JPH0859603A - New aminobenzenesulfonamide derivative and recording medium using the same - Google Patents

Abstract

PURPOSE: To obtain the subject new compound capable of giving heat-sensitive media or optical recording media having sufficient heat resistance to a certain extent so as to be subjected to hot laminating when using it as a developer. CONSTITUTION: This new aminobenzenesulfonamide derivative is expressed by formula I or II (X is a 1-6C alkyl or electron-attracting group; (m) is 0-3), e.g. 2-(N-phenylcarbamoyl) aminobenzenesulfonamide or 3-(N-phenylcarbamoyl) aminobenzenesulfonamide. The compound is obtained by reaction of 2- aminobenzenesulfonamide or 3-aminobenzenesulfonamide with phenyl isocyanate. In a heat-sensitive recording medium obtained by providing the surface of a substrate with a recording layer containing, as the main ingredients, a colorless or pale dye precursor and a developer capable of developing color by its reaction with the precursor, or in an optical recording medium having the recording layer containing a light absorber to absorb light to the recording layer to convert it into heat, at least one kind of the compound of formula I or II as a developer is incorporated in the recording layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel N-phenylcarbamoylaminobenzenesulfonamide derivative, and a heat-sensitive recording material or optical recording material which uses this compound as a developer and has excellent heat resistance.

[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 heat energy. 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. Has 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]

[Problems to be Solved by the Invention] 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) or (2).

[0015]

Embedded image (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) or (2) of the present invention can be produced by the reaction of 2-aminobenzenesulfonamide or 3-aminobenzenesulfonamide with phenyl isocyanate. it can. That is, the reaction is 2-aminobenzenesulfonamide,
Alternatively, 1-2.5 mol of phenyl isocyanate is added to 1 mol of 3-aminobenzenesulfonamide. 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, Diethyl ether, ethers such as tetrahydrofuran, acetonitrile, nitrites such as propionitrile, esters such as ethyl acetate, acetone, ketones such as methyl ethyl ketone, dimethylformamide, aprotic donor polar solvents such as dimethyl sulfoxide, methanol, Examples thereof include alcohols such as ethanol, or a mixed solvent thereof. The reaction temperature is 0 to 150 ° C, preferably 2
It is in the range of 0 to 100 ° C.

Specific examples of the compound represented by the general formula (1) or (2) of the present invention include, but are not limited to, the followings.

[0018]

[Chemical 3]

[Chemical 4]

The aminobenzenesulfonamide derivative represented by the above general formula (1) or (2) is a novel compound, and can be used as a developer, a physiologically active substance, a drug, etc. for thermosensitive recording paper. it can.

The aminobenzenesulfonamide derivative represented by the above general formula (1) or (2) of the present invention is obtained by reacting a colorless or pale dye precursor with a dye precursor on a support. In a thermosensitive recording medium provided with a recording layer containing a color developing agent as a main component, by using it as a color developing agent, the above-mentioned problems that have been problems of the conventional thermosensitive recording paper can be solved at once. It was done.

A compound in which X in the general formula (1) or (2) is a lower alkyl group having 1 to 6 carbon atoms or an electron-withdrawing group, and m is an integer of 0 to 3 is a color developer. Although the thermal recording material used as a recording medium can be recorded with a thermal head or the like, on the other hand, it is considered in the conventional thermal recording paper that the ground color is less developed even in a thermal environment of about 120 ° C to 140 ° C. It has characteristics that cannot be obtained.

2- (N) represented by the general formula (1) of the present invention.
-Phenylcarbamoyl) aminobenzenesulfonamide compound, or 3-in the general formula (2) of the present invention.
(N-phenylcarbamoyl) aminobenzenesulfonamide-based compound was added to 4- (N-phenylcarbamoyl)
When compared with the color developing agent characteristics of the aminobenzenesulfonamide compound, the above general formula (1) or (2) of the present invention is used.
The compound of 1 improves the recording characteristics at low energy,
On the other hand, the heat resistance is somewhat inferior. However, 120 ℃ -140 ℃
The heat resistance to some extent and the resistance to heat treatment for a short time such as thermal lamination are far superior to those of conventional phenol-based color developing agents.

