JPH0853407A - New aminobenzenesulfonamide derivative and recording material using the same - Google Patents

Abstract

PURPOSE:To obtain a heat-sensitive recording material excellent in heat resistance or an optical recording material by using a partially new aminobenzenesulfonamide derivative as a developer. CONSTITUTION:This heat-sensitive recording material is provided with a recording layer consisting essentially of a colorless or a light-colored dye precursor and a developer, reactive with the precursor and developing a color on a support. Furthermore, this compound of formula I [X is O or S; R1 is a (substituted) aralkyl, naphthyl, a 1-6C alkyl, a 2-6C alkenyl or a 3-6C cycloalkyl] is used as the developer. A compound of formula II (R2 is R1) in the compound of formula I is new and can be utilized as a physiologically active substance, a medicine, a developer, etc., for heat-sensitive recording paper. After carrying out the heat sensitive recording on the heat-sensitive recording material, a plastic film is preferably laminated to the recording surface or the whole recording material. Otherwise, a light absorber may be added to the recording layer. The compound of formula I is obtained by reacting, e.g. sulfanilamide with isocyanic acid esters.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel aminobenzenesulfonamide derivative, and a heat-sensitive recording material or optical recording material using this compound as a color developer and having 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 them together to prepare a binder and a filler. The coating solution obtained by adding the agent, the sensitivity improver, the lubricant and the other auxiliary agent is applied to a support 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 thermosensitive recording media are recorders for measurement,
It has been applied to a wide range of fields such as computer terminal printers, facsimiles, automatic ticket vending machines, and bar code labels, but with the diversification and high performance of these recording devices, the required quality for thermal recording sheets has become more important. It is advanced. 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, and on the other hand, storage stability such as light resistance, heat resistance, water resistance, oil resistance and plasticizer resistance is required. Excellent thermal recording sheets are 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) approaches that of plain paper recording. Is required. In addition, since the heat-sensitive recording paper is used as a food label that is sterilized at high temperature, and the heat-lamination process is performed when it is used for cards such as lift tickets, it is possible to improve the stability of the background color against heat of 100 ° C or higher. The demand is increasing.

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 liable to deteriorate. Further, in the thermal head, there is a limit in increasing the integration density of the heating elements. The main resolution is around / mm,
Higher resolution recording than this is difficult. 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. ing. 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,
Unless the output is considerably increased, the thermal 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
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 discloses a recording layer comprising a colorless or light-colored coloring substance, a phenolic substance and an organic polymer binder containing benzenedithiol nickel complexes as a light absorber and recording with a laser beam. An optical recording medium is described.
Japanese Unexamined Patent Publication No. 58-94494 discloses one or more near-red materials comprising one or more heat-sensitive coloring materials and a compound having a maximum absorption wavelength in the near infrared region of 0.7 to 3 μm. Disclosed is a recording medium in which an outer absorption material is coated on a substrate. JP 58-209594 A discloses
Disclosed is an optical recording medium characterized in that 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 are laminated on a substrate.

[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.

In addition, it has been impossible to thermally laminate the recording surface after heat-sensitive recording or the entire recording medium with a film or the like because of the heat resistance of the conventional thermal recording medium using a phenol-based developer as a recording material. . On the other hand, even in the heat resistance of conventional optical recording materials using a phenol-based developer as a recording material, it is necessary to thermally laminate the recording surface of the unrecorded optical recording material or the entire recording material with a film or the like, and to perform thermal recording or optical recording. When the recording surface after 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.

Therefore, it is an object of the present invention to provide a thermal recording material or an optical recording material which can be heat-laminated and has a certain degree of heat resistance and excellent oil resistance.

[0014]

DISCLOSURE OF THE INVENTION The above-mentioned problem is that 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. It was achieved by using at least one compound represented by the following general formula (1) as a developer in the heat-sensitive recording material provided with.

[0015]

[Chemical 4] (In the formula, X represents an oxygen atom or a sulfur atom, R ₁ is an unsubstituted or substituted aralkyl group, a naphthyl group,
It represents a lower alkyl group having 1 to 6 carbon atoms, a lower alkenyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. )

The thermal recording material using the compound represented by the general formula (1) as a color developer can be recorded with a thermal head or the like, but on the other hand, even in a thermal environment at about 160 ° C. It exhibits characteristics that are unthinkable with conventional thermal recording papers, such as less color development. Further, this heat-sensitive recording material is superior in image stability to oil as compared with the heat-sensitive recording material using the conventional color developer.

Specific examples of the compound represented by the general formula (1) include the following (1-1) to (1-40), but the compound is not limited to these.

[0018]

[Chemical 5]

[Chemical 6]

[0019]

[Chemical 7]

Embedded image

The aminobenzenesulfonamide derivative of the present invention undergoes a structural change from the neutral structure (keto type structure in the case of urea) represented by the general formula (1) to give an acidic structure (enol type in the case of urea). It is considered that the color development ability is exhibited by changing the structure. In order to stabilize the acidic structure which is considered to exhibit color developing ability after heating, N of the urea structure or thiourea structure of the general formula (1) of the present invention is used.
It suffices if an aromatic ring having an aminosulfonyl group is present at position (or position 1). Therefore, R ₁ in the general formula (1) is not particularly limited as long as it does not impair the color developing ability and stability. An alkyl group,
Lower alkenyl group having 1 to 6 carbon atoms or 3 to 6 carbon atoms
The cycloalkyl group of is mentioned. Further, R ₁ in the general formula (1) may be substituted with a substituent that does not impair color development and heat resistance. Examples of the substituent include hydrocarbon groups such as methyl group, ethyl group and isopropenyl group, and halogen groups such as chlorine and fluorine. When these substituents are introduced into R ₁ , the solubility in oil is reduced, and the oil stability of the image can be improved as compared with the unsubstituted one.

