JPH07304727A - New aminobenzenesulfonamide derivative and recording substance using the same - Google Patents

Abstract

PURPOSE:To obtain a new aminobenzene sulfonamide derivative useful as a developer capable of providing a heat-sensitive recording substance or a photosensitive recording substance excellent in heat resistance. CONSTITUTION:A compound of formula I [X is a 1-6C alkyl or an electron- attracting group; (m) is 0-3], e.g. 4-(N-p tolylcarbamoyl)amino benzenesulfonamide and 4-(N-phenylcarbamoyl) aminobenzene-sulfonamide of formula II. The compound of formula I is obtained by reacting 4- aminobenzenesufonamide with isocyanic acid phenyl esters. In a heat-sensitive recording substance providing a recording layer containing colorless or pale color dye precursor and a developer capable of coloring by reaction with the dye precursor as main ingredients on a support, a compound of formula I or formula II is used as the developer. The group in the compound of formula I is preferably an electron-attracting group from the aspect of stability of recording image to heat and oil and the electron-attracting group is especially preferably a halogen atom, a 1-6C alkoxy group, a nitro group or a cyano group from the aspect of heat resistance, recording sensitivity, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel 4- (N-phenylcarbamoyl) aminobenzenesulfonamide derivative, and a heat-sensitive recording material or optical recording material using this compound as a color developer and having excellent heat resistance. Is.

[0002]

2. Description of the Related Art Generally, a heat-sensitive recording sheet is generally prepared by grinding and dispersing a colorless or light-colored dye precursor and a color developing agent such as a phenolic compound into fine particles, and then mixing the two, mixing them, and binding them. Coating solution obtained by adding agents, sensitivity improvers, lubricants and other auxiliaries to a substrate such as paper, synthetic paper, film, plastic, etc., thermal head, hot stamp, heat The color is developed by an instantaneous chemical reaction caused by heating with a pen, laser light or the like to obtain a recorded image.

These thermal recording materials are used for measuring recorders, computer terminal printers, facsimiles,
It has been applied to a wide range of fields such as automatic ticket vending machines and bar code labels, but with the diversification and high performance of these recording devices, the quality requirements for thermal recording sheets have become more sophisticated. There is. For example, with the increase in recording speed, it is required to obtain a clear color image with high density even with a small amount of thermal energy, while the storage stability such as light resistance, heat resistance, water resistance, oil resistance and plasticizer resistance is required. An excellent thermosensitive recording sheet is required.

More recently, as the method of recording on plain paper such as the electrophotographic method and the ink jet method has become widespread, thermal recording is often compared with these plain paper recordings. For example, the image stability is close to that of toner recording, and the stability of the non-recorded portion (white paper portion or background color portion) before and after recording (hereinafter referred to as background color stability) is similar to that of plain paper recording. Is required, and since heat-sensitive recording paper is used as a food label that is sterilized at a high temperature, and heat-laminating processing is performed when used for cards such as lift tickets, the temperature is 100 ° C or higher. There is an increasing demand for ground color stability against heat.

Regarding the stability of the background color to heat, JP-A-4-353490 discloses 3-dibutylamino-7-.
(O-chloroanilino) fluorane, 4-hydroxydiphenylsulfone compound having a melting point of 120 ° C. or higher, and a mixture of sodium salt of 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate and magnesium silicate, etc. A thermal recording material containing 90%
It is disclosed that the ground color portion and the recorded image portion are excellent in stability even in a high temperature environment of around ℃.

On the other hand, the recording on the thermal recording medium is generally carried out by heating the thermal recording medium by directly contacting the thermal head or the heat-generating IC pen, which is a heating element, with the thermal recording paper. In this method, a coloring melt or the like adheres to the heating element to cause deposition and the recording function is apt to deteriorate, and there is a limit in increasing the integration density of the heating elements in the thermal head. Since the main resolution is about book / mm, it is difficult to record at higher resolution. Therefore, a non-contact recording method using light has been proposed as a method for further improving the resolution without degrading the recording function.

Japanese Unexamined Patent Publication (Kokai) No. 58-148767 discloses that a carbon dioxide gas laser is used as a recording light source and the laser is converged and scanned on a thermal recording paper for a general thermal head to enable thermal recording. Disclosure. In this recording method, a high laser output is required although the thermal recording paper absorbs the oscillation wavelength of the carbon dioxide laser. Including the use of a gas laser as a recording light source, the recording device cannot be miniaturized, and there is a problem in cost.

Further, since a general thermal recording paper does not easily absorb light in the visible or near infrared region, when a laser having an oscillation wavelength in the visible or near infrared region is used as a recording light source, the laser output is comparable. If it is not increased, the heat energy required for color development cannot be obtained.

Further, an optical recording material comprising a combination of a conventional heat sensitive recording material and a light absorbing material is disclosed in JP-A-54-4142.
JP-A-57-11090, JP-A-58-9449
No. 4 and JP-A-58-209594.

Japanese Unexamined Patent Publication No. 54-4142 discloses a thermosensitive recording medium prepared by coating a support with a thermosensitive recording layer containing a leuco dye as a main component, by using a metal compound having a lattice defect. It is disclosed that the metal compound absorbs light in the visible or infrared region and converts it into heat to enable thermal recording. JP-A-57-11090
Japanese Patent Laid-Open Publication No. 2003-242242 discloses an optical recording material in which a recording layer composed of a colorless or light-colored coloring material, a phenolic material, and an organic polymer binder has benzenedithiol-based nickel complexes as a light absorber and records with a laser beam. Have been described. Japanese Unexamined Patent Publication (Kokai) No. 58-94494 discloses one or two or more types of thermosensitive color-developing materials and one or more types of compounds having a maximum absorption wavelength in the near infrared region of 0.7 to 3 μm. A recording medium in which an infrared absorbing material is coated on a substrate is disclosed. Japanese Unexamined Patent Publication (Kokai) No. 58-209594 discloses an optics characterized by laminating at least one set of a near-infrared absorber having an absorption wavelength in the near-infrared region of 0.8 to 2 μm and a thermosensitive coloring material on a substrate. The recording medium is disclosed.

[0011]

[Patent Document 1] Japanese Patent Application Laid-Open No. 4-35349
The thermal stability of the background color (hereinafter referred to as thermal stability) of the heat-sensitive recording material disclosed in JP-A No. 0-5 is 5 in a hot air dryer at 95 ° C.
The Macbeth density of the background color after the time treatment is 0.11, and although it shows considerable stability, it is still insufficient at the heat resistant temperature.

[0012] Further, due to the heat resistance of conventional thermal recording materials using a phenol-based developer as a recording material, it is impossible to thermally laminate the recording surface after thermal recording or the entire recording material with a film or the like. It was On the other hand, even in the heat resistance of conventional optical recording materials using a phenolic developer as a recording material, the recording surface of an unrecorded optical recording material or the entire recording material is thermally laminated with a film or the like, and thermal recording. When the recording surface after optical recording or the entire recording body is thermally laminated with a film or the like, the entire surface is colored, which makes practical use impossible.

In view of the above, it is an object of the present invention to provide a heat-sensitive recording material or an optical recording material that can be heat-laminated and has heat resistance to some extent.

[0014]

The aminobenzenesulfonamide derivative according to the present invention is represented by the following general formula (1).

[0015]

[Chemical 3] (In the formula, X represents a lower alkyl group having 1 to 6 carbon atoms or an electron-withdrawing group. M represents an integer of 0 to 3.)

The compound represented by the general formula (1) of the present invention can be produced by reacting sulfanilamide (also known as 4-aminobenzenesulfonamide) with phenyl isocyanate. That is, in the reaction, 1 to 2.5 mol of phenyl isocyanate is added to 1 mol of sulfanilamide. The solvent used may be one that dissolves sulfanilamide and phenyl isocyanate, for example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated aromatic hydrocarbons such as chloroform, dichloromethane and chlorobenzene, Ethers such as diethyl ether and tetrahydrofuran, acetonitrile, nitriles such as propionitrile, esters such as ethyl acetate, acetone,
Ketones such as methyl ethyl ketone, aproton-donating polar solvents such as dimethylformamide and dimethylsulfoxide, alcohols such as methanol and ethanol,
Or it is a mixed solvent thereof. The reaction temperature is 0 to
The temperature is 150 ° C, preferably 20 to 100 ° C.

Specific examples of the compound represented by the general formula (1) of the present invention include the followings, but the invention is not limited thereto.

[0018]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

The aminobenzenesulfonamide derivative represented by the above general formula (1) is a novel compound and can be used as a physiologically active substance, a drug, a developer for heat-sensitive recording paper and the like. From the viewpoint of industrial utilization, these aminobenzenesulfonamide derivatives according to the present invention are preferably monosubstituted or disubstituted chloro groups for X in the general formula (1), and further, are unsubstituted compounds. 4- (N-phenylcarbamoyl) aminobenzenesulfonamide represented by the following structural formula (2) is more preferable.

[0020]

[Chemical 8]

The aminobenzenesulfonamide derivative of the present invention comprises a support, a colorless or pale color dye precursor, and
In a heat-sensitive recording material provided with a recording layer containing as a main component a color developing agent which reacts with the dye precursor to develop a color, the use as a color developing agent causes problems of conventional heat-sensitive recording paper. The above problems were solved at once.

X in the general formula (1) has 1 to 6 carbon atoms.
Is a lower alkyl group or an electron withdrawing group, and m is 0 to
Although a thermal recording material using a compound that is an integer of 3 as a color developer can record with a thermal head or the like, on the other hand, the background color is less developed even in a thermal environment of about 160 ° C. It has properties that cannot be considered with the thermal papers up to.