The aminobenzenesulfonamide derivative of the present invention exhibits a color developing ability by undergoing tautomerism from the keto type structure represented by the general formula (1) or (2) to an enol type structure. it is conceivable that. Therefore, when the stability of the recorded image against heat or oil is taken into consideration, in the general formula (1) or (2), X in the general formula (1) or (2) has 1 to 6 carbon atoms in order to stabilize the enol type structure exhibiting color developing ability. Although the lower alkyl group of 7 shows sufficient stability of recorded images, the electron withdrawing group is more preferable. As the electron-withdrawing group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, or a cyano group is preferable from the viewpoints of heat resistance, recording sensitivity and the like.

Further, in consideration of industrial productivity and practicality, it is represented by the above structural formula (A-10) 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)
Aminoanilinofluoran 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 more conventionally known color developing agents that cause the dye precursor to develop a color are used in the formula (1) of the present invention, within the range that does not impair the desired effects for the above problems. Alternatively, it can be used in combination with the compound represented by (2). 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 added in an appropriate amount and used in combination with the compound of the general formula (1) or (2) of the present invention.
Examples of such a color developer include, for example, JP-A-3-20768.
No. 8, bisphenol A described in JP-A-5-24366, 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
Examples include-(hydroxyphenyl) -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-Hydroxyphenylarylsulfone> 4-hydroxy-4′-isopropoxydiphenylsulfone 4-hydroxy-4′-propoxydiphenylsulfone 4-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-hydroxybenzoyloxy propyl benzoate 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 4-benzoyloxybenzoic acid α-naphthyl 4-hydroxybenzoyloxy β-naphthyl 4-hydroxybenzoyloxy sec-butyl 4-hydroxybenzoyloxybenzoate

<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 '
-Hydroxyphenylsulfone 2-hydroxy-5-t-octylphenyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3'-chloro-4'-hydroxyphenylsulfone 2-hydroxy-5-t -Butylphenyl-3'-methyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3'-isopropyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3 '-Chloro-4'-hydroxyphenylsulfone2-hydroxy-5-tert-butylphenyl-3'-methyl-4'-hydroxyphenylsulfone2-hydroxy-5-tert-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 thermal recording, the developer of the present invention, a conventionally known developer, a dye precursor, and a sensitizer for thermal 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 absorbent 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), is 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, 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 the storability and the sensitivity, like the thermal recording material of the present invention. 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, a sand grinder or an appropriate emulsifying device until the particle diameter becomes several microns or less, and various additives are added according to the binder and the purpose. To make the coating liquid.

As a light source for performing optical recording on the optical recording medium 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, either before or after recording with heat or light, with a plastic film for thermal lamination and a commercially available laminator,
A card protected by a plastic film and excellent in heat resistance and various types of stability can be easily manufactured. 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 base material for the plastic film for heat lamination include polyethylene terephthalate (PET) and polypropylene (PP), and examples of the heat sealant for the plastic film for heat lamination include low density polyethylene and ethylene / vinyl acetate copolymer. Thermoplastic resins such as polymer (EVA), ethylene / ethyl acrylate copolymer (EEA), ethylene / methyl methacrylate copolymer (EMAA), and ethylene / methacrylic acid copolymer (EMAA) can be used.

In addition, the thermosensitive recording material and the optical recording material of the present invention may be subjected to extrusion coating treatment by using an extrusion coating resin capable of extrusion treatment. Examples of the extrusion coating resin include various thermoplastic resins useful as the heat seal agent, polypropylene (P
P) and polyethylene terephthalate (PET).