The compound represented by the general formula (1) of the present invention can be produced by reacting sulfanilamide (also known as 4-aminobenzenesulfonamide) with isocyanic acid esters or isothiocyanic acid esters. That is, in the reaction, 1 to 2.5 mol of isocyanic acid ester or isothiocyanic acid ester is added to 1 mol of sulfanilamide. The solvent to be used may be any solvent capable of dissolving sulfanilamide, isocyanic acid esters and isothiocyanic acid esters, for example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated aromatic compounds such as chloroform, dichloromethane and chlorobenzene. Aromatic hydrocarbons, ethers such as diethyl ether and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, aproton donating properties such as dimethylformamide and dimethyl sulfoxide Examples include polar solvents, alcohols such as methanol and ethanol, and mixed solvents thereof. Reaction temperature is 0-15
The temperature is 0 ° C, preferably 20 to 100 ° C.

The aminobenzenesulfonamide derivative used as the color developer in the recording material of the present invention takes into consideration the reactivity (yield) of the isocyanic acid esters or isothiocyanic acid esters with sulfanilamide or the economical efficiency. In this case, the compound represented by the following general formula (2) is preferable.

[0023]

[Chemical 9] (In the formula, R ₂ represents an unsubstituted or substituted aralkyl group, a naphthyl group, a lower alkyl group having 1 to 6 carbon atoms, a lower alkenyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. .)

Specific examples of the compound represented by the above general formula (2) of the present invention include the following compounds (3) to (3).
(7) can be mentioned, but the invention is not limited thereto.

[0025]

[Chemical 10]

The aminobenzenesulfonamide derivative represented by the general formula (2) 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. In particular, the thermosensitive recording medium using the compounds (3) to (7) as a color developer has excellent heat resistance and oil resistance.

A general method for producing the heat-sensitive recording material of the present invention is to disperse a dye precursor and at least one compound represented by the above-mentioned general formula (1) as a developer together with a binder. According to this method, auxiliary agents such as a filler, a lubricant, an ultraviolet absorber, a water-proofing agent, and a defoaming agent are added to prepare a coating solution, which is then coated on a support by a usual method and dried.

It is possible to add a conventionally known sensitizer for coloring the dye precursor to the above coating material within a range that does not impair the desired effect for the above problems.

As the dye precursor 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 are not particularly limited, but 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 two or more kinds of conventionally known color developing agents 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, a conventionally known developer can be used. Can be used in combination with the compound of the general formula (1) of the present invention. Examples of such a developer include:
Bisphenol A, 4-hydroxybenzoic acid esters, 4-hydroxyphthalic acid diesters, phthalic acid monoesters, bis- (hydroxyphenyl) described in JP-A-3-207688 and JP-A-5-24366. Sulfides, 4-hydroxyphenylarylsulfones, 4-hydroxyphenylarylsulfonates, 1,3-di [2- (hydroxyphenyl) -2
Examples include -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'-isopropylidenediphenol (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> 4-hydroxyphthalic acid dimethyl 4-hydroxyphthalic acid diisopropyl 4-hydroxyphthalic acid dibenzyl 4-hydroxyphthalic acid dihexyl

<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-Hydroxyphenyl aryl sulfonates> 4-hydroxyphenylbenzene sulfonate 4-hydroxyphenyl-p-tolyl sulfonate 4-hydroxyphenylmethylene sulfonate 4-hydroxyphenyl-p-chlorobenzene sulfonate 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-Hydroxybenzoyloxybenzoate> Benzyl 4-hydroxybenzoyloxybenzoate 4-Methyl 4-hydroxybenzoyloxybenzoate 4-Hydroxybenzoyloxyethyl benzoate 4-Hydroxybenzoyloxypropyl benzoate 4-Hydroxybenzoyloxy Butyl benzoate 4-Hydroxybenzoyloxy isopropyl benzoate 4-Hydroxybenzoyloxybenzoate tert-Butyl 4-Hydroxybenzoyloxyhexyl benzoate 4-Hydroxybenzoyloxy octyl benzoate 4-Hydroxybenzoyloxy nonyl 4-hydroxybenzoyloxy benzoate 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 sulfone (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

<Bisphenolsulfones (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 preferable to add an appropriate amount of the sensitizer according to the heat resistance temperature characteristic to the intended thermal environment. it 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, a completely saponified polyvinyl alcohol having a polymerization degree of 200 to 1900, a partially saponified polyvinyl alcohol, a carboxy modified polyvinyl alcohol, an amide modified polyvinyl alcohol, a sulfonic acid modified polyvinyl alcohol, and a butyral modified polyvinyl are used. 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 on 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 to the above, 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, defoamers, 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 kinds 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.