It is considered that the aminobenzenesulfonamide derivative of the present invention exhibits a color developing ability by changing from the keto type structure represented by the general formula (1) to an enol type structure by causing tautomerism. Therefore, in consideration of heat and oil stability of the recorded image, X in the general formula (1) may be a lower alkyl group having 1 to 6 carbon atoms in order to stabilize the enol type structure exhibiting color developing ability. An electron-withdrawing group is more preferable, though it shows sufficient recorded image stability.
As the electron-withdrawing group, in terms of heat resistance, recording sensitivity, etc.,
A halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, or a cyano group is preferable.

In consideration of industrial productivity and practicality, X in the general formula (1) is preferably a mono-substituted or di-substituted chloro group. In particular, in the case of focusing on economical efficiency, 4-the compound represented by the structural formula (2), which is an unsubstituted compound,
(N-phenylcarbamoyl) aminobenzenesulfonamide is preferred.

A general method for producing the thermosensitive recording medium of the present invention is to disperse a dye precursor and at least one compound represented by the general formula (1) as a developer together with a binder. This is a method in which an auxiliary agent such as a filler, a lubricant, an ultraviolet absorber, a water-proofing agent, and a defoaming agent is added, if necessary, to prepare a coating solution, which is coated on a support by a usual method and dried.

A conventionally known developer and a conventionally known sensitizer for coloring a dye precursor may be added to the coating liquid as long as the desired effects for the above problems are not impaired.

As the dye precursor to be used in the recording material of the present invention, all those known in the conventional pressure-sensitive or heat-sensitive recording paper field can be used, and although not particularly limited, triphenylmethane-based ones can be used. Compounds, fluoran compounds, fluorene compounds, divinyl compounds and the like are preferable. Specific examples of typical dye precursors are shown below. These dye precursors may be used alone or in combination of two or more.

<Triphenylmethane Leuco Dye> 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide [also known as crystal violet lactone] 3,3-bis (p-dimethylaminophenyl) phthalide [ Also known as malachite green lactone]

<Fluoran Leuco Dye> 3-Diethylamino-6-methylfluorane 3-diethylamino-6-methyl-7-anilinofluorane 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) ) Fluoran 3-diethylamino-6-methyl-7-chlorofluorane 3-diethylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane 3-diethylamino-6-methyl-7- (o-chloroanilino) Fluorane 3-diethylamino-6-methyl-7- (p-chloroanilino) fluorane 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluorane 3-diethylamino-6-methyl-7-n-octylanilino Fluoran 3-diethylamino-6-methyl-7-benzylanili Nofluorane 3-diethylamino-6-methyl-7-dibenzylanilinofluorane 3-diethylamino-6-chloro-7-methylfluorane 3-diethylamino-6-chloro-7-anilinofluorane 3-diethylamino-6- Chloro-7-p-methylanilinofluorane 3-diethylamino-6-ethoxyethyl-7-anilinofluorane 3-diethylamino-7-methylfluorane 3-diethylamino-7-chlorofluorane 3-diethylamino-7- (M-Trifluoromethylanilino) fluorane 3-diethylamino-7- (o-chloroanilino) fluorane 3-diethylamino-7- (p-chloroanilino) fluorane 3-diethylamino-benzo [a] fluorane 3-diethylamino-benzo [c ] Fluoran 3-Di Butylamino-6-methyl-fluorane 3-dibutylamino-6-methyl-7-anilinofluorane 3-dibutylamino-6-methyl-7- (o, p-dimethylanilino) fluorane 3-dibutylamino-6 -Methyl-7- (o-chloroanilino) fluorane 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluorane 3-dibutylamino-6-methyl-7- (o-fluoroanilino) fluorane 3-dibutyl Amino-6-methyl-7- (m-trifluoromethylanilino) fluorane 3-dibutylamino-6-methyl-chlorofluorane 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane 3-dibutylamino -6-chloro-7-anilinofluorane 3-dibutylamino-6-methyl-7-p-methyl Anilinofluorane 3-dibutylamino-7- (o-chloroanilino) fluorane 3-n-dipentylamino-6-methyl-7-anilinofluorane 3-n-dipentylamino-6-methyl-7- (p- Chloroanilino) fluorane 3-n-dipentylamino-6-chloro-7-anilinofluorane 3-n-dipentylamino-7- (p-chloroanilino) fluorane 3-pyrrolidino-6-methyl-7-anilinofluorane 3 -Piperidino-6-methyl-7-anilinofluorane 3- (N-methyl-N-propylamino) -6-methyl-7-anilinofluorane 3- (N-methyl-N-cyclohexylamino) -6 −
Methyl-7-anilinofluorane 3- (N-ethyl-N-cyclohexylamino) -6-
Methyl-7-anilinofluorane 3- (N-ethyl-N-xylamino) -6-methyl-
7- (p-chloroanilino) fluorane 3- (N-ethyl-p-toluidino) -6-methyl-
7-anilinofluorane 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane 3- (N-ethyl-N-isoamylamino) -6-chloro-7-anilino Fluorane 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane 3-cyclohexylamino-6-chlorofluorane 2- (4-oxahexyl) -3-dimethylamino -6
-Methyl-7-anilinofluorane 2- (4-oxahexyl) -3-diethylamino-6
-Methyl-7-anilinofluorane 2- (4-oxahexyl) -3-dipropylamino-
6-methyl-7-anilinofluorane 2-methyl-6-p- (p-dimethylaminophenyl)
Aminoanilinofluorane 2-Methoxy-6-p- (p-dimethylaminophenyl) aminoanilinofluorane 2-chloro-3-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane 2 -Chloro-6-p- (p-dimethylaminophenyl)
Aminoanilinofluorane 2-nitro-6-p- (p-diethylaminophenyl)
Aminoanilinofluorane 2-amino-6-p- (p-diethylaminophenyl)
Aminoanilinofluorane 2-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane 2-phenyl-6-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane 2- Benzyl-6-p- (p-phenylaminophenyl) aminoanilinofluorane 2-hydroxy-6-p- (p-phenylaminophenyl) aminoanilinofluorane 3-methyl-6-p- (p-dimethyl Aminophenyl)
Aminoanilinofluorane 3-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluorane 3-diethylamino-6-p- (p-dibutylaminophenyl) aminoanilinofluorane

<Fluorene Leuco Dye> 3,6,6′-Tris (dimethylamino) spiro [fluorene-9,3′-phthalide] 3,6,6′-Tris (diethylamino) spiro [fluorene-9,3] ´-phthalide]

<Divinyl Leuco Dye> 3,3-Bis- [2- (p-dimethylaminophenyl)
-2- (p-Methoxyphenyl) ethenyl] -4,5,
6,7-Tetrabromophthalide 3,3-bis- [2- (p-dimethylaminophenyl)
-2- (p-Methoxyphenyl) ethenyl] -4,5,
6,7-Tetrachlorophthalide 3,3-bis- [1,1-bis (4-pyrrolidinophenyl) ethylene-2-yl] -4,5,6,7-tetrabromophthalide 3,3- Bis- [1- (4-methoxyphenyl) -1-
(4-Pyrrolidinophenyl) ethylene-2-yl]-
4,5,6,7-tetrachlorophthalide

<Others> 3- (4-diethylamino-2-ethoxyphenyl)-
3- (1-ethyl-2-methylindol-3-yl)
-4-azaphthalide 3- (4-diethylamino-2-ethoxyphenyl)-
3- (1-octyl-2-methylindol-3-yl) -4-azaphthalide 3- (4-cyclohexylethylamino-2-methoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) ) -4-Azaphthalide 3,3-bis (1-ethyl-2-methylindole-3)
-Yl) phthalide 3,6-bis (diethylamino) fluorane-γ- (3
′ -Nitro) anilinolactam 3,6-bis (diethylamino) fluorane-γ- (4
′ -Nitro) anilinolactam 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2,
2-Dinitrileethane 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2-
β-naphthoylethane 1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2,
2-Diacetylethane bis- [2,2,2 ', 2'-tetrakis- (p-dimethylaminophenyl) -ethenyl] -methylmalonic acid dimethyl ester

In the present invention, one or two or more conventionally known color formers for coloring a dye precursor are represented by the general formula (1) of the present invention within a range that does not impair the desired effects on the above problems. It can be used in combination with the represented compounds. In the case of producing a heat-sensitive recording material having extremely excellent heat resistance, it is better to avoid the combined use of a conventionally known developer, but according to the heat resistance temperature characteristic to the intended thermal environment, the conventionally known developer is used. Can be used in combination with the compound of the general formula (1) of the present invention. Examples of such a developer include JP-A-3-207688 and JP-A-5-24366.
Bisphenol A, 4-hydroxybenzoic acid esters, 4-hydroxyphthalic acid diesters, phthalic acid monoesters, bis- (hydroxyphenyl) sulfides, 4-hydroxyphenyl aryl sulfones, 4 -Hydroxyphenyl aryl sulfonates, 1,3-di [2- (hydroxyphenyl)-
Examples include 2-propyl] -benzenes, 4-hydroxybenzoyloxybenzoic acid esters, and bisphenol sulfones. Specific examples of typical known color developing agents are shown below, but the invention is not particularly limited thereto.