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) or (2) of the present invention functions as a developer of a dye precursor used in a heat-sensitive recording material or an optical recording material, The reason why the heat-sensitive recording material composed of the dye precursor and the color developer of the present invention exhibits extremely high heat resistance, similarly, the light composed of the dye precursor, the color developer of the present invention, and the light absorber. The reason why the recording material exhibits extremely 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 a high temperature is necessary in order to cause tautomerism from a keto type to an enol type.

[0075]

[Chemical 5]

In the case of the above-mentioned thermal recording, the thermal head momentarily reaches a high temperature of 200 to 300 ° C. or more, so that the general formula (1) or () contained in the recording layer of the thermal recording medium which comes into contact with the thermal head is used. The compound that can be represented by 2) undergoes tautomerism to become an enol type and develops a color developing function. It is considered that this causes the lactone ring of the dye precursor to be cleaved to develop a color. Furthermore, an aminosulfonyl group (-SO ₂ N on one aromatic ring of the diphenylurea skeleton)
H ₂ ) is considered to contribute to the promotion of the color developing function and the stabilization of the enol type structure, and therefore it is presumed that a high recorded image density and 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 is instantaneously increased to 200 to 300 ° C. or higher, the compound of the general formula (1) or (2) contained in the recording layer undergoes tautomerism as in the heat-sensitive recording to give an enol type compound. And the color developing 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) or (2) does not exhibit the developer function and does not react with the dye precursor until the temperature at which the structure changes to an enol type structure. No color development occurs. This seems to be the reason for the high heat resistance. The temperature at which the compound of the general formula (1) or (2) is enolized is considered to be higher than the temperature required for thermal lamination, and therefore, even in a high temperature thermal environment such as thermal lamination treatment, the background color is not developed. It won't happen.

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) or (2); Synthesis Examples 1 and 2> Compounds (A-1) and (A-10) were synthesized as follows. Thermal analysis is SSC5200 type TG /
DTA (Seiko Instruments Inc.) was used.

[Synthesis Example 1] <Compound (A-1); 2-
Synthesis of (N-phenylcarbamoyl) aminobenzenesulfonamide> 2-aminobenzenesulfonamide 20 g (116.1)
(mM) was dissolved in 200 ml of acetonitrile, and 29.1 g (243.9 m) of phenyl isocyanate was added with stirring.
M) was added and refluxed for 2 hours. The reaction mixture was filtered to give 29.8 g of white product (yield 88.1%).
The results of NMR measurement (in DMSO-d6) are as follows. 6.98 ppm (t, 1H), 7.17 ppm (td,
1H), 7.29ppm (t, 2H), 7.51ppm
(D, 2H), 7.54 ppm (td, 1H) 7.63 ppm (s, 2H), 7.81 ppm (dd,
1H), 8.06ppm (d, 1H), 8.51ppm
(S, 1H), 9.71 ppm (s, 1H) The decomposition temperature determined by thermal analysis is 181.1 ° C,
The molecular weight determined by mass spectrometry was 291. From the above, the obtained compound was identified as the target product.

[Synthesis Example 2] <Compound (A-10); 3-
Synthesis of (N-phenylcarbamoyl) aminobenzenesulfonamide> 3-aminobenzenesulfonamide 20 g (116.1)
(mM) was dissolved in 200 ml of acetonitrile, and 29.1 g (243.9 m) of phenyl isocyanate was added with stirring.
M) was added and refluxed for 2 hours. The reaction mixture was filtered to obtain 25.8 g (yield 76.3%) of a white product.
The results of NMR measurement (in DMSO-d6) are as follows. 6.99ppm (t, 1H), 7.29ppm (t, 2
H), 7.35 ppm (s, 2H), 7.43 ppm
(T, 1H), 7.46 ppm (t, 1H) 7.49 ppm (t, 2H), 7.56 ppm (d, 1)
H), 8.07 ppm (s, 1H), 8.71 ppm
(S, 1H), 9.00 ppm (s, 1H) The decomposition temperature determined by thermal analysis is 208.4 ° C,
The molecular weight determined by mass spectrometry was 291. From the above, the obtained compound was identified as the target product.