Further, an overcoat layer of a polymer substance or the like may be provided on the thermosensitive color developing layer for the purpose of improving the storage stability. Further, 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, attritor or sand grinder or an appropriate emulsifying device until the particle size 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 containing a light absorbing agent which absorbs light and converts it into heat in the heat-sensitive recording layer or the like. 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, JP-A-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 excellent in terms of size reduction, safety, price, modulation and the like 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 absorbing agent used in the optical recording material of the present invention may be simply mixed in various materials required for the optical recording material, but as described in JP-A-2-217287, It is possible to use a material in which a light absorbing agent is previously melt-mixed and dissolved or dispersed in various materials of the recording medium. Examples of various materials that melt-mix and dissolve or disperse a light absorber in advance include, for example, sensitizers for heat-sensitive recording,
The developer of the present invention, a conventionally known developer, a dye precursor, a composition of the sensitizer for heat-sensitive recording and the developer of the present invention, a sensitizer for heat-sensitive recording and a conventionally known developer And a composition of a heat-sensitive recording sensitizer and a dye precursor.

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 a binder is preferably 10 to 25% of the total solid content. 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 to perform optical recording on the optical recording material of the present invention. Further, optical scanning recording may be performed using a mirror or the like.

Since the heat-sensitive recording material and the optical recording material of the present invention have excellent heat resistance and extremely high thermal stability of the background color, it is possible to provide a strong protective film by heat-laminating 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 / methyl methacrylate copolymer (EMAA), and ethylene / A thermoplastic resin such as methacrylic acid copolymer (EMAA) can be used.

In addition, extrusion coating 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 present 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 and the light absorber of the invention is extremely high. The reason why it shows heat resistance and the reason why it has excellent image stability against oil have not been clearly clarified, but it can be considered as follows.

In the aminobenzenesulfonamide derivative of the present invention, the following formula (hereinafter, neutral form is keto type,
Structural changes (hereinafter referred to as keto-enol tautomerism) such as the acidic form may be referred to as the enol form).
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 11] (In the formula, X represents an oxygen atom or a sulfur atom.)

In the case of the above-mentioned thermal recording, the thermal head momentarily reaches a high temperature of 200 to 300 ° C. or more, and therefore the thermal recording is represented by the general formula (1) contained in the recording layer of the thermal recording medium which is in contact with the thermal head. The compound capable of undergoing keto-enol tautomerism becomes 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. Further, the aminosulfonyl group (—SO ₂ NH ₂ ) is considered to contribute to the promotion of the color developing function and the stabilization of the enol type structure. Therefore, the dark recorded image density and the thermal stability of the image and the background color are considered. It is presumed that

Further, the heat-sensitive recording material using the compound represented by the general formula (1) of the present invention as a developer is excellent in image stability against oil because the conventional phenol-type developer is used. It is presumed that the discoloration of the image area is less likely to occur because the solubility in oil is lower than that of.

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) contained in the recording layer is
Similar to the thermosensitive recording, keto-enol tautomerism occurs to form 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.

Further, the compound of the general formula (1) does not exhibit a color developing agent function up to a temperature at which the structure changes to an enol type structure and does not react with a dye precursor, so that a ground 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) changes to an enol type 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. Absent.

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.

[0081]

【Example】

<Production of Compound of General Formula (1); Synthesis Examples 1 to 7> Compounds (3) to (7), (1-20) and (1-24) were synthesized as follows. The thermal analysis was carried out using SSC5200 type TG / DTA (Seiko Denshi Kogyo KK).

[Synthesis Example 1] <Compound (3); 4- (N-
Synthesis of cyclohexylcarbamoyl) aminobenzenesulfonamide> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, 30.5 g (243.7 mM) of cyclohexyl isocyanate was added with stirring, and the mixture was refluxed for 2 hours. The reaction mixture was filtered to obtain 15.2 g of white product (yield 44.0%). The results of NMR measurement (in DMSO-d6) are as follows. 1.47 ppm (dt, 2H), 1.54 ppm (d
t, 4H), 1.55 ppm (dt, 4H), 3.47
ppm (t, 1H), 6.22 ppm (d, 1H),
7.14 ppm (s, 2H), 7.51 ppm (d, 4
H), 7.66 ppm (d, 4H), 8.69 ppm
(S, 1H) The decomposition temperature of this substance determined by thermal analysis was 225.7 ° C., and the molecular weight determined by mass spectrometry (ionization method) was 297. From the above, it was identified that the obtained compound was the target product.

[Synthesis Example 2] <Compound (4); 4- (N-
Synthesis of Normal Propylcarbamoyl) aminobenzenesulfonamide> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, 11.9 g (139.8 mM) of normal propyl isocyanate was added with stirring, and the mixture was refluxed for 2 hours. . The reaction mixture was filtered to obtain 14.5 g of white product (yield 48.5%). NMR
The results of the measurement (in DMSO-d6) are as follows. 0.87ppm (t, 3H), 1.45ppm (td,
2H), 3.05ppm (dd, 2H), 6.29pp
m (t, 1H), 7.14 ppm (s, 2H), 7.5
3 ppm (d, 2H), 7.66 ppm (d, 2H),
The decomposition temperature of this substance determined by 8.80 ppm (s, 1H) thermal analysis was 213.4 ° C, and the molecular weight determined by mass spectrometry (ionization method) was 257. From the above, it was identified that the obtained compound was the target product.