<Bisphenol A>4,4'-isopropylidene diphenol (also known as bisphenol A) 4,4'-cyclohexylidene diphenol p, p '-(1-methyl-normalhexylidene) diphenol 1, 7-di (hydroxyphenylthio) -3,5-dioxaheptane

<4-Hydroxybenzoic Acid Esters> Benzyl 4-hydroxybenzoate 4-Ethyl 4-hydroxybenzoate 4-Propyl 4-hydroxybenzoate Isopropyl 4-hydroxybenzoate 4-Butyl 4-hydroxybenzoate Isobutyl 4-hydroxybenzoate 4- Methylbenzyl hydroxybenzoate

<4-Hydroxyphthalic acid diesters> Dimethyl 4-hydroxyphthalate 4-Diisopropyl 4-hydroxyphthalate 4-Dibenzyl 4-hydroxyphthalate 4-Dihexyl 4-hydroxyphthalate

<Phthalic acid monoesters> Phthalic acid monobenzyl ester Phthalic acid monocyclohexyl ester Phthalic acid monophenyl ester Phthalic acid monomethylphenyl ester Phthalic acid monoethylphenyl ester Phthalic acid monopropylbenzyl ester Phthalic acid monohalogen benzyl ester Phthalic acid Monoethoxybenzyl ester

<Bis- (hydroxyphenyl) sulfides> Bis- (4-hydroxy-3-tert-butyl-6-)
Methylphenyl) sulfide bis- (4-hydroxy-2,5-dimethylphenyl)
Sulfide Bis- (4-hydroxy-2-methyl-5-ethylphenyl) sulfide Bis- (4-hydroxy-2-methyl-5-isopropylphenyl) sulfide Bis- (4-hydroxy-2,3-dimethylphenyl)
Sulfide Bis- (4-hydroxy-2,5-dimethylphenyl)
Sulfide Bis- (4-hydroxy-2,5-diisopropylphenyl) sulfide Bis- (4-hydroxy-2,3,6-trimethylphenyl) sulfide Bis- (2,4,5-trihydroxyphenyl) sulfide Bis- ( 4-hydroxy-2-cyclohexyl-5-methylphenyl) sulfide bis- (2,3,4-trihydroxyphenyl) sulfide bis- (4,5-dihydroxy-2-tert-butylphenyl) sulfide bis- (4- Hydroxy-2,5-diphenylphenyl) sulfide bis- (4-hydroxy-2-tert-octyl-5
-Methylphenyl) sulfide

<4-Hydroxyphenylarylsulfones>4-hydroxy-4'-isopropoxydiphenylsulfone4-hydroxy-4'-propoxydiphenylsulfone4-hydroxy-4'-n-butyloxydiphenylsulfone 4-hydroxy- 4'-n-propoxydiphenyl sulfone

<4-Hydroxyphenylarylsulfonates> 4-hydroxyphenylbenzenesulfonate 4-hydroxyphenyl-p-tolylsulfonate 4-hydroxyphenylmethylenesulfonate 4-hydroxyphenyl-p-chlorobenzenesulfonate 4- Hydroxyphenyl-p-tert-butylbenzenesulfonate 4-Hydroxyphenyl-p-isopropoxybenzenesulfonate 4-Hydroxyphenyl-1'-naphthalenesulfonate 4-Hydroxyphenyl-2'-naphthalenesulfonate

<1,3-Di [2- (hydroxyphenyl) -2-propyl] benzenes> 1,3-di [2- (4-hydroxyphenyl) -2-propyl] benzene 1,3-di [ 2- (4-hydroxy-3-alkylphenyl) -2-propyl] benzene 1,3-di [2- (2,4-dihydroxyphenyl)-
2-Propyl] benzene 1,3-di [2- (2-hydroxy-5-methylphenyl) -2-propyl] benzene

<Resorcinols> 1,3-dihydroxy-6 (α, α-dimethylbenzyl) -benzene

<4-hydroxybenzoyloxybenzoic acid ester> benzyl 4-hydroxybenzoyloxybenzoate 4-hydroxybenzoyloxy methyl benzoate 4-hydroxybenzoyloxy ethyl benzoate 4-hydroxybenzoyloxypropyl propyl 4-hydroxybenzoyloxy Butyl benzoate 4-Hydroxybenzoyloxy isopropyl benzoate 4-Hydroxybenzoyloxybenzoate tert-butyl 4-hydroxybenzoyloxyhexyl benzoate 4-Hydroxybenzoyloxy octyl benzoate 4-Hydroxybenzoyloxy nonyl 4-hydroxybenzoyloxybenzoate Cyclohexyl benzoate 4-hydroxybenzoyloxy β-phenethyl benzoate 4-hydroxybenzoyloxy Phenyl benzoate 4-hydroxy-benzoyloxy benzoate α- naphthyl 4-hydroxy-benzoyloxy benzoate β- naphthyl 4-hydroxy-benzoyloxy benzoate sec- butyl

<Bisphenol Sulfones (I)> Bis- (3-1-butyl-4-hydroxy-6-methylphenyl) sulfone Bis- (3-ethyl-4-hydroxyphenyl) sulfone Bis- (3-propyl-) 4-hydroxyphenyl) sulfone bis- (3-methyl-4-hydroxyphenyl) sulfone bis- (2-isopropyl-4-hydroxyphenyl)
Sulfone Bis- (2-ethyl-4-hydroxyphenyl) sulfone Bis- (3-chloro-4-hydroxyphenyl) sulfone Bis- (2,3-dimethyl-4-hydroxyphenyl)
Sulfone Bis- (2,5-dimethyl-4-hydroxyphenyl)
Sulfone Bis- (3-methoxy-4-hydroxyphenyl) sulfone 4-Hydroxyphenyl-2'-ethyl-4'-hydroxyphenyl sulfone 4-Hydroxyphenyl-2'-isopropyl-4'-
Hydroxyphenyl sulfone 4-hydroxyphenyl-3'-isopropyl-4'-
Hydroxyphenyl sulfone 4-hydroxyphenyl-3'-sec butyl-4'-
Hydroxyphenyl sulfone 3-chloro-4-hydroxyphenyl-3'-isopropyl-4'-hydroxyphenyl sulfone 2-hydroxy-5-t-butylphenyl-4'-hydroxyphenyl sulfone 2-hydroxy-5-t-aminophenyl -4'-hydroxyphenyl sulfone 2-hydroxy-5-t-isopropylphenyl-4 '
-Hydroxyphenyl sulfone 2-hydroxy-5-t-octylphenyl-4'-hydroxyphenyl sulfone 2-hydroxy-5-t-butylphenyl-3'-chloro-4'-hydroxyphenyl sulfone 2-hydroxy-5-t -Butylphenyl-3'-methyl-4'-hydroxyphenyl sulfone 2-hydroxy-5-t-butylphenyl-3'-isopropyl-4'-hydroxyphenyl sulfone 2-hydroxy-5-t-butylphenyl-3 '-Chloro-4'-hydroxyphenyl sulfone 2-hydroxy-5-t-butylphenyl-3'-methyl-4'-hydroxyphenyl sulfone 2-hydroxy-5-t-butylphenyl-3'-isopropyl-4'- Hydroxyphenyl sulfone 2-hydroxy-5-t-butyl Eniru 2'-methyl-4'-hydroxyphenyl sulfone

<Bisphenol sulfones (II)>4,4'-sulfonyldiphenol2,4'-sulfonyldiphenol3,3'-dichloro-4,4'-sulfonyldiphenol3,3'-dibromo-4 , 4'-Sulfonyldiphenol 3,3 ', 5,5'-Tetrabromo-4,4'-sulfonyldiphenol 3,3'-Diamino-4,4'-sulfonyldiphenol

<Others> p-tert-butylphenol 2,4-dihydroxybenzophenone novolac type phenol resin 4-hydroxyacetophenone p-phenylphenol benzyl-4-hydroxyphenylacetate p-benzylphenol

In the present invention, conventionally known sensitizers can be used as long as the desired effects for the above problems are not impaired. In the case of producing a heat-sensitive recording material having extremely excellent heat resistance, it is generally preferable not to use a sensitizer, but it is necessary to add an appropriate amount of the sensitizer according to the heat resistance temperature characteristic to the intended thermal environment. You can

Examples of such sensitizers include fatty acid amides such as stearic acid amide and palmitic acid amide, ethylenebisamide, montanic acid wax, polyethylene wax, 1,2-di- (3-methylphenoxy) ethane, p
-Benzylbiphenyl, β-benzyloxynaphthalene, 4-biphenyl-p-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, di (p-chlorobenzyl) oxalate, di (oxalate) p-methylbenzyl), dibenzyl terephthalate, p
Benzyl benzyloxybenzoate, di-p-tolyl carbonate, phenyl-α-naphthyl carbonate,
1,4-diethoxynaphthalene, 1-hydroxy-2-
Naphthoic acid phenyl ester, o-xylelin-bis-
Examples thereof include (phenyl ether) and 4- (m-methylphenoxymethyl) biphenyl, but are not particularly limited thereto. You may use these sensitizers individually or in mixture of 2 or more types.

As the binder used in the present invention, completely saponified polyvinyl alcohol having a degree of polymerization of 200 to 1900, partially saponified polyvinyl alcohol, carboxy modified polyvinyl alcohol, amide modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, butyral modified polyvinyl. Modified polyvinyl alcohol such as alcohol, cellulose derivative such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, acetyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, polyvinyl chloride, polyvinyl acetate, polyacrylamide , Polyacrylic acid ester, polyvinyl butyral, polystyrene and their copolymers, polyamide resin, silicone Butter, petroleum resins, terpene resins, ketone resins, and coumarone resins. These polymeric substances are water, alcohols, ketones, esters,
In addition to being used by being dissolved in a solvent such as a hydrocarbon, it may be used in a state of being emulsified in water or another medium or dispersed in a paste form, and may be used together depending on the required quality.