<Production of Thermal Recording Material; Examples 1 to 18 and Comparative Examples 1 to 6> The thermal 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 1 to 10] In Examples 1 to 10, the thermosensitive recording material of the present invention was prepared by using the compound (A-1) as a color developer,
(A-2), (A-4), (A-7), (A-8),
(A-10) or (A-12) to (A-15) is an example using 3-diethylamino-6-methyl-7-anilinofluorane (ODB) as a dye precursor. 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 [ODB] dispersion liquid) 9.2 parts Kaolin clay (50% dispersion liquid) 12.0 parts 50 g / m ^{2 of the} above coating liquids 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.

[Examples 11 to 14] Examples 11 to 14
Is an example in which the compound (A-10) is used as the developer and the dye precursors shown below other than ODB are used as the dye precursor. (Dye precursor) ODB-2; 3-dibutylamino-6-methyl-7-anilinofluorane Green40; 3-diethylamino-7- (o-chloroanilino) fluorane PSD-150; 3- (N-cyclohexyl-N) -Methylamino) -6-methyl-7-anilinofluorane CVL; 3,3-bis (p-dimethylaminophenyl)
Dye precursor dispersion liquids other than -6-dimethylaminophthalide ODB (C liquid) were separately wet-milled with a sand grinder 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 (A-10 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 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.

[Example 15] Example 15 is an example in which the compound (A-10) was used as the color developer and ODB and PSD-150 were used as the dye precursor. Examples 1-10
The developer dispersion liquid (A liquid) and the ODB dispersion liquid (B liquid) were treated in the same manner as in, and P was treated in the same manner as in Examples 11 to 14.
The SD-150 dispersion liquid (C liquid) was processed. 3. Liquid A (developing agent [A-1] dispersion liquid) 36.0 parts Liquid B (dye precursor [ODB] dispersion liquid) 4.6 parts Liquid C (dye precursor [PSD-150] dispersion liquid) 4. 6 parts Kaolin clay (50% dispersion liquid) 12.0 parts After applying each of the above-mentioned coating liquids to one side of 50 g / m ² of 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.

Example 16 In Example 16, compound (A-10) was used as the color developer, and ODB- was used as the dye precursor.
2 and PSD-150. Example 1
In the same manner as in Example 10, the color developer dispersion (solution A) was used.
The ODB-2 dispersion liquid (C liquid) and the PSD-150 dispersion liquid (C liquid) were treated in the same manner as in 1 to 14. Liquid A (developer [A-1] dispersion liquid) 36.0 parts Liquid C (dye precursor [ODB-2] dispersion liquid) 4.6 parts Liquid C (dye precursor [PSD-150] dispersion liquid) 4.6 parts Kaolin clay (50% dispersion liquid) 12.0 parts After applying each of the above coating liquids to one side of a base paper of 50 g / m ² ,
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.

[Example 17] Example 17 is an example in which the compound (A-1) and the compound (A-10) were used as the color-developing agents and ODB was used as the dye precursor. Examples 1 to 1
In the same manner as in 0, the compound (A-1) and the compound (A-1
0) developer dispersion (liquid A) and ODB dispersion (B)
Liquor) was processed. Liquid A (developing agent [A-1] dispersion) 18.0 parts Liquid A (developing agent [A-10] dispersion) 18.0 parts Liquid B (dye precursor [ODB] dispersion) 9. 2 parts Kaolin clay (50% dispersion liquid) 12.0 parts After applying each of the above-mentioned coating liquids to one side of 50 g / m ² of 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.

