye precursor (leuco dye), and is not particularly limited.
Conventionally known compounds, for example, triphenylmethanephthalide compounds, fluoran compounds, phenothiazine compounds, leuco auramine compounds, indolinophthalide compounds, azaphthalide compounds and the like can be selected. For example, the following color formers may be mentioned, but the present invention is not limited thereto.

2-anilino-3-methyl-6-diethylaminofluoran, 2- (o-chloroanilino) -6
Dibutylaminofluoran, 2- (N-methyl-o-chloroanilino) -6-dibutylaminofluoran, 2-
Anilino-3-methyl-6- (Nn-propyl-N-
Methylamino) fluoran, 2-anilino-6- (N-
n-hexyl-N-ethylamino) fluoran, 2,3
-Dimethyl-6-dimethylaminofluoran, 2- (o
-Chloroanilino) -3-chloro-6-diethylaminofluoran, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindo-3)
-Yl) -4-azaphthalide and the like.

In the reversible thermosensitive recording medium, the ratio of the compound of the present invention to the color former varies in an appropriate range depending on the combination of the compounds used. It is in the range of from 1 to 20, preferably in the range of from 0.2 to 10. If the amount of the compound of the present invention is smaller or larger than this range, the density of the color-developed state is lowered and is not suitable for practical use.

The recording layer may be of any type as long as the compound of the present invention and the color former are present. In general, a state in which the color former and the compound of the present invention are finely and uniformly dispersed in a binder resin. Used. The color former and the compound of the present invention may form particles individually, but more preferably form a dispersed state as composite particles. This can be achieved by melting or dissolving the color former and the compound of the present invention once. The formation of such a recording layer is performed by dispersing and dissolving each material in a solvent, and then mixing and mixing them.
Alternatively, the method is carried out by mixing the respective materials, applying a liquid dispersed or dissolved in a solvent onto a support, and then drying. The color former and the compound of the present invention can be used by being encapsulated in microcapsules.

In the reversible thermosensitive recording medium using the phenolic compound of the present invention, an additive for improving or controlling the coating properties of the recording layer and the coloring and decoloring properties can be used as necessary. These additives include, for example, dispersants,
Examples include surfactants, conductive agents, fillers, lubricants, antioxidants, light stabilizers, ultraviolet absorbers, color stabilizers, and decolorization accelerators.

As the binder resin used for forming the recording layer, for example, polyvinyl chloride, polyvinyl acetate,
Vinyl chloride vinyl acetate copolymer, ethyl cellulose, polystyrene, styrene copolymer, phenoxy resin, polyester, aromatic polyester, polyurethane, polycarbonate, polyacrylate, polymethacrylate, acrylic copolymer, maleic acid Copolymers, polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, starches and the like. The role of these binder resins is to maintain a state in which the materials of the composition are uniformly dispersed without bias due to the application of heat for recording and erasing. Therefore, it is preferable to use a resin having high heat resistance as the binder resin. Further, a thermosetting resin may be used.

The curable resin is, for example, a combination of a cross-linking agent and a resin having an active group which reacts with the cross-linking agent, and is a resin which can be cross-linked and cured by heat, electron beam, ultraviolet ray or the like. Resins used for thermosetting include, for example, phenoxy resin, polyvinyl butyral resin, cellulose acetate propionate, cellulose acetate butyrate, and the like, a resin having a group that reacts with a crosslinking agent such as a hydroxyl group, a carboxyl group, or a hydroxyl group, a carboxyl group, or the like. There is a resin obtained by copolymerizing a monomer having the same and another monomer. Copolymer resins include, for example, resins of vinyl chloride type, acrylic type, styrene type and the like, specifically, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinyl acetate-hydroxypropyl acrylate copolymer,
Examples thereof include a vinyl chloride-vinyl acetate-maleic anhydride copolymer.

The crosslinking agent for thermal crosslinking includes, for example, isocyanates, amines, phenols, epoxy compounds and the like. For example, the isocyanates are polyisocyanate compounds having a plurality of isocyanate groups, specifically, hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI),
Examples thereof include xylylene diisocyanate (XDI), and adduct types, burette types, isocyanurate types, and blocked isocyanates thereof with trimethylolpropane and the like. As the amount of the crosslinking agent added to the resin, the ratio of the functional group of the crosslinking agent to the number of active groups contained in the resin is preferably 0.01 to 2.0, and below this, the thermal strength is insufficient, and Addition of more than this has an adverse effect on the color development / decoloration characteristics. Further, a catalyst used in this type of reaction may be used as a crosslinking accelerator. Examples of the crosslinking accelerator include tertiary amines such as 1,4-diazabicyclo [2,2,2] octane and metal compounds such as organic tin compounds.

Next, examples of monomers used for curing with an electron beam and an ultraviolet ray include the following. Examples of monofunctional monomers Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, Cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylate methyl chloride salt, diethylaminoethyl methacrylate, glycidyl methacrylate, methacrylic acid Acid tetrahydrofurfuryl, allyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene dimethacrylate Glycol, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, methacrylic acid 2-
Ethoxyethyl, 2-ethylhexyl acrylate, 2
-Ethoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, dicyclopentenylethyl acrylate, N-vinylpyrrolidone,
Vinyl acetate and the like.