[Synthesis Example 3] <Compound (5); 4- (N-
Synthesis of naphthylcarbamoyl) aminobenzenesulfonamide> Dissolve 20 g (116.1 mM) of sulfanilamide in 200 ml of acetonitrile, and add 23.6 g (139.5 mM) of naphthyl isocyanate while stirring.
Refluxed for 2 hours. The reaction mixture was filtered to give 25.7 g of white product (yield 64.8%). NMR measurement (D
The results of (in MSO-d6) are as follows. 7.23 ppm (s, 2H), 7.49 ppm (td,
1H), 7.58ppm (d, 1H), 7.62ppm
(S, 1H), 7.66 ppm (d, 1H), 7.69
ppm (s, 2H), 7.77 ppm (d, 2H),
7.95ppm (d, 1H), 8.00ppm (d, 1
H), 8.12 ppm (d, 1H), 8.88 ppm
(S, 1H), 9.42 ppm (s.1H) The decomposition temperature of this substance determined by thermal analysis was 251.8 ° C, and the molecular weight determined by mass spectrometry (ionization method) was 341. From the above, it was identified that the obtained compound was the target product.

[Synthesis Example 4] <Compound (6); 4- (N-
Synthesis of benzylcarbamoyl) aminobenzenesulfonamide> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, and 18.6 g (139.5 mM) of benzyl isocyanate was added with stirring.
Refluxed for 2 hours. The reaction mixture was filtered to give a white product 22.0 (62.0%). NMR measurement (DMSO
The result of (in d6) is as follows. 4.31 ppm (d, 2H), 6.78 ppm (t, 1
H), 7.15 ppm (s, 2H), 7.23 ppm
(Td, 1H), 7.29 ppm (td, 2H), 7.
36 ppm (td, 2H), 7.55 ppm (d, 2
H), 7.68 ppm (d, 2H), 8.97 ppm
(S, 1H) The decomposition temperature of this substance determined by thermal analysis was 249.7 ° 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 5] <Compound (7); 4- [N-
Synthesis of (isopropenyl-α, α-dimethylbenzyl) carbamoyl] aminobenzenesulfonamide> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, and isopropenyl-α, α-dimethylbenzyl isocyanate 28 was stirred. .1
g (139.5 mM) was added and refluxed for 2 hours. The reaction mixture was filtered to give 10.9 g of white product (yield 2
5.2%) was obtained. The results of NMR measurement (in DMSO-d6) are as follows. 1.62ppm (s, 6H), 2.10ppm (d, 3
H), 5.09ppm (t, 1H), 5.38ppm
(S, 1H), 6.77 ppm (s, 1H), 7.14
ppm (s, 1H), 7.31 ppm (d, 1H),
7.32ppm (d, 1H), 7.34ppm (d, 1)
H), 7.45 ppm (d, 2H), 7.49 ppm
(D, 2H), 7.64 ppm (d, 2H), 8.81
The decomposition temperature of this substance determined by ppm (s, 1H) thermal analysis was 209.0 ° C., and the molecular weight determined by mass spectrometry (ionization method) was 373. From the above, it was identified that the obtained compound was the target product.

[Synthesis Example 6] <Compound (1-20); 4-
Synthesis of (N-cyclohexylthiocarbamoyl) aminobenzenesulfonamide> Dissolve 20 g (116.1 mM) of sulfanilamide in 200 ml of acetonitrile, add 34.4 g (243.6 mM) of cyclohexyl isothiocyanate while stirring, and add for 2 hours. Refluxed. The reaction mixture is filtered,
A white product (9.7 g, yield 26.6%) was obtained. NMR
The results of the measurement (in DMSO-d6) are as follows. 1.37 ppm (dd, 2H), 1.50 ppm (d
d, 4H), 1.58 ppm (dd, 4H), 4.09
ppm (s, 1H), 7.24 ppm (s, 2H),
7.68ppm (t, 2H), 7.73ppm (t, 2)
H), 7.92 ppm (d, 1H), 9.62 ppm
(S, 1H) The decomposition temperature of this substance determined by thermal analysis was 202.7 ° C., and the molecular weight determined by mass spectrometry (ionization method) was 313. From the above, it was identified that the obtained compound was the target product.

[Synthesis Example 7] <Compound (1-24); 4-
(Synthesis of (N-benzylthiocarbamoyl) aminobenzenesulfonamide)> 20 g (116.1 mM) of sulfanilamide was dissolved in 200 ml of acetonitrile, and 36.4 g (243.9 mM) of benzyl isothiocyanate was added while stirring to obtain 2 Reflux for hours. The reaction mixture was filtered to obtain 14.6 g (yield 39.1%) of a white product. The results of NMR measurement (in DMSO-d6) are as follows. 4.75ppm (d, 2H), 7.27ppm (s, 2
H), 7.30 ppm (t, 1H), 7.35 ppm
(S, 2H), 7.36 ppm (s, 2H), 7.68
ppm (d, 2H), 7.74 ppm (d, 2H),
8.44ppm (s, 1H), 9.90ppm (s, 1
H) The decomposition temperature of this substance determined by thermal analysis was 193.0 ° 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 13 and Comparative Examples 1 to 7> The thermal recording medium of the present invention will be described below with reference to Examples. The numbers of parts and% in the description mean parts by weight and% by weight, respectively.