Example 18 In Example 18, compound (A-10) and bisphenol A (hereinafter referred to as B) were used as color developers.
This is an example in which ODB is used as the dye precursor (developer mixture). In the same manner as in Examples 1-10,
Compound (A-10) developer dispersion (solution A), and OD
The dispersion B (solution B) was treated. Further, the known BPA dispersion liquid (D liquid), which is a known developer, was wet-milled with a sand grinder until the average particle diameter became 1 micron. Liquid D (known developer [BPA] dispersion liquid) Bisphenol A (BPA) 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts water 11.2 parts Next, the dispersion liquids are mixed in the following proportions to obtain a coating liquid. And Liquid A (developing agent [A-10] dispersion liquid) 30.0 parts D liquid (known developer [BPA] dispersion liquid) 6.0 parts Liquid B (dye precursor [ODB] dispersion liquid) 9. 2 parts Kaolin clay (50% dispersion liquid) 12.0 parts After applying each of the above-mentioned coating liquids to one side of 50 g / m ² of 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 6] Comparative Examples 1 to 6 are examples in which the following known color developing agents and the various dye precursors shown in Examples 1 to 14 are used as the color developing agents. (Publicly Known Developer) BPA: Bisphenol A D-8: 4-Hydroxy-4'-isopropoxydiphenylsulfone In the same manner as in Examples 1 to 14, a thermal recording material for Comparative Example was prepared. The BPA dispersion liquid (D liquid) was treated in the same manner as in Example 18, and further, the D-8 dispersion liquid (D ′ liquid).
Was wet-milled with a sand grinder until the average particle diameter became 1 micron. D'solution (known developer [D-8] dispersion) D-8 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts water 11.2 parts Next, the dispersion liquids are mixed and coated at the following ratios. It was a liquid. Liquid D or liquid D '(known developer dispersion liquid) 36.0 parts Liquid B or liquid C (dye precursor dispersion liquid) 9.2 parts Kaolin clay (50% dispersion liquid) 12.0 parts After applying each coating solution to one side of 50 g / m ² 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 Thermosensitive Recording Materials; Examples 1 to 18, Comparative Examples 1 to 6> With respect to the thermal recording materials of Examples 1 to 18 and Comparative Examples 1 to 6, thermal recording test and thermal stability of background color. Tests were carried out (Table 1 "Recording density and ground color heat stability of thermal recording bodies of Examples 1 to 18" and Table 2 "Recording density and ground color heat stability of thermal recording bodies of Comparative Examples 1 to 6". "reference).

[Thermal recording test (dynamic color density)] Personal word processor Rupo-90FII (manufactured by Toshiba Corp.)
The printer was used to perform thermal recording on the thermal recording bodies of Examples 1 to 18 and Comparative Examples 1 to 6 at the maximum applied energy (the thermal recordings shown below are all under the same conditions).
The recording density of the recording unit is Macbeth densitometer (RD-914,
The measurement was performed using an amber filter, and the same conditions below). Examples 1 to 18 using the compound of the present invention as a developer
In the thermosensitive recording medium of No. 3, a sufficient recording density was obtained by the printer. 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
Heat resistance tests at 0 ° C., 120 ° C., and 140 ° C. for 30 minutes each were performed on the thermal recording materials of Examples 1 to 18 and Comparative Examples 1 to 6. 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. Example 1 using the compound of the present invention as a developer
The heat-sensitive recording materials of Nos. 18 to 18 had a background color density of 0.4 after 30 minutes at 140 ° C. and a background color density of 0.2 after 120 ° C. for 30 minutes. All of the thermal papers using the phenol-based color developers of ~ 5 already exceed 0.5 at 100 ° C for 30 minutes. It can be said that the thermosensitive recording materials of Examples 1 to 18 have a high contrast between the recorded image and the ground color even after 30 minutes at 140 ° C. and exhibit extremely high heat stability.