Examples of difunctional monomers 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, tripropylene Glycol diacrylate, polypropylene glycol diacrylate, bisphenol A ethylene oxide adduct diacrylate, glycerin methacrylate acrylate, diacrylate of neopentyl glycol 2 mol propylene oxide adduct, diethylene glycol diacrylate, polyethylene glycol (400) diacrylate, hydroxypivalin Diacrylate of ester of acid and neopentyl glycol,
2,2-bis (4-acryloxydiethoxyphenyl)
Propane, diacrylate of neopentyl glycol diadipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2
-(2-hydroxy-1,1-dimethylethyl) -5-
Hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol diacrylate, ε-caprolactone adduct of tricyclodecane dimethylol diacrylate, diacrylate of glycidyl ether of 1,6-hexanediol, etc. .

Examples of polyfunctional monomers Trimethylolpropane triacrylate, glycerin propylene oxide addition acrylate, trisacryloyloxyethyl phosphate, pentaerythritol acrylate, triacrylate of trimethylolpropane 3 mol adduct of propylene oxide, dipentaerythritol. Polyacrylate, polyacrylate of caprolactone adduct of dipentaerythritol,
Dipentaerythritol triacrylate propionate, hydroxypivalaldehyde-modified dimethylolpropane triacrylate, tetraacrylate dipentaerythritol propionate, ditrimethylolpropane tetraacrylate, pentaacrylate dipentaerythritol propionate, dipentaerythritol hexaacrylate, dipentaerythritol Ε-caprolactone adduct of pentaerythritol hexaacrylate and the like.

Examples of oligomers Bisphenol A-diepoxyacrylic acid adducts and the like.

When crosslinking is carried out using ultraviolet rays, the following photopolymerization initiators and photopolymerization accelerators are used.
Examples of the photopolymerization initiator include benzoin ethers such as isobutyl benzoin ether, isopropyl benzoin ether, benzoin ethyl ether and benzoin methyl ether; 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime Α-acyloxime esters; benzyl ketals such as 2,2-dimethoxy-2-phenylacetophenone, benzyl, and hydroxycyclohexylphenyl ketone; diethoxyacetone phenone, 2-hydroxy-2-methyl-1-
Acetophenone derivatives such as phenylpropan-1-one; benzophenone, 1-chlorothioxanthone, 2-
Chlorothioxanthone, isopropylthioxanthone,
Ketones such as 2-methylthioxanthone and 2-chlorobenzophenone are exemplified. These photopolymerization initiators,
Used alone or in combination of two or more. The amount of addition is 0.1 to 1 part by weight of the monomer or oligomer.
The amount is preferably from 005 to 1.0 part by weight, more preferably from 0.01 to 0.5 part by weight.

Examples of the photopolymerization accelerator include tertiary aromatic amines and aliphatic amines. Specific examples include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester. These photopolymerization accelerators are used alone or in combination of two or more. The addition amount is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 1 part by weight, based on 1 part by weight of the photopolymerization initiator.
３3 parts by weight.

As the light source for the ultraviolet irradiation used in the present invention, there are a mercury lamp, a metal halide lamp, a gallium lamp, a mercury xenon lamp, a flash lamp, etc., and the ultraviolet absorption of the above-mentioned photopolymerization initiator and photopolymerization accelerator. A light source having an emission spectrum corresponding to the wavelength may be used. As the UV irradiation conditions, the lamp output and the transport speed may be determined according to the irradiation energy required for crosslinking the resin.

As the electron beam irradiation device, either a scanning type or a non-scanning type may be selected according to the purpose such as the irradiation area and the irradiation dose. The irradiation condition is set to a dose necessary for crosslinking the resin. The electron flow, irradiation width, and transport speed may be determined accordingly.

The reversible thermosensitive recording medium using the phenolic compound of the present invention basically has the above-mentioned recording layer provided on a support. However, in order to improve the characteristics as a recording medium, a protective layer is used. , Adhesive layer, intermediate layer, undercoat layer,
A back coat layer or the like can be provided.

In printing using a thermal head, the surface of the recording layer may be deformed due to heat and pressure, resulting in so-called dents. In order to prevent this, it is preferable to provide a protective layer on the surface. For the protective layer, a UV-curable resin, an electron beam-curable resin, and the like can be used in addition to polyvinyl alcohol, styrene-maleic anhydride copolymer, carboxy-modified polyethylene, melamine-formaldehyde resin, urea-formaldehyde resin. Further, an additive such as an ultraviolet absorber can be contained in the protective layer.

An intermediate layer is provided between the recording layer and the protective layer for the purpose of improving the adhesion between the recording layer and the protective layer, preventing deterioration of the recording layer due to application of the protective layer, and preventing migration of additives in the protective layer to the recording layer. It is also preferred. Further, it is preferable to use a resin having low oxygen permeability for the protective layer and the intermediate layer provided on the recording layer. It is possible to prevent or reduce the oxidation of the color former and the developer in the recording layer.

In order to effectively use the applied heat,
A heat-insulating undercoat layer can be provided between the support and the recording layer. The heat insulating layer can be formed by applying organic or inorganic fine hollow particles using a binder resin. An undercoat layer may be provided for the purpose of improving the adhesion between the support and the recording layer and preventing the penetration of the recording layer material into the support.