[Examples 1 to 7] In Examples 1 to 7, compounds (3) to (7) were used as color developers in the heat-sensitive recording material of the present invention.
(1-20) and (1-24) are used, and 3-diethylamino-6-methyl-7-anilinofluorane (ODB) is used as a dye precursor. The dispersant (liquid A) of the developer and the dispersion (liquid B) of the dye precursor having the following formulations were separately prepared with a sand grinder so that the average particle diameter was 1
Wet milling was done to micron. Liquid A (developer dispersion liquid) Developer 6.0 parts 10% polyvinyl alcohol aqueous solution 18.8 parts Water 11.2 parts Liquid B (dye precursor dispersion liquid) 3-diethylamino-6-methyl-7 -Anilinofluoran 2.0 parts 10% aqueous solution of polyvinyl alcohol 4.6 parts water 2.6 parts Then, the dispersion liquids were mixed at the following ratios to prepare a coating material. A solution (developer dispersion) 36.0 parts B solution (dye precursor dispersion) 9.2 parts kaolin clay - (50% dispersion) 12.0 parts The above respective coating of 50 g / m ² base paper After applying on one side,
After drying, the sheet was treated with a super calender 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 8 to 13] In Examples 8 to 13, the compound (5) was used as a developer and OD was used as a dye precursor.
This is an example in which the following dye precursors other than B are used. (Dye precursor) ODB-2; 3-dibutylamino-6-methyl-7-anilinofluorane PSD-150; 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinoflu Oran 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 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.

[Example 14] Example 14 is an example in which the compound (5) was used as the color developer and ODB and PSD-150 were used as the dye precursor. The ODB dispersion liquid (B liquid) was treated in the same manner as in Examples 1 to 7, and the PSD-150 dispersion liquid (C liquid) was treated in the same manner as in Examples 8 to 13. 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) 4.6 parts Liquid C (dye precursor [PSD-150] dispersion liquid) 4.6 parts Kaolin clay ( 50% dispersion) 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 15 In Example 15, compound (5) and compound (7) were used as color developers, and OD was used as a dye precursor.
This is an example using B. In the same manner as in Examples 1 to 7, the developer dispersion liquid (solution A) of the compound (5) and the compound (7) and the ODB dispersion liquid (solution B) were treated. Liquid A (developer (5) dispersion) 18.0 parts Liquid A (developer (7) dispersion) 18.0 parts Liquid B (dye precursor [ODB] dispersion 9.2 parts Kaolin clay ( 50% dispersion) 12.0 parts After applying each of the above coating materials 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 16 Example 16 is an example in which the compound (5) and bisphenol A (hereinafter referred to as BPA) are used as the color developer, and ODB is used as the dye precursor. The developer dispersion liquid (liquid A) and the ODB dispersion liquid (liquid B) of the compound (5) were treated in the same manner as in Examples 1 to 7. Further, the BPA dispersion liquid (D liquid), which is a known developer, was wet ground by 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% polyvinyl alcohol aqueous solution 18.8 parts water 11.2 parts Then, the dispersion liquids are mixed at the following ratios. And made it paint. Liquid A (developer (5) dispersion) 30.0 parts Liquid D (known developer [BPA] dispersion) 6.0 parts Liquid B (dye precursor [ODB] dispersion) 9.2 parts Kaolin clay (50% dispersion liquid) 12.0 parts After applying each of the above coating materials 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.

[Comparative Examples 1 to 7] Comparative Examples 1 to 7 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. Thermal recording media for comparative examples were prepared in the same manner as in Examples 1-13. (Known developer) BPA: Bisphenol A D-8: 4-hydroxy-4'-isopropoxydiphenyl sulfone The BPA dispersion was treated in the same manner as in Example 16, and further the D-8 dispersion (D 'solution). 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% polyvinyl alcohol aqueous solution 18.8 parts water 11.2 parts Then, the dispersions are mixed in the following proportions. Coating solution. Liquid D or liquid D '(known developer dispersion liquid) 36.0 parts Liquid B, liquid C (dye precursor dispersion liquid) 9.2 parts Kaolin clay (50% dispersion liquid) 12.0 parts each of the above After applying the coating liquid on 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 Thermal Recording Material; Examples 1 to 16 and Comparative Examples 1 to 7> [Thermal Recording Property Test (Dynamic Color Density)] (See Table 1, Table 2 and Table 3) Personal Word Processor Rupo-90FII Using a printer (manufactured by Toshiba Corp.), the thermal recording was performed on the thermal recording bodies of Examples 1 to 16 and Comparative Examples 1 to 7 at the maximum applied energy (the thermal recordings shown below are all the same. conditions). The recording density of the recording unit is Macbeth densitometer (RD-9
14, using an amber filter, and the same conditions below). Example 1 using the compound of the present invention as a developer
With respect to the thermosensitive recording materials Nos. 16 to 16, 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] (See Table 1, Table 2 and Table 3) Using a gear type aging tester (Toyo Seiki Seisakusho Co., Ltd.), test temperatures of 100 ° C, 120 ° C and 140 ° C. And 160
C., heat resistance test for 30 minutes each, the above Examples 1-16
And the thermal recording materials of Comparative Examples 1 to 7 above. 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 heat-sensitive recording materials of Examples 1 to 16 in which the compound of the present invention was used as a color developer were 1
The density of the background color after 30 minutes at 40 ° C. does not exceed 0.3, whereas the thermal recording papers using the phenol-based color developers of Comparative Examples 1 to 7 have already been completely exposed at 100 ° C. for 30 minutes. Is 0.
It is over 5. The thermal recording materials of Examples 1 to 15 had 16
Even after 30 minutes at 0 ° C., the contrast between the recorded image and the background color is high, and extremely high heat resistance stability is exhibited.