[0094]

[Table 1]

[Table 2]

<Thermal Lamination and Toner Recording Tests; Examples 19 to 27 and Comparative Examples 7 to 9> Next, various thermal treatment tests were performed on the thermal recording material of the present invention by thermal lamination and toner recording by an electrophotographic copying machine. (Table 3, "Examples 1, 4, 6-8, 11, 16-18, Comparative Example 1,
Various heat treatment tests for thermal recording materials 2 and 4 ").

[Thermal Laminating Test] A simple laminating apparatus (MS Pouch H-140, Meiko Shokai Co., Ltd.) and a laminating film (MS Pouch Film MP10-609).
5) was used. The thermal recording materials of Examples 1, 4, 6 to 8, 11, 16 to 18 or Comparative Examples 1, 2, and 4 which have already been subjected to thermal recording under the conditions described above are sandwiched between the laminate films, and the feed rate is set. Laminated thermosensitive recording media having thermosensitive recording areas were produced at 20 mm / sec (Examples 19 to 27, Comparative Examples 7 to 9). 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 ground color developed, almost no (heat lamination possible) △ …… Ground color developed × …… Ground color markedly developed The laminated thermal recording medium with the contrast evaluation of × It was difficult to read, and thermal lamination was practically impossible (Comparative Examples 7 to 9). On the other hand, Examples 19 to 2
Regarding 7, the contrast evaluation is good (○),
Thermal lamination was possible.

[Toner Recording Test by Electrophotographic Copying Machine] The heat-sensitive recording bodies of Examples 1, 4, 6 to 8, 11, 16 to 18 or Comparative Examples 1, 2 and 4 were applied to an electrophotographic copying machine (Vivece 400 Fuji). Toner recording was performed as paper of Xerox Co., Ltd. The possibility of being used as an electronic copying machine paper was evaluated based on the degree of color development of the background color (the evaluation of the background color is the same as the "thermal lamination test"). The thermal recording material of the present invention (Examples 1, 4, 6 to 8, 11, 16 to 18) is
There was almost no background coloration, and it was possible to use as electrophotographic copying machine paper (Examples 19 to 27).

[0098]

[Table 3]

<Production of Optical Recording Material; Examples 28 to 32, Comparative Example 10> 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 28 to 32] Examples 28 to 32
Is a compound (A-1), (A-4), or (A-10) to (A-10) as a developer in the optical recording material of the present invention.
-12), or bis (1-methyl-3,4-dithiophenolate) nickel tetra-n- as a light absorber.
This is an example of using a hot melt of butylammonium and a sensitizer and 3-diethylamino-6-methyl-7-anilinofluorane (ODB) as a dye precursor. Examples 1 to 4
The developer dispersion liquid (A liquid), the dye precursor dispersion liquid (B liquid), and the light absorber dispersion liquid (E liquid) having the following composition were used.
Wet grinding was carried out separately with a sand grinder until the average particle size 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 a light absorber. Light absorber 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 dispersion liquid) 20.0 parts Liquid B (dye precursor [ODB] dispersion liquid) 9.2 parts Kaolin clay (50% dispersion liquid) 12.0 parts After applying each of the above-mentioned coating liquids 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.

[Comparative Example 10] Comparative Example 10 is a known developer, and is bisphenol A (BP) shown in Comparative Examples 1 to 3.
A), a hot melt of bis (1-methyl-3,4-dithiophenolate) nickeltetra-n-butylammonium as a light absorber and a sensitizer, and Example 1 as a dye precursor.
4 is a comparative example for the optical recording material of the present invention using ODB shown in FIG. In the same manner as in Example 18, the color developer dispersion (B
PA; D liquid), a light absorber dispersion liquid (E liquid) was prepared in the same manner as in Examples 28 to 32, and a dye precursor dispersion liquid was prepared in the same manner as in Examples 1 to 10. The coating liquid was prepared and mixed at the following ratios to obtain a coating liquid. Liquid D (developer [BPA] dispersion) 36.0 parts Liquid E (light absorber dispersion) 20.0 parts Liquid B (dye precursor [ODB] dispersion) 9.2 parts Kaolin clay (50%) Dispersion) 12.0 parts After applying the above-mentioned 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.