For the intermediate layer and the undercoat layer, the same resins as those for the recording layer described above can be used. Further, the protective layer, the intermediate layer, the recording layer and the undercoat layer include calcium carbonate, magnesium carbonate, titanium oxide,
A filler such as silicon oxide, aluminum hydroxide, kaolin, and talc can be contained. In addition, a lubricant, a surfactant, a dispersant and the like can be contained.

In the reversible thermosensitive recording medium using the compound of the present invention, in order to form a colored image, the recording medium may be once heated to a color developing temperature or higher and then rapidly cooled. Specifically, for example, when the recording layer is heated for a short time with a thermal head or a laser beam, the recording layer is locally heated.
Immediate diffusion of heat causes rapid cooling, and the color development state can be fixed. On the other hand, in order to erase the color, heating may be performed by using an appropriate heat source for a relatively long time to cool, or heating may be temporarily performed to a temperature slightly lower than the coloring temperature. If the recording medium is heated for a long time, the temperature of a wide area of the recording medium rises, and the subsequent cooling is slowed down. As a heating method in this case, a heat roller, a heat stamp, hot air, or the like may be used, or heating may be performed for a long time using a thermal head. In order to heat the recording layer to the decoloring temperature range, the applied energy may be slightly reduced from that at the time of recording, for example, by adjusting the applied voltage and the pulse width to the thermal head. Using this method, recording and
Erasing is possible, so-called overwriting becomes possible. Of course, it can be erased by heating to a decoloring temperature range by a heat roller or a heat stamp.

In the reversible thermosensitive recording medium using the compound of the present invention, if necessary, one or more colored layers may be provided on the entire surface or a part of the recording medium. A layer may be provided. At this time, it is preferable that the coloring layer and the protective layer satisfy repeated durability. The protective layer only needs to cover the coloring layer. When the coloring layer is provided on a part of the recording medium, only the portion covering the coloring layer may be provided, or the entire recording medium may be covered. Further, the top layer on the front and back surfaces of the reversible thermosensitive recording medium of the present invention should have, in addition to the above-mentioned repetition durability, transportability, resistance to dirt and deposits such as fingerprint resistance, and a printing apparatus. Cleaning properties. The reversible thermosensitive recording medium using the compound of the present invention can be processed into an arbitrary shape, and can be attached to another medium via an adhesive or the like.

[0034]

The present invention will be described in detail with reference to the following examples.

Example 1 [N- (4-hydroxyphenyl) -6-[(Nn-
Synthesis of octadecylcarbamoyl) amino] hexaneamide (compound No. 3 in Table 1) 18.4 g of sodium salt of ε-aminocaproic acid, 35.5 g of octadecyl isocyanate, and 900 ml of 2-butanone were charged and stirred under reflux for 6 hours. did. Next, the precipitated crystals were separated by filtration,
After washing with water, the mixture was poured into an aqueous solution of acetic acid, stirred for 3 hours, filtered again, and the obtained crystals were washed with water, dried and recrystallized from toluene. The obtained crystals were treated with tetrahydrofuran (1200 m).
and heated to 65 ° C. While stirring the suspension, 16.2 g of 1-hydroxybenztriazole,
15.1 g of diisopropylcarbodiimide and 13.1 g of p-aminophenol were added and reacted under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, filtered, washed with water, and recrystallized from ethanol to obtain the desired product. Table 1 shows the yield, melting point, and elemental analysis results of the target product at this time. Elemental analysis and infrared absorption spectrum confirmed that it was the desired product. Similarly, in Table 1, compound N
o. 1, 2 and No. 4-No. Compound 7 was synthesized. The results are shown in Table 1.

Example 2 [N- (4-hydroxyphenyl) -3- (n-octadecanoylamino) propanamide (in Table 1, compound N
o. Synthesis of 8)] 9.7 g of β-alanine, 6.7 g of sodium hydroxide, 200 ml of acetone and 150 ml of water were charged, and 25.3 g of octadecanoic acid chloride was added dropwise with stirring. After the dropwise addition, the temperature was raised, and the mixture was stirred at 50 to 60 ° C. for 3 hours, then made acidic with a 30% aqueous sulfuric acid solution, and the precipitated crystals were separated by filtration, washed with water, and dried. The crystals were recrystallized from toluene. Next, the obtained crystals were placed in tetrahydrofuran 120
Suspended in 0 ml and heated to 65 ° C. While stirring the suspension, 1-hydroxybenztriazole 6.8
g, diisopropylcarbodiimide 6.3 g and p-aminophenol 5.5 g were added, and the mixture was reacted under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, filtered, washed with water, and recrystallized from ethanol to obtain the desired product. Table 1 shows the yield, melting point, and elemental analysis results of the target product at this time. Similarly, in Table 1, Compound No. 9-13
Was synthesized. The results are shown in Table 1.

Example 3 [N- (4-hydroxyphenyl) -3- (n-octadecylsulfonyl) propanamide (in Table 1, compound N
o. Synthesis of 14)]
15.1 g of octadecene and 5.3 g of thiopropionic acid were dissolved and stirred at 80 to 90 ° C. for 8 hours. Then, water was added, and the precipitated crystals were separated by filtration, washed with water, and recrystallized from hexane. 75 g of acetic acid was added to the obtained crystals, and 90 to 1
At 00 ° C., 50 g of aqueous hydrogen peroxide (33%) was added dropwise, and the mixture was stirred for 7 hours. The precipitated crystals were separated by filtration, washed with water, and recrystallized with ethanol. Further, the obtained crystals were dissolved in 250 ml of tetrahydrofuran, and 3.9 g of 1-hydroxybenzotriazole and 3.93 g of diisopropylcarbodiimide.
5 g and 2.7 g of p-aminophenol were added, and the mixture was stirred at room temperature for 6 hours. Thereafter, the precipitated crystals were separated by filtration, washed with water, and recrystallized from toluene to obtain the desired product. Table 1 shows the yield, melting point, and elemental analysis results of the target product at this time. Elemental analysis and infrared absorption spectrum confirmed that it was the desired product.