Further, in the present invention, p-nitrobenzoic acid metal salt (Ca, Zn), which is a known stabilizer showing an oil resistance effect of a recorded image, etc., within a range that does not impair the desired effect for the above problems, Alternatively, phthalic acid monobenzyl ester metal salt (Ca, Zn) can be added.

As the filler which can be used in the present invention, silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, zinc oxide, aluminum hydroxide, polystyrene resin, urea-formalin resin, styrene- Examples thereof include methacrylic acid copolymers, styrene-butadiene copolymers, and inorganic or organic fillers such as hollow plastic pigments.

In addition, release agents such as fatty acid metal salts, lubricants such as waxes, UV absorbers such as benzophenone and triazole, water resistance agents such as glyoxal, dispersants, defoaming agents, antioxidants, and fluorescent agents. A dye or the like can be used.

The amounts of the color developer and the dye precursor used in the heat-sensitive recording material of the present invention and the types and amounts of other various components are determined according to the required performance and recording suitability and are not particularly limited. , Usually to 1 part of dye precursor,
1 to 8 parts of the color developer of the present invention and 1 to 20 parts of the filler are used, and 10 to 25% of the total solid content of the binder is suitable.

As the support, paper, synthetic paper, plastic film, non-woven fabric, metal foil or the like can be used, and a composite sheet in which these are combined may be used. The desired thermosensitive recording medium can be obtained by applying a coating solution having the above composition to any one of these supports.

An overcoat layer of a polymer substance or the like may be provided on the thermosensitive coloring layer for the purpose of further improving the storage stability.

An undercoat layer containing an organic filler or an inorganic filler may be provided between the color forming layer and the support for the purpose of enhancing the storage stability and sensitivity.

The above-mentioned color developer, dye precursor and, if necessary, the material to be added are atomized by a crusher such as a ball mill, an attritor, a sand grinder or an appropriate emulsifying device until the particle diameter becomes several microns or less, A binder and various additive materials are added depending on the purpose to prepare a coating liquid.

The heat-sensitive recording material of the present invention can be made into an optical recording material by including a light absorbing agent which absorbs light into heat and converts it into heat. The light absorber for converting light into heat used in the recording material of the present invention may be any substance that absorbs the emission wavelength of various light sources, various dyes, various pigments,
A near infrared absorber or the like can be used and is not particularly limited.

When a stroboscopic flash having a continuous emission wavelength is used as a recording light source, examples of light absorbers that convert light into heat include, for example, Japanese Patent Application Laid-Open No. 2-206583 and Japanese Patent Application No. 5-30954. The heating reaction product of a thiourea derivative and a copper compound described in the specification, graphite, copper sulfide, lead sulfide, molybdenum trisulfide, black titanium and the like described in JP-A-3-86580. Other,
Carbon black can also be used as a light absorber. These light absorbers can also be light absorbers for laser recording.

When a semiconductor laser which is excellent in miniaturization, safety, price, modulation, etc. is used as a recording laser, particularly when a semiconductor laser having an oscillation wavelength from the visible wavelength region to the near infrared region is used. As materials having absorption according to the oscillation wavelength, Japanese Patent Laid-Open Nos. 54-4142, 58-94494 and 58-209594 are available.
No. 2-217287, No. 3-73814, and “Near-infrared absorbing dye” (Chemical Industry 43, 198).
Polymethine dyes (cyanine dyes), azulenium dyes, pyrylium dyes, thiopyrylium dyes, squarylium dyes, croconium dyes, dithiol metal complex salt dyes, mercaptophenol metal complexes disclosed in May 2006 issue). Type dyes, mercaptonaphthol metal complex dyes, phthalocyanine dyes, naphthalocyanine dyes, triallylmethane dyes, immonium dyes, diimmonium dyes, naphthoquinone dyes, anthraquinone dyes, metal complex salt dyes, etc. can be used. .

Specific examples of the polymethine dye (cyanine dye) include, for example, indocyanine green (manufactured by Daiichi Pharmaceutical Co., Ltd.), NK-2014 (manufactured by Japan Photosensitive Dye Research Institute), NK-. 2612 (manufactured by Japan Photosensitive Dye Research Institute), 1,1,5,5-tetrakis (p-dimethylaminophenyl) -3-methoxy-1,4-pentadiene, 1,1,5,5-tetrakis ( p-diethylaminophenyl) -3-methoxy-1,4-pentadiene and the like. Examples of squarylium dyes include:
NK-2772 (manufactured by Japan Photosensitive Dye Research Institute) and the like. Examples of the dithiol metal complex salt-based dye include toluenedithiol nickel complex, 4-tertbutyl-1,2-benzenedithiol nickel complex, bisdithiobenzylnickel complex, PA-1005 (manufactured by Mitsui Toatsu Dye Co., Ltd.), PA -1006 (manufactured by Mitsui Toatsu Dye Co., Ltd.), bis (4-ethyldithiobenzyl) nickel complex described in Japanese Patent Application No. 4-80646, bis (4-n-propyldithiobenzyl) nickel complex and the like are available. Can be mentioned. Examples of immonium dyes or diimmonium dyes include IRG002 (Nippon Kayaku Co., Ltd.).
Manufactured by Nippon Kayaku Co., Ltd.) and the like. Examples of naphthalocyanine dyes include NIR
-4 (manufactured by Yamamoto Kasei Co., Ltd.) and NIR-14 (manufactured by Yamamoto Kasei Co., Ltd.). Examples of the anthraquinone dye include IR-750 (manufactured by Nippon Kayaku Co., Ltd.) and the like. You may use these light absorbers individually or in mixture of 2 or more types.

The light absorber used in the optical recording material of the present invention is
Although it may be simply mixed in various materials required for the optical recording material, as described in JP-A-2-217287, the light absorbing agent is previously melted in the various materials of the optical recording material of the present invention. What was mixed and melt | dissolved or disperse | distributed can be used. Examples of various materials in which the light absorber is melt-mixed and dissolved or dispersed in advance include, for example, a sensitizer for heat-sensitive recording, the developer of the present invention, a conventionally known developer, a dye precursor, and a sensitizer for heat-sensitive recording. And a developer of the present invention, a composition of a heat-sensitive recording sensitizer and a conventionally known developer, a composition of a heat-sensitive recording sensitizer and a dye precursor, and the like.

The light absorbing agent used in the optical recording material of the present invention is prepared by dissolving or dispersing the materials and the light absorbing material of the optical recording material of the present invention in advance with a solvent to dissolve or disperse the materials and the light absorbing material. The dispersed mixture can also be used after it has been separated from the solvent. As the materials for dissolving or dispersing the light absorbing agent in the solvent, the same materials as the examples of the materials for previously melting and mixing the light absorbing agent to dissolve or disperse may be mentioned.

Further, the light absorber used in the optical recording material of the present invention may be used by being co-dispersed (simultaneous mixing dispersion) with any one of a dye precursor, a developer and a sensitizer. . In addition, a dye precursor and a sensitizer or a combination of a color developer and a sensitizer and a light absorber may be codispersed (simultaneous mixing and dispersion).

The light absorbing agent used in the optical recording material of the present invention or the light absorbing agent which has been subjected to any treatment such as heat melting with the above-mentioned materials, solvent mixing, co-dispersion (simultaneous mixing dispersion), etc. It may be used as a constituent material in the light-absorbing heat-sensitive recording layer by being mixed with the heat-sensitive recording material comprising the developer or dye precursor of the invention. Further, the light absorbing agent may be used as a constituent material in the light absorbing layer above or below the heat-sensitive recording layer comprising the developer or dye precursor of the present invention. Further, it may be used as a constituent material in both the light absorbing layers above and below the heat-sensitive recording layer. In addition, the light absorbing agent may be internally added or impregnated into a support to be used as a constituent material of the light absorbing support. The heat-sensitive recording layer or the light-absorbing heat-sensitive recording layer may be formed on this light-absorbing support. The heat-sensitive recording layer on the light-absorbing support or the light-absorbing heat-sensitive recording layer may have a multilayer structure.

The amounts of the color developer and the dye precursor used in the optical recording material of the present invention and the types and amounts of other various components are determined according to the required performance and recording suitability, and are not particularly limited. Usually, 1 to 8 parts of an organic developer and 1 to 20 parts of a filler are used with respect to 1 part of a dye precursor, and 10 to 25% of a total solid content of a binder is suitable. The addition amount of the light absorber is determined according to its light absorption performance and the like.

Further, in the optical recording material of the present invention, like the heat-sensitive recording material of the present invention, an overcoat layer of a polymer substance or the like may be provided on the recording layer of the optical recording material for the purpose of enhancing storage stability and sensitivity. An undercoat layer containing an organic filler or an inorganic filler may be provided between the recording layer and the support. You may add the said light absorber to these overcoat layers and undercoat layers.

The above-mentioned light absorber is atomized by a crusher such as a ball mill, an attritor, or a sand grinder or an appropriate emulsifying device to a particle size of several microns or less, and various binders and various additives are added depending on the purpose. To make the coating liquid.

As a light source for performing optical recording on the optical recording material of the present invention, various lasers such as a semiconductor laser and a semiconductor-excited YAG laser, a xenon flash lamp, a halogen lamp and the like can be used. it can. Further, the light emitted from these light sources may be converged by a light converging means such as a lens, and optical recording may be performed on the optical recording material of the present invention. Furthermore, using a mirror etc.,
Optical scanning recording may be performed.