<Evaluation of Optical Recording Material; Examples 28 to 32, Comparative Example 10> Optical recording tests and thermal stability tests of ground color were conducted on the optical recording materials of Examples 28 to 32 and Comparative Example 10 ( See Table 4 "optical recording density and ground color thermal stability of optical recording bodies of Examples 28 to 32 and Comparative Example 10").

[Optical Recording Test 1] The optical recording materials of Examples 28 to 32 and Comparative Example 10 were prepared according to the method disclosed in JP-A-3-23959.
Laser recording was carried out by the following method using the laser plotter device described in Japanese Patent No. 8: As a light source for optical recording,
Semiconductor laser L with an oscillation wavelength of 830 nm and an output of 30 mW
T015MD (manufactured by Sharp Corporation) was used, and two AP4545 (manufactured by Konica), which are aspherical plastic lenses having a numerical aperture of 0.45 and a focal length of 4.5 mm, were used as a condenser lens. A laser recording head composed of these semiconductor lasers and lenses is used for recording speed 50 mm / se
By scanning at a recording line spacing of 50 microns, a solid color image of 1 cm square was obtained. The density of this solid color image of 1 cm square was measured with a Macbeth densitometer (RD-914, using an amber filter). This value is shown in "Optical recording density 1" in Table 4. Sufficient recording density was obtained by the laser recording of the optical recording materials of Examples 28 to 32 using the compound of the present invention as the color developer.

[Optical Recording Test 2] Optical recording using strobe flash light was performed on the optical recording bodies of Examples 28 to 32 or Comparative Example 10 by the following method. As an optical recording method, a stroboscopic flash auto 4330 for a camera is used.
The light emitting window (manufactured by Sunpack) was narrowed down to 5% and light irradiation was performed. This color-developed image was recorded on a Macbeth densitometer (RD-
914, using an amber filter). This value is shown in "Optical recording density 2" in Table 4. The optical recording bodies of Examples 28 to 32 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)] As with 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%.
A heat resistance test was carried out at 30 ° C., 120 ° C., and 140 ° C. for 30 minutes on each of the optical recording bodies of Examples 28 to 32 and Comparative Example 10. After the heat resistance test, the background color density was measured with a Macbeth densitometer. In this case, the smaller the value of Macbeth density, the less the development of the background color and the higher the thermal stability of the background color. Examples 28 to 3 using the compound of the present invention as a developer
The optical recording medium of No. 2 has a background color density of 140 ° C. after 30 minutes.
4, the density of the background color after 120 minutes at 120 ° C. does not exceed 0.25, while the optical recording material using the phenol-based developer of Comparative Example 10 has already reached 0 at 100 ° C. for 30 minutes. .4
Far beyond. The optical recording bodies of Examples 28 to 32 have a high contrast between the recorded image and the background color even after 30 minutes at 140 ° C., and exhibit extremely high heat stability.

[0106]

[Table 4]

<Thermal Lamination and Toner Recording Test; Examples 33 to 37 and Comparative Example 11> Next, various thermal treatment tests were performed on the optical recording material of the present invention as a thermal lamination test and a toner recording test by an electrophotographic copying machine. (See Table 5 “Examples 28 to 32, various heat treatment tests of optical recording materials of Comparative Example 10 (thermal lamination and toner thermal fixing treatment)”).