Example 4 [N- (n-octadecanoylamino) -N '-(4-
Synthesis of hydroxyphenyl) hexane-1,6-diamide (compound No. 15 in Table 1) In 400 ml of tetrahydrofuran, 20 g of stearic hydrazide, 11.6 g of monoethyl adipate, 10.2 g of diisopropylcarbodiimide, 1-hydroxybenzotriazole 1
0.8 g was dissolved and stirred at room temperature for 12 hours. Next, after filtration, recrystallized from acetone, the obtained crystals were added to 400 ml of an 85% aqueous ethanol solution to obtain 4.6 g of sodium hydroxide.
In a solution in which was dissolved, and stirred under reflux for 4 hours. The reaction solution was acidified with a 30% aqueous sulfuric acid solution, cooled, filtered, washed with water and dried. The obtained crystals were dissolved in 200 ml of tetrahydrofuran, and 5.6 g of p-aminophenol, 6.4 g of diisopropylcarbodiimide,
6.8 g of -hydroxybenzotriazole was added, and the mixture was stirred under reflux for 3 hours. After cooling, the precipitated crystals were separated by filtration, dried and recrystallized from isopropyl alcohol to obtain the desired product. Table 1 shows the yield, melting point, and elemental analysis results of the target product at this time. Elemental analysis and infrared absorption spectrum confirmed that it was the desired product.

Example 5 [Nn-octadecyl-N '-(5- (N- (4-hydroxyphenyl) -carbamoyl) pentyl) ethane-1,2-diamide (Compound No. 16 in Table 1) Synthesis of 17.0 g of stearylamine and 6.5 g of pyridine in 100 ml of tetrahydrofuran.
At 50 ° C., 12.5 g of monoethyl oxalate was added dropwise and stirred for 5 hours. Next, after the precipitated solid was removed by filtration, water was added to the obtained liquid, the suspended oily substance was collected, dissolved in acetone, cooled, and the precipitated crystal was filtered. The crystals were transferred into a solution in which 4.1 g of sodium hydroxide was dissolved in 100 ml of a 90% aqueous ethanol solution, and stirred under reflux for 2 hours. Then, the mixture was acidified with aqueous hydrochloric acid, and the precipitated crystals were washed with water and recrystallized from acetone. 10 g of the obtained crystals were dissolved in 150 ml of tetrahydrofuran, and aminocaproic acid ethyl ester hydrochloride 14.6 was added thereto.
g, 3.5 g of pyridine and 6.8 g of 1-hydroxybenzotriazole were added, and 5.6 g of diisopropylcarbodiimide was added dropwise with stirring at room temperature, followed by stirring for 16 hours. The precipitated crystals are separated by filtration, and a 60% aqueous ethanol solution 2
The solution was transferred into a solution in which 3.8 g of sodium hydroxide was dissolved in 50 ml, and the mixture was stirred under reflux for 4 hours, acidified with aqueous sulfuric acid, and the precipitated crystals were washed with water and dried. The crystals were dissolved in 100 ml of tetrahydrofuran, and p-aminophenol 2.5 was dissolved.
g, 2.3 g of 1-benzotriazole and 2.2 g of diisopropylcarbodiimide, and the mixture was stirred at room temperature for 8 hours. The precipitated crystals were separated by filtration, washed with water and tetrahydrofuran, and recrystallized from toluene to obtain the desired product. Table 1 shows the yield, melting point, and elemental analysis results of the target product at this time. Elemental analysis and infrared absorption spectrum confirmed that it was the desired product.

Example 6 Synthesis of N- (n-octadecyl) -N ′-(4-hydroxyphenyl) hexane-1,6-diamide (Compound No. 17 in Table 1) Octadecylamine 13.5
g, pyridine 3.7 g in tetrahydrofuran 150 ml
Then, 9.6 g of adipic acid monoethyl chloride was added dropwise at room temperature. After the dropwise addition, the mixture was stirred at 50 to 60 ° C. for 4 hours.
A solution in which 20 g of sodium hydroxide was dissolved in 00 ml was added, and the mixture was stirred under reflux for 4 hours. 500 ml of water was added to the reaction solution, the mixture was acidified with 4N hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water, and washed with water.
After drying, it was recrystallized from 2-butanone. The obtained crystals were suspended in 1200 ml of tetrahydrofuran and heated to 65 ° C. While stirring the suspension, 3.7 g of 1-hydroxybenztriazole, 3.4 g of diisopropylcarbodiimide and 3.0 g of p-aminophenol were added, and the mixture was reacted under reflux for 2 hours. After completion of the reaction, the reaction product was cooled to room temperature, filtered, washed with water, and recrystallized from ethanol.
The desired product was obtained. Table 1 shows the yield, melting point, and elemental analysis results of the target product at this time. Elemental analysis and infrared absorption spectrum confirmed that it was the desired product.