[0098]

[Table 1]

[Table 2]

[Table 3]

[Stability Test of Image Area] (See Table 4) The stability test of the image area against oil was conducted on the thermal recording materials of Examples 1 to 7. In this test, a heat-sensitive recording material on which heat-sensitive recording is performed is immersed in salad oil and left at room temperature for 30 minutes,
After the excess salad oil was wiped off, the Macbeth concentration in the image area was measured, and the residual rate (%) in the image area was calculated and evaluated. The "remaining rate (%) of the image area" was calculated by the following formula. Residual rate (%) = 100 × (recording density after treatment) / (untreated recording density) The thermal recording materials of Examples 1 to 7 in which the compound of the present invention was used as a color developer had an image residual rate of 50. %, While that of the thermal recording paper using the phenol-based developer is 20%.
It is the following. This is compound (3) used as a developer
It can be inferred that (7), (1-20), and (1-24) have lower solubility in oil than the phenol-based color developer.

[0100]

[Table 4]

<Thermal Lamination and Toner Recording Test; Examples 17 to 38, Comparative Examples 8 to 13> 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 5) A simple laminating apparatus (MS Pouch H-140, Meiko Shokai) and a laminating film (MS Pouch Film MP10-6095) were used. The thermal recording materials of Examples 1 to 8, 11, 15, 16 and Comparative Examples 1, 4, 6 which had already been subjected to thermal recording under the above-mentioned conditions were sandwiched between the laminate films, and the feed speed was 20 mm / sec. A laminated thermal recording material having a thermal recording portion was produced (Examples 17 to 27, Comparative Examples 8 to 10). After the heat-laminating treatment, the color-developed portion and the ground-colored portion due to the heat-sensitive recording were measured with the Macbeth densitometer through the laminated film of the laminated heat-sensitive recording material (it becomes a high value because it is measured through the 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 is developed, almost no color (image can be read) △: Ground color is colored (image is difficult to read) ×: Ground color is significantly colored (image cannot be read) ) It was difficult to read the laminated thermal recording material with the contrast evaluation of Δ to ×, and thermal lamination was substantially impossible (Comparative Examples 14 to 16). On the other hand, in Examples 17 to 27, the contrast evaluation is good (◯).
And thermal lamination was possible.

[0103]

[Table 5]

[Toner Recording Test by Electrophotographic Copier] (See Table 6) Examples 1 to 7, 9, 10, 15, 16 and Comparative Example 1,
The thermosensitive recording media of Nos. 4 and 6 were replaced with electrophotographic copying machines
Toner recording was performed on a sheet of 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 causing background color development (Examples 28 to 38).

[0105]

[Table 6]