Since the heat-sensitive recording material and the optical recording material of the present invention are excellent in heat resistance and have extremely high heat stability of the background color, it is possible to provide a strong protective film by thermal lamination of a plastic film. Therefore, before or after recording with heat or light, it is possible to easily prepare a card protected by a plastic film and excellent in heat resistance and various stability by a film for thermal lamination and a commercially available laminator. it can. In particular, in the case of the optical recording material of the present invention, additional recording by light can be performed on the laminated plastic film. Examples of the plastic film for heat lamination include low density polyethylene, ethylene / vinyl acetate copolymer (EVA), ethylene / ethyl acrylate copolymer (EEA), ethylene /
A thermoplastic resin such as methyl methacrylate copolymer (EMAA) and ethylene / methacrylic acid copolymer (EMAA) can be used.

In addition, an extrusion coating treatment can be performed on the heat-sensitive recording material and the optical recording material of the present invention by using an extrusion coating resin such as low density polyethylene which can be extruded at a relatively low temperature.

The thermal recording material and the optical recording material of the present invention are
Since it has excellent heat resistance, it does not develop a background color even when it comes into contact with the toner heat fixing portion of the electrophotographic copying machine. Therefore, it can also be used as paper for an electrophotographic copying machine. Thermal recording or optical recording is also possible before or after toner recording by an electrophotographic copying machine.

[0073]

The reason why the aminobenzenesulfonamide derivative represented by the general formula (1) of the present invention functions as a developer for a dye precursor used in a heat-sensitive recording material or an optical recording material, the dye precursor and the The reason why the heat-sensitive recording material composed of the developer of the invention exhibits extremely high heat resistance, similarly, the optical recording material composed of the dye precursor, the developer of the invention, and the light absorber is extremely high. The reason why it exhibits high heat resistance has not been clarified yet, but it can be considered as follows.

In the aminobenzenesulfonamide derivative of the present invention, a structural change (keto
Enol tautomerism) can occur. It is considered that these compounds need to have an enol type structure in order to function as a color developer, and high temperature is necessary in order to cause tautomerism from a keto type to an enol type.

[0075]

[Chemical 9]

In the case of the above-mentioned thermal recording, the temperature of the thermal head instantaneously rises to a high temperature of 200 to 300 ° C. or more, and therefore, it is represented by the above-mentioned general formula (1) contained in the recording layer of the thermal recording material which is in contact with the thermal head. The compound capable of undergoing tautomerism becomes an enol type, and a color developing function is exhibited. It is considered that this causes the lactone ring of the dye precursor to be cleaved to develop a color. Furthermore one aromatic ring aminosulfonyl group of diphenyl urea skeleton (-SO ₂ NH ₂₎ is provided with promotion of the color developing function, believed to contribute to stabilization of the enol-type structure, and dark recording image density for the It is estimated that the thermal stability of the image and the background color can be obtained.

On the other hand, in the case of the optical recording, since the light absorbing agent exists in the optical recording layer, the light emitted from the recording light source is efficiently absorbed by the light absorbing agent and converted into heat.
At this time, since the temperature momentarily rises to 200 to 300 ° C. or higher, the compound of the general formula (1) contained in the recording layer undergoes tautomerism, becomes an enol type, and develops a color as in thermal recording. Function is developed. It is considered that this causes the lactone ring of the dye precursor to be cleaved to develop a color.

Further, the compound of the general formula (1) does not exhibit the color developing agent function up to a temperature at which the structure changes to an enol type structure and does not react with the dye precursor, so that the background color is developed. There is no such thing. This seems to be the reason for the high heat resistance. The temperature at which the compound of the general formula (1) is enolized is considered to be higher than the temperature required for thermal lamination, and therefore the background color does not develop even in a high temperature thermal environment such as thermal lamination treatment.

Further, in the case of the optical recording body having the above-mentioned structure which has been heat-laminated, the light emitted from the recording light source is
Since it passes through the plastic film existing on the optical recording layer, reaches the light absorber in the optical recording layer and is converted into heat, additional recording can be performed even after lamination.

[0080]

【Example】

<Production of Compound of General Formula (1); Synthesis Examples 1 to 8> Compounds (2), (A-1), (A-2), (A-12) and (A
-13), (A-14), (A-15), (A-1)
7) and (A-34) were synthesized as follows.
For the thermal analysis, SSC5200 type TG / DTA (Seiko Instruments Inc.) was used.

[Synthesis Example 1] <Compound (2); 4- (N-
Synthesis of Phenylcarbamoyl) aminobenzenesulfonamide> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, and 29.1 g (244.3 mM) of phenyl isocyanate was added with stirring.
After white precipitation, add 300 ml of acetonitrile,
Refluxed for 2 hours. The reaction mixture was filtered to obtain 30.6 g of white product (yield 90.4%). NMR
The results of the measurement (in DMSO-d6) are as follows.
7.00 ppm (t, 1H), 7.21 ppm (s, 2
H), 7.30 ppm (t, 2H), 7.46 ppm
(D, 2H), 7.61 ppm (d, 2H), 7.73
ppm (d, 2H) 8.79 ppm (s, 1H), 9.
05 ppm (s, 1H) In IR measurement (KBr tablet method), the following characteristic absorption was confirmed. 3460cm ^-1 (derived from primary amines) 1690 cm (from carbonyl) ^-1 1340cm ^-1, 1150cm ^-1 (derived from the sulfonyl group) decomposition temperature of the material obtained from the thermal analysis is 236.4 ° C. And the molecular weight determined by mass spectrometry (ionization method) was 291. From the above, the obtained compound was identified as the target product.

[Synthesis Example 2] <Compound (A-1); 4-
Synthesis of (Np-tolylcarbamoyl) aminobenzenesulfonamide> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, and 18.6 g (139.4 mM) of p-tolyl isocyanate was added with stirring. Refluxed for 2 hours. The reaction mixture was filtered to obtain 23.5 g of white product (yield 66.3%). The results of NMR measurement (in DMSO-d6) are as follows. 2.
25ppm (s, 3H), 7.10ppm (d, 2
H), 7.20 ppm (s, 2H), 7.35 ppm
(D, 2H), 7.60 ppm (d, 2H), 7.72
ppm (d, 2H), 8.67 ppm (s, 1H),
The decomposition temperature of this substance determined by 9.01 ppm (s, 1H) thermal analysis was 249.4 ° C., and the molecular weight determined by mass spectrometry (ionization method) was 305. From the above, it was identified that the obtained compound was the target product.

[Synthesis Example 3] <Compound (A-2); 4-
Synthesis of (Nm-tolylcarbamoyl) aminobenzenesulfonamide> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, and 18.6 g (139.4 mM) of m-tolyl isocyanate was added with stirring. Refluxed for 2 hours. The reaction mixture was filtered to obtain 26.5 g of white product (yield 74.7%). The results of NMR measurement (in DMSO-d6) are as follows. 2.
29 ppm (s, 3H), 6.82 ppm (d, 1
H), 7.16 ppm (d, 1H), 7.21 ppm
(S, 2H), 7.24 ppm (d, 1H), 7.31
ppm (s, 1H), 7.61 ppm (d, 2H),
7.73 ppm (d, 2H), 8.71 ppm (s, 1
H), 9.03 ppm (s, 1H) The decomposition temperature of this substance determined by thermal analysis is 244.3 ° C, and the molecular weight determined by mass spectrometry (ionization method) is 3
It was 05. From the above, it was identified that the obtained compound was the target product.

[Synthesis Example 4] <Compound (A-12); 4-
(Synthesis of (N- (p-chlorophenyl) carbamoyl) aminobenzenesulfonamide)> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, and 21.4 g (139.4 mM) of p-chlorophenyl isocyanate was added with stirring. And refluxed for 2 hours. The reaction mixture was filtered,
32.0 g (yield 84.6%) of a white product was obtained. NM
The results of R measurement (in DMSO-d6) are as follows. 7.21 ppm (s, 2H), 7.34 ppm
(D, 2H), 7.50 ppm (d, 2H), 7.61
ppm (d, 2H), 7.74 ppm (d, 2H),
8.94 ppm (s, 1H), 9.10 ppm (s ,,
1H) The decomposition temperature of this substance determined by thermal analysis was 256.2 ° C., and the molecular weight determined by mass spectrometry 4 (ionization method) was 325. From the above, the obtained compound was identified as the target product.

[Synthesis Example 5] <Compound (A-13); 4-
(Synthesis of (N- (m-chlorophenyl) carbamoyl) aminobenzenesulfonamide)> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, and 21.4 g (13) of isocyanic acid m-chlorophenyl ester was stirred.
9.4 mM) was added and the mixture was refluxed for 2 hours. The reaction mixture was filtered and 31.8 g of white product (yield 84.0%)
Got The results of NMR measurement (in DMSO-d6) are as follows. 7.05 ppm (dt, 1H), 7.2
2ppm (s, 2H), 7.30ppm (s, 1H),
7.34 ppm (d, 1H), 7.61 ppm (d, 2)
H), 7.72 ppm (s, 1H), 7.74 ppm
(D, 2H), 9.00 ppm (s, 1H), 9.14
The decomposition temperature of this substance determined by ppm (s, 1H) thermal analysis was 238.3 ° C., and the molecular weight determined by mass spectrometry (ionization method) was 325. From the above, it was identified that the obtained compound was the target product.