[0041]

[Table 1- (1)]

[0042]

[Table 1- (2)]

Application Example 1 (Production Example 1 of Reversible Thermosensitive Recording Medium) The following composition was pulverized and dispersed to a particle size of 1 to 4 μm using a ball mill to prepare a coating solution for a recording layer. 2-anilino-3-methyl-6-dibutyl aminoaminofluorane 2 parts Compound of the present invention shown in Table 2 8 parts Vinyl chloride-vinyl acetate copolymer 20 parts (Union Carbide Co., Ltd., VYHH) Methyl ethyl ketone 45 parts Toluene 45 parts of a recording layer coating solution having the above composition was applied to a 100 μm-thick polyester film using a wire bar, and dried to prepare a reversible thermosensitive recording medium having a recording layer having a thickness of about 6.0 μm.

The obtained recording medium was printed by an 8 dot / mm thermal head under the conditions of an applied voltage of 13.3 V and an applied pulse width of 1.2 milliseconds to obtain a colored image. The optical density of this color image was measured using a Macbeth densitometer RD-914. Next, the colored recording medium was heated at an erasing temperature shown in Table 2 for 0.2 second, 0.5 second and 1 second using a hot stamp, and then the density was measured. Table 2 shows the results. Table 2 shows the results of repeating this printing and heating and erasing for 1 second 10 times. From Table 2,
It can be seen that the recording medium of the present invention decolors to the same level as the background density by heating for 0.2 seconds to 0.5 seconds. Further, it can be seen that printing and erasing are stably repeated. Also,
The colored recording medium was kept under drying conditions at 40 ° C. for 24 hours, and the storability was measured by measuring the background density and the color density before and after storage. Table 2 shows the results. Note that the concentration retention rate in the table is given by the following equation. Density retention rate (%) = {(color density after storage−texture density after storage) / (color density before storage−texture density before storage)} × 100 From these results, this recording medium can be used in an environment of 40 ° C. It can be seen that there is no fading of the image. Therefore,
It has been clarified that the recording medium using the compound of the present invention is a reversible thermosensitive recording medium that can be erased at high speed and has excellent storage stability.

[0045]

[Table 2]

Application Example 2 (Preparation Example 2 of Reversible Thermosensitive Recording Medium) The following composition was pulverized and dispersed to a particle size of 1 to 4 μm using a ball mill to prepare a coating liquid for a recording layer. 2-anilino-3-methyl-6-diethylaminofluoran 2 parts Compound No. of the present invention 18 parts Polyester polyol resin (Takelac U-21 manufactured by Takeda Pharmaceutical Co., Ltd.) 15% tetrahydrofuran (THF) solution 150 parts To the obtained dispersion, Coronate HL manufactured by Nippon Polyurethane Co., Ltd.
(Adduct type hexamethylenediamine diisocyanate 75% ethyl acetate solution) (20 parts) was added, and the mixture was stirred well to prepare a recording layer coating solution. The recording layer coating solution having the above composition was applied on a 100 μm-thick polyester film using a wire bar, dried at 80 ° C., and then heated at 60 ° C. for 24 hours to form a recording layer having a thickness of about 6 μm. .

On the recording layer, an intermediate layer coating solution having the following composition was applied using a wire bar, dried at 80 ° C., and heated at 60 ° C. for 24 hours to form an intermediate layer having a thickness of about 2 μm. . <Intermediate layer coating liquid> 100 parts of a 10% methyl ethyl ketone (MEK) solution of a polyester polyol resin (Takelac U-21 manufactured by Takeda Pharmaceutical Co., Ltd.) 10 parts Ultrafine silicon nitride (average particle diameter 70 nm) 10 parts Coronate HL 15 parts

Further, a protective layer solution having the following composition was applied on the intermediate layer using a wire bar, and then passed under an ultraviolet lamp having an irradiation energy of 80 W / cm at a transport speed of 9 m / min to cure the film. A protective layer having a thickness of 3 μm was provided to produce a reversible thermosensitive recording medium. <Protective layer coating liquid> Urethane acrylate UV curable resin (C7-157, manufactured by Dainippon Ink) 10 parts Silica (P-527, manufactured by Mizusawa Chemical) 0.1 part Ethyl acetate 90 parts

The recording medium manufactured as described above was applied with an applied voltage of 13.3 V by a thermal head of 8 dots / mm.
The applied pulse width was 1.2 milliseconds. The optical density of the printing portion and the background portion was measured using a Macbeth densitometer RD-91.
4, the print density was 1.16 and the background density was 0.10. Next, when the printed portion was erased at 150 ° C. for 0.5 second using a hot stamp, the erase density was 0.10. In addition, the printing
When erasing was repeated 50 times, there was almost no decrease in the printing density and no increase in the erasing density, and there was no dent. In addition, a print sample was prepared using a fluorescent lamp of 5500lu.
When irradiation was performed for 100 hours at x, the discoloration and the unerased residue at the time of erasing were not recognized in both the printed portion and the background portion, and the condition was excellent.