<Manufacture of Optical Recording Material; Examples 39 to 57 and Comparative Examples 20 to 25> 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 39 to 43] (See Table 7) Examples 39 to 43 are compounds (4) to (7) and (1-20) as a color developer, and light absorption in the optical recording material of the present invention. Bis (1-methyl-3,4-dithiophenolate) nickel tetra-n-butylammonium as a sensitizer and a hot melt of a sensitizer (light absorber 1), 3-diethylamino-6-methyl-as a dye precursor 7-anilinofluoran (O
This is an example using DB). The developer dispersion liquid (A liquid), the dye precursor dispersion liquid (B liquid), and the light absorbing agent 1 dispersion liquid (E liquid) having the following composition, which were used in Examples 1 to 7, were separately separated by a sand grinder. Wet grinding was performed until the average particle size was 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% aqueous solution of polyvinyl alcohol 10.0 parts water 6.0 parts Then, the dispersion liquids were mixed in the following proportions to obtain 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 44 to 48] (see Table 7) Examples 44 to 48 are compounds (4) to (7) and (1-20) as a color developer, and light absorption in the optical recording material of the present invention. This is an example in which NK-2612 (light absorber 2; manufactured by Japan Photosensitive Dye Research Institute Co., Ltd.) is used as an agent and 3-diethylamino-6-methyl-7-anilinofluorane (ODB) is used as a dye precursor. The developer dispersion liquid (A liquid) and the dye precursor dispersion liquid (B liquid) used in Examples 1 to 7 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 49 to 53] (See Table 7) Examples 49 to 53 are compounds (4) to (7) and (1-20) as a color developer in the optical recording material of the present invention, and light absorption. A hot melt of bis (1-methyl-3,4-dithiophenolate) nickel tetra-n-butylammonium as a sensitizer and a sensitizer (light absorber 1; see Examples 39 to 43), 3 as a dye precursor -Dibutylamino-6-methyl-7-
This is an example in which a light absorbing color forming layer using anilinofluorane (ODB-2) is provided on a light absorbing under layer composed of a filler and graphite (light absorbing agent 3) on a base paper. 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 It was applied on one side of paper and then 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 liquid) and a light absorber 1 dispersion liquid (E liquid) were prepared in the same manner as in Examples 39 to 43.
Further, as in Examples 8 to 14, the dye precursor dispersion liquid (C liquid).
Was prepared 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 54 to 57] (See Table 8) In Examples 54 to 57, the compound (5) 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, Inc.), as a dye precursor, PSD-150, G shown in Examples 8 to 14
It is an example using reen40, CVL, and I-Red. Developer dispersion (liquid A) and light absorber 2 aqueous solution (F
Liquid) was prepared in the same manner as in Examples 44 to 48. Also,
Dye precursor dispersion liquids (C liquids) were prepared in the same manner as in Examples 8 to 14, and the obtained liquids A, F and C were mixed at the following ratios to prepare coating materials. 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 14 to 19] (See Table 9) Comparative Examples 14 to 19 are comparative examples 1 to 4 as known color developers.
Bisphenol A (BPA), N as a light absorber
K-2612 (light absorber 2; manufactured by Japan Photosensitive Dye Research Institute), ODB shown in Examples 1 to 7 as a dye precursor, ODB-2 shown in Examples 8 to 13, PSD-150, and Gr.
It is a comparative example to the optical recording medium of the present invention using een40, CVL, and I-Red. Developer dispersion (BP
(A; D liquid) was prepared in the same manner as in Comparative Examples 1 to 4, and the light absorbent 2 aqueous solution (F liquid) was prepared in the same manner as in Examples 44 to 48. Further, various dye precursors (solution B or solution C) were prepared in the same manner as in Examples 1 to 7 and Examples 8 to 14, and the obtained solutions D, F, B and C were prepared as follows. The mixture was mixed at a ratio to obtain a paint. 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 Material; Examples 39 to 57 and Comparative Examples 14 to 19> [Optical Recording Test 1] Examples 39 to 48 and Examples 54 to 5
7 and the optical recording bodies of Comparative Examples 14 to 19,
Laser recording was performed by the following method using a laser plotter device described in Japanese Patent No. 239598. 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.
Two AP4545 (made by Konica) which is an aspherical plastic lens with a numerical aperture of 0.45 and a focal length of 4.5 mm was used for the condenser lens. A laser recording head composed of these semiconductor lasers and lenses is used at a recording speed of 50 mm / s.
By scanning at ec with a recording line interval of 50 microns, a solid color image of 1 cm square was obtained. The 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" in Tables 7, 8 and 9. Sufficient recording density was obtained by the laser recording of the optical recording materials of Examples 39 to 48 or Examples 54 to 57 in which the compound of the present invention was used as a developer.

[Optical Recording Test 2] The optical recording bodies of Examples 49 to 53 were subjected to optical recording using strobe flash light by the following method. As an optical recording method, light emission was performed by narrowing down the light emission window of a strobe flash auto 4330 for camera (manufactured by Sunpack) to 5%. The density of this developed image was measured by a Macbeth densitometer (RD-914, using an amber filter). This value is shown in Table 7 (Example 4).
9 to 53) "optical recording density". The optical recording materials of Examples 49 to 53 using the compound of the present invention as a color developer were able to obtain a sufficient recording density by the above-mentioned strobe flash recording.

[Ground color thermal stability test (optical recording material)] The heat resistance of the optical recording materials of Examples 39 to 57 and Comparative Examples 14 to 19 was the same as that of the thermal recording material. Using a gear type aging tester (Toyo Seiki Seisakusho Co., Ltd.), test temperatures of 100 ° C, 120 ° C, 140 ° C and 160
A heat resistance test was performed at 30 ° C. for 30 minutes each, and the Macbeth density of the background color was measured. This value is shown in Tables 7, 8 and
And 9 are shown. 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 39 to which the compound of this invention was used for the color developer.
The optical recording material of No. 57 has a background color density of 140 ° C. after 30 minutes,
There is nothing that exceeds 0.3, while Comparative Examples 14 to 19
The optical recording material using the phenol-based color developer of
It's already over 0.6 in 30 minutes. Example 3
The optical recording materials Nos. 9 to 56 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.

[0115]

[Table 7]

[Table 8]

[Table 9]

<Thermal Laminating, Optical Additional Recording and Toner Recording Test; Examples 58 to 87, Comparative Examples 20 to 25> Thermal lamination is performed on the optical recording material of the present invention, and further, the laminated optical recording material is subjected. Attempted optical recording. In addition, toner recording was performed using an electrophotographic copying machine.

[Thermal Laminating Test (See Table 10)] The thermal laminating test is performed by a simple laminating device (MS pouch H
-140 Meiko Shokai Co., Ltd. and laminated film (M
S pouch film MP10-6095). Example 3 in which optical recording (see [optical recording test 1] or [optical recording test 2]) has already been performed under the conditions described above.
9, 43, 44, 45, 50, 51, 54, 55, 5
The optical recording bodies of Nos. 6 and 57 and Comparative Examples 14, 15 and 18 were sandwiched between the laminate films, and the feeding speed was 20 mm / s.
A laminated optical recording body having an optical recording portion was produced by ec (Examples 58 to 67, Comparative Examples 20 to 22). 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. ○: There is no background color, there is almost no (image can be read) △: Background color is present (image is difficult to read) ×: Ground color is noticeable (image cannot be read) ) It was difficult to read the laminated optical recording material with the contrast evaluation of Δ to ×, and thermal lamination was substantially impossible (Comparative Examples 20 to 22). On the other hand, Example 58
About -67, the contrast evaluation was good (◯), and heat lamination was possible. No fading of the optical recording image portion due to heat was observed.