[Synthesis Example 6] <Compound (A-14); 4-
(Synthesis of (N- (o-chlorophenyl) carbamoyl) aminobenzenesulfonamide)> 20 g (116.1 mM) of sulfanilamide was placed in an eggplant-shaped flask and dissolved in 200 ml of acetonitrile. While stirring this solution with a magnetic stirrer, 21.4 g (139.4 mM) of isocyanic acid orthochlorophenyl ester was added, and the mixture was refluxed for 2 hours. The reaction mixture is filtered and the white product 25.
3 g (yield 66.9%) was obtained. NMR measurement (DMSO
The result of (in d6) is as follows. 7.06ppm
(Td, 1H), 7.23 ppm (s, 2H), 7.3
2ppm (td, 1H), 7.48ppm (dd, 1
H), 7.63 ppm (d, 2H), 7.76 ppm
(D, 2H), 8.15 ppm (dd, 1H), 8.4
2ppm (s, 1H), 9.77ppm (s, 1H) The decomposition temperature of this substance determined by thermal analysis was 235.9 ° C, and the molecular weight determined by mass spectrometry (ionization method) was 325. From the above, it was identified that the obtained compound was the target product.

[Synthesis Example 7] <Compound (A-15); 4-
(Synthesis of (N- (3,4-dichlorophenyl) carbamoyl) aminobenzenesulfonamide)> 20 g (116.1 mM) of sulfanilamide was placed in a round bottom flask and dissolved in 200 ml of acetonitrile. While stirring this solution with a magnetic stirrer, 2,4-dichlorophenyl isocyanate was added to 26.2.
g (139.4 mM) was added, and the mixture was refluxed for 2 hours. The reaction mixture was filtered and 38.7 g of white product (yield 9
2.5%) was obtained. The results of NMR measurement (in DMSO-d6) are as follows. 7.22 ppm (s, 2
H), 7.35 ppm (dd, 1H), 7.54 ppm
(D, 1H), 7.61 ppm (d, 2H), 7.74
ppm (d, 2H), 7.89 ppm (d, 1H),
9.11 ppm (s, 1H), 9.20 ppm (s, 1
H) The decomposition temperature of this substance determined by thermal analysis was 258.0 ° C., and the molecular weight determined by mass spectrometry (ionization method) was 359. From the above, it was identified that the obtained compound was the target product.

[Synthesis Example 8] <Compound (A-17); 4-
(Synthesis of (N- (2,5-dichlorophenyl) carbamoyl) aminobenzenesulfonamide)> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, and 26.2 g of 2,5-dichlorophenyl ester of isocyanic acid was stirred.
(139.4 mM) was added. After the white precipitate was deposited, 50 ml of acetonitrile was added, and the mixture was refluxed for 2 hours. The reaction mixture was filtered to yield 37.2 g of white product (yield 89.0).
%) Was obtained. The results of NMR measurement (in DMSO-d6) are as follows. 7.13 ppm (dd, 1H),
7.24 ppm (s, 2H), 7.52 ppm (d, 1
H), 7.63 ppm (d, 2H), 7.77 ppm
(D, 2H), 8.31 ppm (d, 1H), 8.56
ppm (s, 1H), 9.87 ppm (s, 1H) The decomposition temperature of this substance determined by thermal analysis was 264.0 ° C., and the molecular weight determined by mass spectrometry (ionization method) was 359. From the above, it was identified that the obtained compound was the target product.

[Synthesis Example 9] <Compound (A-34); 4-
Synthesis of (N- (p-methoxyphenyl) carbamoyl) aminobenzenesulfonamide> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, and 20.8 g (139. 4m
M) was added. White precipitate after precipitation, acetonitrile 200
Additional ml was added and the mixture was refluxed for 2 hours. The reaction mixture was filtered to obtain 20.3 g of white product (yield 54.4%).
The results of NMR measurement (in DMSO-d6) are as follows. 3.72 ppm (s, 3H), 6.88 ppm
(D, 2H), 7.19 ppm (s, 2H), 7.37
ppm (d, 2H), 7.59 ppm (d, 2H),
7.72 ppm (d, 2H), 8.59 ppm (s, 1
H), 8.98 ppm (s, 1H) The decomposition temperature of this substance determined by thermal analysis was 232.0 ° C., and the molecular weight determined by mass spectrometry (ionization method) was 321. From the above, it was identified that the obtained compound was the target product.

<Production of Thermosensitive Recording Medium; Examples 1 to 31 and Comparative Examples 1 to 13> The thermal recording medium of the present invention will be described below with reference to Examples. In the description, parts and% represent parts by weight and% by weight, respectively.

Examples 1 to 16 (see Table 1) In Examples 1 to 16, compounds (2), (A-1) to (A-3) were used as color developers in the thermosensitive recording materials of the present invention. , (A-1
2) to (A-15), (A-17), (A-19),
(A-24), (A-32), (A-34), (A-3
5), and (A-38), 3-diethylamino-6-methyl-7-anilinofluorane (OD
It is an example using B). The developer dispersion (A liquid) and the dye precursor dispersion (B liquid) having the following formulations were separately wet-milled with a sand grinder until the average particle diameter became 1 micron. Liquid A (developer dispersion liquid) Developer 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts Water 11.2 parts Liquid B (dye precursor dispersion liquid) 3-diethylamino-6-methyl-7-ani Rinofluoran (ODB) 2.0 parts 10% aqueous polyvinyl alcohol solution 4.6 parts water 2.6 parts Next, the dispersion liquids were mixed at the following ratios to prepare coating liquids. Liquid A (developer dispersion liquid) 36.0 parts Liquid B (dye precursor dispersion liquid) 9.2 parts Kaolin clay (50% dispersion liquid) 12.0 parts Each of the above coating liquids is 50 g / m ² of base paper. After applying to one side of
After drying, the sheet was treated with a super calendar so that the smoothness was 500 to 600 seconds, and the coating amount was 6.0.
A thermosensitive recording material having a g / m ² was obtained.

[Examples 17 to 31] (See Table 2) Examples 17 to 31 are compound (2) [Examples 17 to 21], compound (A-13) [Examples 22 to 21] as a developer.
26] or the compound (A-15) [Examples 27 to 3]
1] is an example in which the following dye precursor other than ODB is used as the dye precursor. (Dye precursor) ODB-2; 3-dibutylamino-6-
Methyl-7-anilinofluorane PSD-150; 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane Green40; 3-diethylamino-7- (o-chloroanilino) fluorane CVL 3,3-bis (p-dimethylaminophenyl)
-6-Dimethylaminophthalide I-Red; 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide Dye precursor dispersion liquids other than ODB (C liquid) are separately sand grinders. Was wet-milled until the average particle size became 1 micron. Liquid C (dye precursor dispersion liquid other than ODB) Dye precursor 2.0 parts 10% aqueous polyvinyl alcohol solution 4.6 parts water 2.6 parts The dispersion liquids were mixed at the following ratios to prepare a coating liquid. . Liquid A (developer dispersion liquid) 36.0 parts Liquid C (dye precursor dispersion liquid other than ODB) 9.2 parts Kaolin clay (50% dispersion liquid) 12.0 parts Each of the above coating liquids is 50 g / m ² After applying to one side of the base paper,
After drying, the sheet was treated with a super calendar so that the smoothness was 500 to 600 seconds, and the coating amount was 6.0.
A thermosensitive recording material having a g / m ² was obtained.

[Comparative Examples 1 to 13] (See Table 3) In Comparative Examples 1 to 13, the following known color developing agents and the various dye precursors shown in Examples 1 to 31 were used as the color developing agents. Here is an example. Thermal recording media for comparative examples were prepared in the same manner as in Examples 1-31. (Public Developer) BPA: Bisphenol A BPS: Bisphenol SPOB: p-Hydroxybenzoic Acid Benzyl Ester D-8: 4-Hydroxy-4′-isopropoxydiphenylsulfone Known Developer Dispersion Liquid (D Liquid) Were separately wet-milled with a sand grinder until the average particle diameter became 1 micron. Liquid D (known developer dispersion) The known developer 6.0 parts 10% polyvinyl alcohol aqueous solution 18.8 parts water 11.2 parts Next, the dispersions were mixed at the following ratio to form a coating liquid. . Liquid D (known developer dispersion) 36.0 parts Liquid A, or liquid C (dye precursor dispersion) 9.2 parts Kaolin clay (50% dispersion) 12.0 parts 50 g of each of the above coating liquids / M ² After applying to one side of the base paper,
After drying, the sheet was treated with a super calendar so that the smoothness was 500 to 600 seconds, and the coating amount was 6.0.
A thermosensitive recording material having a g / m ² was obtained.

<Evaluation of Thermal Recording Material; Examples 1 to 31 and Comparative Examples 1 to 13> [Thermal Recording Performance Test (Dynamic Color Density)] A printer of personal word processor Rupo-90FII (manufactured by Toshiba Corporation) was used. However, the applied energy is the maximum, and
Further, heat-sensitive recording was performed on the heat-sensitive recording bodies of Comparative Examples 1 to 13 (all the heat-sensitive recordings shown below are under the same conditions). The recording density of the recording portion was measured with a Macbeth densitometer (RD-914, using an amber filter, all the same conditions below). Sufficient recording densities were obtained by the above-mentioned printers for the thermal recording materials of Examples 1 to 31 in which the compound of the present invention was used as the color developer. In the examples using the dye precursors other than the black color development, the recording density measurement filter is amber, and thus shows a low value.

[Ground color thermal stability test] Using a gear type aging tester (Toyo Seiki Seisakusho Co., Ltd.), a test temperature of 10
A heat resistance test was performed at 0 ° C., 120 ° C., 140 ° C., and 160 ° C. for 30 minutes each, and the heat resistance test was performed on each of Examples 1-31 and Comparative Example 1
.About.13 thermal recording materials. After the heat resistance test, the background color density was measured with a Macbeth densitometer. In this case, the smaller the value of the Macbeth density, the less the background color is developed, and the higher the thermal stability of the background color is. The thermosensitive recording materials of Examples 1 to 31 using the compound of the present invention as a color developer have a background color density of 140 ° C. for 30 minutes, which does not exceed 0.2.
All of the thermal papers using the phenol-based developer of Comparative Examples 1 to 13 already exceeded 0.2 at 100 ° C. for 30 minutes.
The thermal recording materials of Examples 1 to 31 have a high contrast between the recorded image and the ground color even after 30 minutes at 160 ° C. and exhibit extremely high heat stability.