Application Example 3 (Production Example 3 of Reversible Thermosensitive Recording Medium) A recording layer was provided in the same manner as in Application Example 2, except that the following recording layer dispersion liquid was used. 3- (4-diethylamino-2-ethoxyphenyl-3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 2 parts Compound No. 4 8 parts of the present invention N, N'-dioctadecyl Urea 0.4 part 15% THF solution of polyester polyol resin (Takeda Pharmaceutical Co., Ltd. Takerak U-21) 150 parts Next, ultrafine silicon particles (average particle diameter 70 nm) from the intermediate layer coating solution used in Application Example 2 The intermediate layer was provided in the same manner as in Application Example 2 except for the following.

Next, a protective layer was provided in the same manner as in Application Example 2, except that the following protective layer coating solution was used. <Protective layer coating liquid> Urethane acrylate UV curable resin (C7-157, manufactured by Dainippon Ink and Chemicals) 10 parts UV absorber having the following structure 0.5 part Ethyl acetate 90 parts UV absorber structural formula

Embedded image Next, Dai Nippon Ink's OP varnish (New Daicure
OL OP varnish) after printing using an R1 tester.
UV irradiation at m / min to provide a 1.5 μm thick OP layer,
A reversible thermosensitive recording medium was produced.

The recording medium manufactured as described above is applied to application example 2.
When the optical density of the printed portion and the background portion was measured using a Macbeth densitometer RD-914,
The print density was 0.88 and the background density was 0.09.
Next, using a hot stamp at 150 ° C.
When the data was erased in 0.5 seconds, the erase density was 0.09. When the above-mentioned printing / erasing was repeated 50 times, there was almost no decrease in the printing density and no increase in the erasing density, and there was no dent. Further, when the printed sample was irradiated with a fluorescent lamp at 5500 lux for 100 hours, discoloration was not observed in both the printed portion and the background portion, and the erased portion at the time of erasing was not recognized.

Application Example 4 (Production Example 4 of Reversible Thermosensitive Recording Medium) A recording layer dispersion liquid was prepared by using the following recording layer dispersion liquid and adding 10 parts of coronate HL to prepare a recording layer dispersion liquid. To provide a recording layer. 2-anilino-3-methyl-6-diethylaminofluorane 2 parts 38 parts 15% THF solution of acrylic polyol resin (LR286 manufactured by Mitsubishi Rayon Co., Ltd.) 150 parts

Next, an intermediate layer was provided in the same manner as in Application Example 2, except that the following intermediate layer coating liquid was used. <Intermediate layer coating liquid> 100 parts of 10% MEK solution of acrylic polyol resin (LR286 manufactured by Mitsubishi Rayon Co.) 100 parts Ultrafine zinc oxide (average particle diameter 20 nm) 10 parts Coronate HL 5 parts

Next, after providing a protective layer in the same manner as in Application Example 2 except that the following coating solution for protective layer was used, an OP layer was provided in the same manner as in Application Example 3, and a reversible thermosensitive recording medium was prepared. Produced. <Protective layer coating liquid> Urethane acrylate UV curable resin 10 parts (Dainippon Ink Co., Ltd. C7-157) Ethyl acetate 90 parts

The recording medium manufactured as described above is applied to application example 2.
When the optical density of the printed portion and the background portion was measured using a Macbeth densitometer RD-914,
The print density was 1.21 and the background density was 0.09. Next, using a hot stamp at 150 ° C.
When the data was erased in 0.5 seconds, the erase density was 0.09. When the above-mentioned printing / erasing was repeated 50 times, there was almost no decrease in the printing density and no increase in the erasing density, and there was no dent. Further, when the printed sample was irradiated with a fluorescent lamp at 5500 lux for 100 hours, discoloration was not observed in both the printed portion and the background portion, and the erased portion at the time of erasing was not recognized.

Application Example 5 (Preparation Example 5 of Reversible Thermosensitive Recording Medium) Recording was performed in the same manner as in Application Example 3, except that N, N'-dioctadecylurea was excluded from the recording layer dispersion liquid of Application Example 3. Layers were provided. Next, a protective layer similar to that of Application Example 3 was provided on the recording layer to produce a reversible thermosensitive recording medium.

Application Example 2 of the recording medium manufactured as described above
When the optical density of the printed portion and the background portion was measured using a Macbeth densitometer RD-914,
The printing density was 0.91 and the background density was 0.10. Next, using a hot stamp at 150 ° C.
When the erasing was performed in 0.5 seconds, the erasing density was 0.10. When the above-mentioned printing / erasing was repeated 50 times, there was almost no decrease in the printing density and no increase in the erasing density, and there was no dent. Further, when the printed sample was irradiated with a fluorescent lamp at 5500 lux for 100 hours, discoloration was not observed in both the printed portion and the background portion, and the erased portion at the time of erasing was not recognized.

Application Example 6 (Production Example 6 of Reversible Thermosensitive Recording Medium) After a recording layer was provided in the same manner as in Application Example 5, an intermediate layer was provided in the same manner as in Application Example 2. Next, an OP layer similar to that of Application Example 3 was provided on the intermediate layer to produce a reversible thermosensitive recording medium.

Application Example 2 of the recording medium manufactured as described above
When the optical density of the printed portion and the background portion was measured using a Macbeth densitometer RD-914,
The print density was 0.89 and the background density was 0.09. Next, using a hot stamp at 150 ° C.
When the data was erased in 0.5 seconds, the erase density was 0.09. When the above-mentioned printing / erasing was repeated 50 times, there was almost no decrease in the printing density and no increase in the erasing density, and there was no dent. Further, when the printed sample was irradiated with a fluorescent lamp at 5500 lux for 100 hours, discoloration was not observed in both the printed portion and the background portion, and the erased portion at the time of erasing was not recognized.