[0118]

[Table 10]

[Optical additional recording test (see Table 11)] Optical recording test 1 and optical recording test 2 shown in Evaluation of optical recording medium with respect to laminated optical recording medium shown in Examples 58 to 67.
Was carried out (Examples 68 to 77). 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 is shown in "Optical recording density" in Table 11. All of the laminated optical recording bodies shown in Examples 58 to 67 are capable of laser recording (optical recording test 1) and strobe flash recording (optical recording test 2) through the laminate film.
Sufficient recording density was obtained.

[0120]

[Table 11]

[Toner recording test by electrophotographic copying machine (see Table 12)] Examples 39, 43, 44, 45, 5
0, 51, 54, 55, 56, 57 and Comparative Examples 14, 1
The optical recording media of Nos. 5 and 18 are electrophotographic copying machines (Vivece 4
Toner recording was performed as a paper of 00 Fuji Xerox Co., Ltd. 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 an electrophotographic copying machine without developing a ground color (Examples 78 to 87).

[0122]

[Table 12]

[0123]

As described above, a heat-sensitive recording material and an optical recording material using the compound represented by the general formula (1) of the present invention as a color developer, can be used up to a temperature environment of about 160 ° C. Although there is almost no fog in the background color, a thermal recording device such as a thermal head, or an optical recording device using a laser or a strobe flash can provide a practical image recording density. 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 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) Image stability to oil is higher than that using a known developer. (4) Optical recording can be further performed on the laminated optical recording medium. (5) Since the background color is stable even after passing through a heat roll, a thermosensitive recording material or an optical recording material can be used as the electrophotographic copying machine paper.

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[Procedure amendment]

[Submission date] August 1, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

Embedded image (In the formula, X represents an oxygen atom or a sulfur atom, R ₁ is an unsubstituted or substituted aralkyl group, a naphthyl group,
It represents a lower alkyl group having 1 to 6 carbon atoms, a lower alkenyl group having 2 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. )

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

Embedded image (In the formula, R ₂ represents an unsubstituted or substituted aralkyl group, a naphthyl group, a lower alkyl group having 1 to 6 carbon atoms, a lower alkenyl group having 2 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. .)

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

[0015]

[Chemical 4] (In the formula, X represents an oxygen atom or a sulfur atom, R ₁ is an unsubstituted or substituted aralkyl group, a naphthyl group,
It represents a lower alkyl group having 1 to 6 carbon atoms, a lower alkenyl group having 2 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. )

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

The aminobenzenesulfonamide derivative of the present invention undergoes a structural change from the neutral structure (keto type structure in the case of urea) represented by the general formula (1) to give an acidic structure (enol type in the case of urea). It is considered that the color development ability is exhibited by changing the structure. In order to stabilize the acidic structure which is considered to exhibit color developing ability after heating, N of the urea structure or thiourea structure of the general formula (1) of the present invention is used.
It suffices if an aromatic ring having an aminosulfonyl group is present at position (or position 1). Therefore, R ₁ in the general formula (1) is not particularly limited as long as it does not impair the color developing ability and stability. An alkyl group,
Lower alkenyl group having 2 to 6 carbon atoms or 3 to 6 carbon atoms
The cycloalkyl group of is mentioned. Further, R ₁ in the general formula (1) may be substituted with a substituent that does not impair color development and heat resistance. Examples of the substituent include hydrocarbon groups such as methyl group, ethyl group and isopropenyl group, and halogen groups such as chlorine and fluorine. When these substituents are introduced into R ₁ , the solubility in oil is reduced, and the oil stability of the image can be improved as compared with the unsubstituted one.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

[0023]

[Chemical 9] (In the formula, R ₂ represents an unsubstituted or substituted aralkyl group, a naphthyl group, a lower alkyl group having 1 to 6 carbon atoms, a lower alkenyl group having 2 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. .)

─────────────────────────────────────────────────── ─── 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 (10)

[Claims] 1. 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 color developer contains at least one compound represented by the following general formula (1). Embedded image (In the formula, X represents an oxygen atom or a sulfur atom, R ₁ is an unsubstituted or substituted aralkyl group, a naphthyl group,
It represents a lower alkyl group having 1 to 6 carbon atoms, a lower alkenyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. ) 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 color developer contains at least one compound represented by the following general formula (2). Embedded image (In the formula, R ₂ represents an unsubstituted or substituted aralkyl group, a naphthyl group, a lower alkyl group having 1 to 6 carbon atoms, a lower alkenyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. .) 3. An aminobenzenesulfonamide derivative represented by the general formula (2) according to claim 2. 4. An aminobenzenesulfonamide derivative represented by the following structural formulas (3) to (7). [Chemical 3] 5. A heat-sensitive recording material comprising the heat-sensitive recording material according to claim 1 or 2, after 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 heat-sensitive recording material according to claim 1 or 2 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 1 or 2, or the optical recording material according to claim 6.