[0096]

[Table 1]

[Table 2]

[Table 3]

<Thermal Lamination and Toner Recording Tests; Examples 32 to 61, Comparative Examples 14 to 21> Next, thermal lamination and toner recording by an electrophotographic copying machine were performed on the thermal recording material of the present invention.

[Thermal Laminating Test] (See Table 4) A simple laminating device (MS Pouch H-140, Meiko Shokai) and a laminating film (MS Pouch Film MP10-6095) were used. Examples 1, 2, 6 to 12, 14, 1 which have already been subjected to thermal recording under the conditions described above.
7, 20, 24, 26, 28, 30, and Comparative Example 1,
The thermal recording media of Nos. 5, 10, and 12 were sandwiched between the laminate films, and laminated thermal recording media having a thermal recording section were prepared at a feed rate of 20 mm / sec (Examples 32 to 45, Comparative Examples 14 to 14). 17). After the thermal laminating process, through the laminated film of the laminated thermosensitive recording material, the color-developed portion and the ground-colored portion due to the thermosensitive recording,
Measured with a Macbeth densitometer (high value because measured over film). Regarding the background color, the smaller the Macbeth density value, the more stable the background color. The contrast between the color-developed portion and the background color of the laminated thermosensitive recording material by thermosensitive recording was evaluated as follows. ◯: No background color developed, almost no (heat lamination possible) △: Ground color developed ×: Ground color markedly developed Laminated thermal recording medium with contrast evaluation of Δ to × Was difficult to read, and thermal lamination was practically impossible (Comparative Examples 14 to 17). On the other hand, in Examples 32 to 45, the contrast evaluation is good (◯).
And thermal lamination was possible. No discoloration of the recorded image area due to heat was observed.

[0099]

[Table 4]

[Toner recording test by electrophotographic copying machine] (see Table 5) Examples 1, 2, 6 to 12, 14, 17, 20, 24, 2
Toner recording was performed using the thermal recording materials of Nos. 6, 28, 30 and Comparative Examples 1, 5, 10, 12 as paper for an electrophotographic copying machine (Vivace 400 Fuji Xerox Co., Ltd.). The potential of the paper as an electronic copying machine paper was evaluated based on the degree of background color development. The heat-sensitive recording material of the present invention could be used as electrophotographic copying machine paper without background color development (Examples 46 to 61).

[0101]

[Table 5]

<Manufacture of Optical Recording Material; Examples 62 to 83, Comparative Examples 22 to 27> The optical recording material of the present invention will be described below with reference to Examples. In the description, parts and% represent parts by weight and% by weight, respectively.

Examples 62 to 67 (see Table 6) Examples 62 to 67 are compounds (2), (A-1) and (A-13) as color developers in the optical recording material of the present invention. ,
(A-15), (A-17), and (A-34), bis (1-methyl-3,4-dithiophenolate) nickel tetra-n-butylammonium as a light absorber and heat of the sensitizer This is an example using 3-diethylamino-6-methyl-7-anilinofluorane (ODB) as a melt (light absorber 1) and a dye precursor. The developer dispersion liquid (A liquid) and the dye precursor dispersion liquid (B) used in Examples 1 to 31.
Liquid) and a light absorber 1 dispersion liquid (E liquid) having the following composition were separately wet-milled with a sand grinder until the average particle diameter became 1 micron. Liquid E (light absorber dispersion liquid) To 94 parts of 4-biphenyl-p-tolyl ether, 6 parts of bis (1-methyl-3,4-dithiophenolate) nickel tetra-n-butylammonium was added, and 100-
The mixture was heated to 150 ° C., melt-mixed, and then pulverized to obtain the light absorber 1. Light absorber 1 4.0 parts 10% polyvinyl alcohol aqueous solution 10.0 parts water 6.0 parts Next, the dispersion liquids were mixed at the following ratios to prepare coating liquids. Liquid A (developer dispersion liquid) 36.0 parts Liquid E (light absorber 1 dispersion liquid) 20.0 parts Liquid B (dye precursor dispersion liquid) 9.2 parts Kaolin clay (50% dispersion liquid) 12. 0 part After applying each of the above coating solutions to one side of a base paper of 50 g / m ² ,
After drying, an optical recording material having a coating amount of 6.0 g / m ² was obtained.

[Examples 68 to 73] (see Table 6) Examples 68 to 73 are compounds (2), (A-1) and (A-13) as color developers in the optical recording material of the present invention. ,
(A-15), (A-17), and (A-34), NK-2612 as a light absorber (light absorber 2; manufactured by Japan Photosensitive Dye Research Institute Co., Ltd.), and 3-diethylamino as a dye precursor. This is an example using -6-methyl-7-anilinofluorane (ODB). The developer dispersion liquid (A liquid) and the dye precursor dispersion liquid (B liquid) used in Examples 1 to 31 were separately wet-milled with a sand grinder until the average particle diameter became 1 micron. Further, a light absorbing agent 2 aqueous solution (F liquid) having the following composition was prepared. Liquid F (light absorber 2 aqueous solution) NK-2612 (light absorber 2) 0.04 parts Water 3.96 parts Next, the dispersion liquids were mixed in the following proportions to prepare coating liquids. Liquid A (developer dispersion liquid) 36.0 parts Liquid F (light absorber 2 aqueous solution) 4.0 parts Liquid B (dye precursor dispersion liquid) 9.2 parts Kaolin clay (50% dispersion liquid) 12.0 After applying each of the above coating solutions to one side of a base paper of 50 g / m ² ,
After drying, an optical recording material having a coating amount of 6.0 g / m ² was obtained.

[Examples 74 to 79] (See Table 6) Examples 74 to 79 are compounds (2), (A-1) and (A-13) as color developers in the optical recording material of the present invention. ,
(A-15), (A-17), and (A-34), bis (1-methyl-3,4-dithiophenolate) nickel tetra-n-butylammonium as a light absorber and heat of the sensitizer Melt (light absorber 1; see Examples 62-67),
3-dibutylamino-6-methyl-7 as a dye precursor
-This is an example in which a light-absorptive coloring layer using anilinofluorane (ODB-2) is provided on a light-absorptive underlayer consisting of a filler on a base paper and graphite (light absorber 3). The method for preparing the coating liquid for the light-absorbing underlayer will be described below. Liquid G (light absorber 3 [for under layer] dispersion) Artificial graphite (G-6S; Chuetsu Graphite Industry Co., Ltd.) 5.0 parts 10% aqueous polyvinyl alcohol solution 12.5 parts water 7.5 parts This light The absorbent dispersion (solution G) was wet-milled with a sand grinder until the average particle diameter became 1 micron. This G liquid was mixed at the following ratio to prepare a coating liquid. Liquid G (light absorber 3 [for under layer] dispersion) 20.0 parts Kaolin clay (50% dispersion) 200.0 parts 10% polyvinyl alcohol aqueous solution 40.0 parts The above coating liquid of 50 g / m ² After coating on one surface of the paper, it was dried to form a light-absorbing underlayer having a coating amount of 4.0 g / m ² , to obtain a light-absorbing undersheet. As the coating liquid for the light-absorbing color forming layer, a developer dispersion (Liquid A) and a light absorber 1 dispersion (E) were prepared in the same manner as in Examples 62 to 67, and Examples 17 to 17 were used. A dye precursor dispersion liquid (C liquid) was prepared in the same manner as in No. 31, and mixed at the following ratios to prepare a coating liquid. Liquid A (developer dispersion liquid) 36.0 parts Liquid E (light absorber dispersion liquid) 4.0 parts Liquid C (dye precursor dispersion liquid) 9.2 parts Kaolin clay (50% dispersion liquid) 12.0 Parts The above coating liquid was applied to the light absorbing underlayer forming surface side of the above light absorbing undersheet and then dried to obtain an optical recording material having a coating amount of 6.0 g / m ² .

[Examples 80 to 83] (See Table 7) In Examples 80 to 83, the compound (2) was used as the color developer and NK-2612 was used as the light absorber in the optical recording material of the present invention.
(Light absorber 2; manufactured by Japan Photosensitive Dye Research Institute Co., Ltd.), as a dye precursor, PSD-150 shown in Examples 17 to 31;
It is an example using Green40, CVL, and I-Red. A developer dispersion (solution A) and a light absorber 2 aqueous solution (solution F) were prepared in the same manner as in Examples 68 to 73, and
A dye precursor dispersion liquid (C liquid) was prepared in the same manner as in Examples 17 to 31, and mixed at the following ratios to prepare a coating liquid. Liquid A (developer dispersion liquid) 36.0 parts Liquid F (light absorber 2 aqueous solution) 4.0 parts Liquid C (dye precursor dispersion liquid) 9.2 parts Kaolin clay (50% dispersion liquid) 12.0 Parts After applying the above coating liquid on one side of a base paper of 50 g / m ² ,
After drying, an optical recording material having a coating amount of 6.0 g / m ² was obtained.