Application Example 7 (Production Example 7 of Reversible Thermosensitive Recording Medium) A recording layer was provided in the same manner as in Application Example 5. An intermediate layer solution having the following composition was applied to the recording layer using a wire bar, dried at 80 ° C., and heated at 60 ° C. for 24 hours to form an intermediate layer having a thickness of about 2 μm. <Intermediate layer coating solution> 100% of a 10% MEK solution of polyester polyol resin (Takelac U-21 manufactured by Takeda Pharmaceutical Co., Ltd.) 100 parts UV absorber having the following structure 10 parts Coronate L 15 parts UV absorber structural formula

Embedded image Next, an OP layer similar to that of Application Example 3 was provided on the intermediate layer to produce a reversible thermosensitive recording medium.

Application Example 2 of the recording medium manufactured as described above
When the optical density of the printed portion and the background portion was measured using a Macbeth densitometer RD-914,
The print density was 0.90 and the background density was 0.09. Next, using a hot stamp at 150 ° C.
When the data was erased in 0.5 seconds, the erase density was 0.09. When the above-mentioned printing / erasing was repeated 50 times, there was almost no decrease in the printing density and no increase in the erasing density, and there was no dent. Further, when the printed sample was irradiated with a fluorescent lamp at 5500 lux for 100 hours, discoloration was not observed in both the printed portion and the background portion, and the erased portion at the time of erasing was not recognized.

Application Example 8 (Production Example 8 of Reversible Thermosensitive Recording Medium) A recording layer was provided in the same manner as in Application Example 2, except that the following recording layer dispersion liquid was used. 3- (4-diethylamino-2-ethoxyphenyl-3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 2 parts Developer No. 9 of the present invention 8 parts Polyester polyol resin (Takeda 150 parts of 15% THF solution of Takelac U-21) manufactured by Yakuhin Kogyo Co., Ltd.

On the recording layer, an intermediate layer similar to that of Application Example 2 was provided, and then a protective layer was provided in the same manner as in Application Example 2 except that the following protective layer coating solution was used. Was prepared. <Protective layer coating liquid> Urethane acrylate UV curable resin 10 parts (Dainippon Ink Co., Ltd. C7-157) Ethyl acetate 90 parts

The recording medium manufactured as described above is applied to application example 2.
When the optical density of the printed portion and the background portion was measured using a Macbeth densitometer RD-914,
The printing density was 0.91 and the background density was 0.10. Next, using a hot stamp at 150 ° C.
When the erasing was performed in 0.5 seconds, the erasing density was 0.10. When the above-mentioned printing / erasing was repeated 50 times, there was almost no decrease in the printing density and no increase in the erasing density, and there was no dent. Further, when the printed sample was irradiated with a fluorescent lamp at 5500 lux for 100 hours, discoloration was not observed in both the printed portion and the background portion, and the erased portion at the time of erasing was not recognized.

Application Example 9 (Production Example 9 of Reversible Thermosensitive Recording Medium) After a recording layer was provided in the same manner as in Application Example 8, a protective layer was provided on the recording layer in the same manner as in Application Example 3, and reversible thermosensitive recording was performed. A medium was prepared.

The recording medium manufactured as described above is applied to application example 2.
When the optical density of the printed portion and the background portion was measured using a Macbeth densitometer RD-914,
The print density was 0.93 and the background density was 0.10. Next, using a hot stamp at 150 ° C.
When the erasing was performed in 0.5 seconds, the erasing density was 0.10. When the above-mentioned printing / erasing was repeated 50 times, there was almost no decrease in the printing density and no increase in the erasing density, and there was no dent. Further, when the printed sample was irradiated with a fluorescent lamp at 5500 lux for 100 hours, discoloration was not observed in both the printed portion and the background portion, and the erased portion at the time of erasing was not recognized.

Application Example 10 (Production Example 10 of Reversible Thermosensitive Recording Medium) The following composition was pulverized and dispersed to a particle size of 1 to 4 μm using a ball mill to prepare a coating solution for a recording layer. 2-anilino-3-methyl-6-diethylaminofluorane 2 parts 88 parts 15% THF solution of poly n-butyl methacrylate resin (BR102, manufactured by Mitsubishi Rayon Co., Ltd.) 150 parts The recording layer coating solution having the above composition was applied to a 100 μm thick white polyester film using a wire bar.
After drying at 0 ° C., a recording layer having a thickness of about 6 μm was provided.

On the recording layer, an intermediate layer having the following composition was applied using a wire bar and dried at 80 ° C. to provide an intermediate layer having a thickness of about 2 μm. <Intermediate layer coating liquid> 100 parts of 10% methyl ethyl ketone (MEK) solution of poly n-butyl methacrylate resin (BR102, manufactured by Mitsubishi Rayon Co.) 10 parts of ultrafine zinc oxide (average particle diameter: 20 nm) 10 parts Next, application example on the intermediate layer A protective layer was provided in the same manner as in Example 2 to produce a reversible thermosensitive recording medium.