[Thermal Laminating Test] A simple laminating device (MS Pouch H-140, Meiko Shokai) and a laminating film (MS Pouch Film MP10-609).
5) was used. The optical recording medium of Examples 28 to 32 or Comparative Example 10 which has already been subjected to optical recording (see [Optical recording test 1] or [Optical recording test 2]) under the conditions described above is sandwiched between the laminate films. , Feed speed 20m
A laminated optical recording body having an optical recording portion was produced at m / sec (Examples 33 to 37, Comparative Example 11). After the thermal lamination treatment, 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 ground color,
The smaller the Macbeth density value is, the more stable the ground color is. 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 remarkably developed Laminated optical recording medium whose contrast evaluation was × Was difficult to read, and thermal lamination was practically impossible (Comparative Example 11). On the other hand, Examples 33 to
Regarding No. 37, the contrast evaluation was good (◯), and the heat lamination was possible.

[Toner recording test by electrophotographic copying machine] Toner recording is performed by using the optical recording material of Examples 28 to 32 or Comparative Example 10 as a sheet of an electrophotographic copying machine (Vivace 400 Fuji Xerox Co., Ltd.). It was The potential of the electrophotographic copying machine paper was evaluated based on the degree of color development of the background color (the evaluation of the background color is the same as the "thermal lamination test"). The optical recording material of the present invention could be used as a paper for an electrophotographic copying machine without developing a ground color (Examples 33 to 37).

[0110]

[Table 5]

<Optical additional recording test; Examples 38 to 42> [Optical additional recording test (see Table 5)] Evaluations of the optical recording materials for the laminated optical recording materials of Examples 33 to 37 are shown. "Optical recording test 1" and "optical recording test 2" were performed (Examples 38 to 42). The color-developed image obtained by this optical additional recording was subjected to density measurement by a Macbeth densitometer (RD-914, using an amber filter). This value
The results are shown in Table 6 under "Optical recording density of laminated optical recording materials of Examples 33 to 37". All of the laminated optical recording bodies shown in Examples 33 to 37 are capable of laser recording (optical recording test 1) and strobe flash recording (optical recording test 2) over the laminated film, and have sufficient recording density. Was obtained.

[0112]

[Table 6]

[0113]

As described above, the general formula (1),
Alternatively, the heat-sensitive recording material or the optical recording material of the present invention, which uses the compound represented by (2) as a developer, has a composition of 120 to 1
Up to a temperature environment of about 40 ° C, practically enough image recording density can be obtained with a thermal recording device such as a thermal head or an optical recording device using a laser or strobe flash, although there is almost no fog of the background color. be able to. Therefore, the following points can be mentioned as effects of the present invention.

(1) A thermosensitive recording medium or an optical recording medium can be used under severe temperature conditions (for example, 90 to 140 ° 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 (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09B 67/44 C 7267-2H B41M 5/26 Y (72) Inventor Toshiaki Minami Kamiochiai, Shinjuku-ku, Tokyo 1-30-6 Nippon Paper Industries Co., Ltd. Product Development Laboratory

Claims (8)

[Claims] 1. An N-phenylcarbamoylaminobenzenesulfonamide derivative represented by the following general formula (1) or (2): Embedded image (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. A heat-sensitive recording material comprising a support and a recording layer containing as a main component 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 N-phenylcarbamoylaminobenzenesulfonamide derivative represented by the general formula (1) or (2) according to claim 1. 3. A heat-sensitive recording material comprising the heat-sensitive recording material according to claim 2 which is heat-sensitively recorded, and then the recording surface or the entire recording material is laminated with a plastic film. 4. An optical recording material, wherein the recording layer of the heat-sensitive recording material according to claim 2 contains a light absorbing agent that absorbs light and converts it into heat. 5. An optical recording body, wherein the recording surface of the optical recording body according to claim 4 or the entire recording body is laminated with a plastic film. 6. An optical recording material comprising the optical recording material according to claim 4, wherein the recording surface or the entire recording material is laminated with a plastic film after thermal recording or optical recording. 7. An optical recording method for performing additional recording on the optical recording medium according to claim 5 or 6 by stroboscopic flash light or laser light. 8. The thermosensitive recording medium according to claim 2, or claim 4.
Sheet for electrophotographic copying machines using the optical recording material of.