[Comparative Examples 22 to 27] (See Table 8) Comparative Examples 22 to 27 are known color developing agents.
13 as bisphenol A (BPA), NK-2612 as a light absorbing agent (light absorbing agent 2; manufactured by Japan Photosensitive Dye Research Institute Co., Ltd.), and O shown in Examples 1 to 16 as a dye precursor.
DB, ODB-2 and PSD-1 shown in Examples 17 to 31
It is a comparative example with respect to the optical recording material of the present invention using 50, Green40, CVL, and I-Red. Comparative Example 1
~ 13 to prepare a developer dispersion (BPA; D solution), and in the same manner as in Examples 68 to 73 to prepare a light absorber 2 aqueous solution (F solution), and further, Example 1 To 16 and Examples 17 to 31, various dye precursors were prepared and mixed at the following ratios to prepare coating solutions. Liquid D (developer dispersion liquid) 36.0 parts Liquid F (light absorber 2 aqueous solution) 4.0 parts Liquid B or liquid C (dye precursor dispersion liquid) 9.2 parts Kaolin clay (50% dispersion liquid) ) 12.0 parts After applying the above coating solution on one side of a base paper of 50 g / m ² ,
After drying, an optical recording material having a coating amount of 6.0 g / m ² was obtained.

<Evaluation of Optical Recording Materials; Examples 62 to 83, Comparative Examples 22 to 27> [Optical Recording Test 1] Examples 62 to 73, Examples 80 to 8
3 and Comparative Examples 22 to 27 are disclosed in JP-A-3-2
Using the laser plotter device described in Japanese Patent No. 39598,
Laser recording was performed by the following method. A semiconductor laser LT015MD (manufactured by Sharp Corporation) having an oscillation wavelength of 830 nm and an output of 30 mW is used as a light source for optical recording,
The condenser lens has a numerical aperture of 0.45 and a focal length of 4.5 mm.
Two AP4545 (made by Konica), which are aspherical plastic lenses of, are used. A laser recording head consisting of these semiconductor lasers and lenses, recording speed 50mm
By scanning at a recording line interval of 50 μm / sec, a solid color image of 1 cm square was obtained. This vertical and horizontal 1c
A solid color image of m-square was obtained using a Macbeth densitometer (RD-91
4, using an amber filter). This value is shown in "optical recording density" in Tables 6, 7, and 8.
Examples 62-73 using compounds of the invention as developers.
Alternatively, in the optical recording bodies of Examples 80 to 83, a sufficient recording density was obtained by the above laser recording.

[Optical Recording Test 2] Optical recording using strobe flash light was performed on the optical recording bodies of Examples 74 to 79 by the following method. As an optical recording method, a strobe flash auto 4330 for camera (manufactured by Sunpack)
The light emitting window was narrowed down to 5% and light irradiation was performed. The density of this color-developed image was measured with a Macbeth densitometer (RD-914, using an amber filter). This value is shown in Table 6
The results are shown in "Optical recording density" in Examples 74 to 79. The optical recording materials of Examples 74 to 79 using the compound of the present invention as a color developer were able to obtain a sufficient recording density by the strobe flash recording.

[Ground color thermal stability test (optical recording medium)] Similarly to the thermal stability test of the thermal recording medium, a gear type aging tester (Toyo Seiki Seisakusho Co., Ltd.) was used and the test temperature was 100%.
C., 120.degree. C., 140.degree. C., 160.degree.
It carried out to the optical recording body of 2-27. After the heat resistance test, the background color density was measured with a Macbeth densitometer. In this case, the smaller the value of the Macbeth density, the less the background color is developed, and the higher the thermal stability of the background color is. In the optical recording materials of Examples 62 to 82 in which the compound of the present invention was used as the color developer, the density of the background color after 30 minutes at 140 ° C. did not exceed 0.3.
The optical recording materials using the phenol-based color developers of Comparative Examples 22 to 27 all exceeded 0.6 at 100 ° C. for 30 minutes. The optical recording materials of Examples 62 to 82 have a high contrast between the recorded image and the background color even after 30 minutes at 160 ° C., and show extremely high heat resistance stability.

[0111]

[Table 6]

[Table 7]

[Table 8]

<Thermal Lamination, Optical Additional Recording and Toner Recording Test; Examples 84 to 122, Comparative Examples 22 to 33> Next, the optical recording material of the present invention was thermally laminated. Optical additional recording was attempted on this laminated optical recording material. In addition, toner recording was performed with an electrophotographic copying machine.

[Thermal Lamination Test (Table 9)] A simple laminating apparatus (MS Pouch H-140, Meiko Shokai),
And laminated film (MS pouch film MP10
-6095) was used. Examples 62, 64, 66, 68, 6 in which optical recording (see [optical recording test 1] or [optical recording test 2]) has already been performed under the conditions described above.
9, 71, 74, 77, 78, 80, 81, 82, 8
The optical recording bodies of No. 3 and Comparative Examples 22, 23, and 26 were sandwiched between the laminate films, and the feeding speed was 20 mm / sec.
Then, a laminated optical recording body having an optical recording portion was produced (Examples 84 to 96, Comparative Examples 28 to 26). After the thermal laminating process, the color-developed portion and the ground-colored portion by the optical recording were measured with a Macbeth densitometer through the laminated film of the laminated optical recording material. Regarding the background color, the smaller the Macbeth density value, the more stable the background color. The contrast between the color-developed portion and the background color by optical recording of the laminated optical recording material was evaluated as follows. ○: No ground color developed, almost no color (heat lamination possible) △: Ground color developed ×: Ground color markedly developed Laminated optical recording medium with contrast of Δ to × Was difficult to read, and thermal lamination was practically impossible (Comparative Examples 28 to 26). On the other hand, Example 8
Regarding 4 to 96, the contrast evaluation was good (∘), and heat lamination was possible. No fading of the optical recording image portion due to heat was observed.

[0114]

[Table 9]

[Optical additional recording test (Table 10)] Example 84
-96, the optical recording test 1 and the optical recording test 2 shown in the evaluation of the optical recording body with respect to the laminated optical recording body
Was carried out (Examples 97 to 109). The color-developed image obtained by this optical additional recording was recorded on a Macbeth densitometer (RD-914,
The concentration was measured by using an amber filter). This value is shown in "Optical recording density" in Table 10. Example 84-
All of the laminated optical recording materials shown in 96 are laser-recorded (optical recording test 1) through the laminated film.
Also, flash flash recording (optical recording test 2) was possible, and a sufficient recording density was obtained.

[0116]

[Table 10]

[Toner recording test by electrophotographic copying machine (Table 11)] Examples 62, 64, 66, 68, 69, 7
1, 74, 77, 78, 80, 81, 82, 83, and Comparative Examples 22, 23, and 26 are used as paper sheets for electrophotographic copying machines (Vivace 400 Fuji Xerox Co., Ltd.) for toner recording. went. The potential for electrophotographic copying machine paper was evaluated based on the degree of background color development. The optical recording material of the present invention could be used as paper for electrophotographic copying machines without causing background color development (Examples 110 to 12).
2).

[0118]

[Table 11]

[0119]

As described above, a heat-sensitive recording material or an optical recording material using the compound represented by the general formula (1) of the present invention as a developer has a temperature environment up to about 160 ° C. Although there is almost no ground color cast,
A thermal recording device such as a thermal head or an optical recording device using a laser or a strobe flash can obtain a practically sufficient image recording density. Therefore, the following points can be mentioned as effects of the present invention.

(1) It is possible to use a thermosensitive recording medium or an optical recording medium under severe temperature conditions (for example, 90 to 160 ° C.) that cannot be used until now. (2) Since a laminator can perform thermal lamination on a recorded thermal recording medium or optical recording medium, a thermal recording card or optical recording card can be easily manufactured. (3) Optical recording can be further performed on the laminated optical recording medium. (4) Since the background color is stable even after passing through a heat roll, a heat-sensitive recording material or an optical recording material can be used as the electrophotographic copying machine paper.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiaki Minami 1-30-6 Kamiochiai, Shinjuku-ku, Tokyo Inside Nippon Paper Industries Co., Ltd. Product Development Laboratory

Claims (10)

[Claims] 1. 4- (N-represented by the following general formula (1):
Phenylcarbamoyl) aminobenzenesulfonamide derivative. [Chemical 1] (In the formula, X represents a lower alkyl group having 1 to 6 carbon atoms or an electron-withdrawing group. M represents an integer of 0 to 3.) 2. 4- (N-) represented by the following structural formula (2):
Phenylcarbamoyl) aminobenzenesulfonamide. [Chemical 2] 3. A thermosensitive recording medium comprising a support and a recording layer containing, as main components, a colorless or light-colored dye precursor and a color developer which reacts with the dye precursor to develop a color. A heat-sensitive recording material, wherein the developer contains at least one compound represented by the general formula (1) according to claim 1. 4. A thermosensitive recording medium comprising a support and a recording layer containing, as main components, a colorless or light-colored dye precursor and a color developer which reacts with the dye precursor to develop a color. The heat-sensitive recording material according to claim 3, wherein the developer is a compound represented by the structural formula (2) according to claim 2. 5. A heat-sensitive recording material comprising the heat-sensitive recording material according to claim 3 or claim 4, after the heat-sensitive recording, the recording surface or the entire recording material is laminated with a plastic film. 6. An optical recording material, wherein the recording layer of the thermal recording material according to claim 3 or 4 contains a light absorbing agent that absorbs light and converts it into heat. 7. An optical recording body, wherein the recording surface of the optical recording body according to claim 6 or the entire recording body is laminated with a plastic film. 8. An optical recording material comprising the optical recording material according to claim 6 which is heat-sensitively recorded or optically recorded, and then the recording surface or the entire recording material is laminated with a plastic film. 9. An optical recording method, wherein the optical recording material according to claim 7 or 8 is additionally recorded by strobe flash light or laser light. 10. A sheet for an electrophotographic copying machine, which uses the heat-sensitive recording material according to claim 3 or 4, or the optical recording material according to claim 6.