The recording medium manufactured as described above is applied to application example 2.
When the optical density of the printed portion and the background portion was measured using a Macbeth densitometer RD-914,
The print density was 1.17 and the background density was 0.10. Next, using a hot stamp at 150 ° C.
When the erasing was performed in 0.5 seconds, the erasing density was 0.10. In addition, a printing sample was prepared using a fluorescent lamp of 5500lu.
When irradiation was performed for 100 hours at x, the discoloration and the unerased residue at the time of erasing were not recognized in both the printed portion and the background portion, and the condition was excellent.

Application Example 11 (Production Example 11 of Reversible Thermosensitive Recording Medium) After a recording layer was provided in the same manner as in Application Example 10, a protective layer similar to that in Application Example 3 was provided on the recording layer. A recording medium was produced.

The recording medium manufactured as described above is applied to application example 2.
When the optical density of the printed portion and the background portion was measured using a Macbeth densitometer RD-914,
The print density was 1.22 and the background density was 0.11. Next, using a hot stamp at 150 ° C.
After erasing for 0.5 seconds, the erase density was 0.11. In addition, a print sample was prepared using a fluorescent lamp of 5500 lux, 10
Irradiation for 0 hour showed that both the printed portion and the background portion were in a good state with no discoloration and no erasure remaining upon erasure.

[0073]

The phenol compound of the present invention is a novel compound. Furthermore, the reversible thermosensitive recording medium using the compound of the present invention as a color developer can be formed by a simple operation of forming and erasing a high-contrast image, and the color image is stable under ordinary use conditions. In addition, a highly practical rewritable recording medium having high durability against repeated recording and erasing can be obtained.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. FIG. 2 is a view showing an infrared absorption spectrum of Sample No. 1;

FIG. 2 shows Compound No. of the present invention. FIG. 2 is a diagram showing an infrared absorption spectrum of Sample No. 2;

FIG. 3 shows Compound No. of the present invention. FIG. 3 is a diagram showing an infrared absorption spectrum of Sample No. 3;

FIG. 4. Compound No. of the present invention. FIG. 4 is a diagram showing an infrared absorption spectrum of Sample No. 4;

FIG. 5: Compound No. of the present invention FIG. 5 is a diagram showing an infrared absorption spectrum of Sample No. 5;

FIG. 6 shows Compound No. of the present invention. 6 is a diagram showing an infrared absorption spectrum of Sample No. 6; FIG.

FIG. 7 shows a compound No. FIG. 7 is a view showing an infrared absorption spectrum of Sample No. 7;

FIG. 8 shows a compound No. FIG. 8 is a view showing an infrared absorption spectrum of Sample No. 8;

FIG. 9 shows Compound No. of the present invention. 9 is a diagram showing an infrared absorption spectrum of Sample No. 9. FIG.

FIG. 10 shows Compound No. of the present invention. It is a figure which shows the infrared absorption spectrum of No. 10.

FIG. 11 shows Compound No. of the present invention. It is a figure which shows the infrared absorption spectrum of No. 11.

FIG. 12 shows Compound No. of the present invention. FIG. 12 is a diagram showing an infrared absorption spectrum of No. 12.

FIG. 13 shows Compound No. of the present invention. 13 is a diagram showing an infrared absorption spectrum of No. 13. FIG.

FIG. 14 shows Compound No. of the present invention. FIG. 14 is a diagram showing an infrared absorption spectrum of No. 14;

FIG. 15 shows a compound No. of the present invention. It is a figure which shows the 15 infrared absorption spectrum.

FIG. 16 shows Compound No. of the present invention. It is a figure which shows the 16 infrared absorption spectrum.

FIG. 17 shows a compound No. of the present invention. FIG. 17 is a diagram showing an infrared absorption spectrum of Sample No. 17;

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location // B41M 5/26 C09B 57/00 Z 5/30 B41M 5/18 101A C09B 57/00 108 ( 72) Inventor Hiromi Furuya 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Fumio Kawamura 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Koji Tsutsui 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Katsuyuki Sugiyama 4-6-1, Horikiri, Katsushika-ku, Tokyo Inside Miyoshi Oil & Fat Co., Ltd. (72) Katsuaki Kokubo, Inventor Miyoshi Oil & Fat Co., Ltd., 4-6-1, Horikiri, Katsushika-ku, Tokyo Koji Kawai Miyoshi Oil & Fat, 4-6-1, Horikiri, Katsushika-ku, Tokyo In-company (72) Inventor Kazuo Hosoda 4-6-1, Horikiri, Katsushika-ku, Tokyo Miyoshi Oil & Fat Co., Ltd. (72) Inventor Masafumi Moriya 4-6-1, Horikiri, Katsushika-ku, Tokyo Miyoshi Oil & Fat Stock In-company (72) Inventor Katsuhisa Kamio 4-6-1, Horikiri, Katsushika-ku, Tokyo Inside Miyoshi Oil & Fats Co., Ltd.

Claims (4)

[Claims] 1. A novel phenol compound represented by the following general formula (I). Embedded image (Wherein X is -NHCONH-, -NHCO-, -CO
NH-, -NHCONH-, -CONHNHCO-
Or -SO ₂ - represents a group represented, n is 2 to 11,
m represents an integer of 6 to 21. ) 2. The phenol compound according to claim 1, wherein said X is -NHCONH-. 3. The phenol compound according to claim 1, wherein said X is —NHCO—. 4. The phenol compound according to claim 1, wherein said X is —CONH—.