JP2819544B2 - Recorded body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive recording medium or an optical recording medium using a thiourea compound as a developer and having excellent heat resistance.

[0002]

2. Description of the Related Art In general, a heat-sensitive recording sheet is usually prepared by grinding and dispersing a colorless or pale-colored dye precursor and a developer such as a phenolic compound into fine particles, and then mixing the two with a binder. Filler, sensitivity enhancer, a coating solution obtained by adding a lubricant and other auxiliaries, paper, synthetic paper, film, is applied to a support such as plastic,
A color is formed by an instantaneous chemical reaction caused by heating of a thermal head, a hot stamp, a hot pen, a laser beam or the like, and a recorded image is obtained.

[0003] These heat-sensitive recording materials include a measuring recorder, a computer terminal printer, a facsimile,
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 advancement of performance of these recording devices, the required quality of thermal recording sheets has become higher. I have. For example, with the speeding up of recording, it is required to obtain a high-density and clear color image even with a small amount of thermal energy. On the other hand, storage stability such as light resistance, heat resistance, water resistance, oil resistance and plasticizer resistance is required. Are required.

[0004] More recently, as systems for recording on plain paper such as the electrophotographic system and the ink jet system have become widespread, there has been an increasing number of opportunities for comparing thermal recording with plain paper recording. For example, the stability of an image approaches the quality of toner recording, and the stability of a non-recorded portion (blank paper or ground color) before and after recording (hereinafter referred to as ground color stability) approaches the quality of plain paper recording. In addition, it is required to use heat-sensitive recording paper as a food label that is sterilized at high temperature, and to perform heat lamination when using it for cards such as lift tickets. There is a growing demand for ground color stability to heat.

Regarding the ground color stability against heat, JP-A-4-353490 discloses 3-dibutylamino-7-
(O-chloroanilino) fluoran, a 4-hydroxydiphenylsulfone compound having a melting point of 120 ° C. or more, a mixture of sodium salt of 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate and magnesium silicate, etc. The heat-sensitive recording medium containing
It is disclosed that the ground color portion and the recorded image portion have excellent stability even in a high-temperature environment of about ° C.

On the other hand, recording on a thermosensitive recording medium is generally performed by a method in which a thermal head or a heat generating IC pen, which is a heating element, is brought into direct contact with a thermosensitive recording paper to perform heat recording. In this method, a coloring melt or the like adheres to the heating element to cause deposition, which tends to deteriorate the recording function. In a thermal head, there is a limit in increasing the integration density of the heating elements. / Mm resolution mainly,
Higher resolution recording is difficult. Therefore, as a method of further improving the resolution without lowering the recording function, a non-contact recording method using light has been proposed.

Japanese Patent Application Laid-Open No. Sho 58-148776 discloses that thermal recording is possible by using a carbon dioxide laser as a recording light source and converging and scanning the laser beam on a general thermal recording paper for a thermal head. Has been disclosed. This recording method requires a high laser output despite the fact that the thermal recording paper absorbs the oscillation wavelength of the carbon dioxide laser. Including a gas laser as a recording light source, it is impossible to reduce the size of the recording device, and there is a problem in cost.

Further, general thermosensitive recording paper hardly absorbs light in the visible or near-infrared region. Therefore, 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 substantially equivalent. If it is not large, the heat energy required for coloring cannot be obtained.

An optical recording medium comprising a combination of a conventional heat-sensitive recording material and a light-absorbing material is disclosed in Japanese Patent Laid-Open No. Sho 54-4142.
JP-A-57-11090, JP-A-58-9449
No. 4, JP-A-58-209594, and the like.

JP-A-54-4142 discloses that a metal compound having lattice defects is used in a heat-sensitive recording material obtained by coating a heat-sensitive recording layer mainly composed of a leuco dye on a support. It discloses that a metal compound absorbs light in the visible or infrared region and converts it into heat to enable thermal recording. JP-A-57-11090
The publication discloses an optical recording medium that has a benzenedithiol-based nickel complex as a light absorber in a recording layer composed of a colorless or light-colored coloring substance, a phenolic substance, and an organic polymer binder, and performs recording with a laser beam. Have been described. JP-A-58-94494 discloses one or two or more thermosensitive coloring materials and a compound comprising a compound 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 base material is disclosed. JP-A-58-209594 discloses an optical device characterized in that at least one pair 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 is laminated on a substrate. Discloses a dynamic recording medium.

[0011]

[Problems to be solved by the invention] JP-A-4-35349
The thermal stability of the ground color of the thermal recording medium disclosed in Japanese Patent Publication No. 0 (hereinafter referred to as thermal stability) is measured in a hot air drier at 95 ° C.
The Macbeth density of the ground color after the time treatment is 0.11, and although it shows considerable stability, it is still insufficient at the heat resistant temperature.

Further, in the heat resistance of a conventional heat-sensitive recording material using a phenolic color developer as a recording material, it is impossible to heat-laminate the recording surface after the heat-sensitive recording or the entire recording material with a film or the like. Was. On the other hand, with respect to the heat resistance of the conventional optical recording medium using a phenolic developer as a recording material, the recording surface of an unrecorded optical recording medium or the entire recording medium is thermally laminated with a film or the like, and thermal recording is performed. When the recording surface after optical recording or optical recording or the entire recording medium is thermally laminated with a film or the like, the entire surface is colored, and practical use has been impossible.

Accordingly, an object of the present invention is to provide a heat-sensitive recording medium or an optical recording medium which can be thermally laminated and has a certain degree of heat resistance.

[0014]

An object of the present invention is to provide a recording apparatus comprising, as a main component, a colorless or pale-colored dye precursor and a color developer which reacts with the dye precursor to form a color. In a thermosensitive recording medium provided with a layer, at least one thiourea compound represented by the following general formula (1) or (2) is contained as the color developer.

[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.)

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

[0017]

Embedded image

Embedded image

Represented by the general formula (1) or (2):
The thiourea compound used in the thermosensitive recording medium of the present invention is 2
-Aminobenzenesulfonamide or 3-aminobenzenesulfonamide and phenyl isothiocyanate can be produced. That is, in the reaction, 1 to 2.5 mol of phenyl isothiocyanate is added to 1 mol of sulfanilamide. As a solvent to be used, any solvent capable of dissolving sulfanilamide or phenyl isothiocyanate may be used.Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aromatic hydrocarbons such as chloroform, dichloromethane, and chlorobenzene; Diethyl ether, ethers such as tetrahydrofuran, acetonitrile, nitriles such as propionitrile, esters such as ethyl acetate, acetone, ketones such as methyl ethyl ketone,
Non-proton-donating polar solvents such as dimethylformamide and dimethylsulfoxide; alcohols such as methanol and ethanol; and mixed solvents thereof.
The reaction temperature is 0 to 150 ° C, preferably 20 to 100 ° C.
Range.

X in the general formula (1) or (2) is
A thermosensitive recording medium using a compound having a carbon number of 1 to 6 as a lower alkyl group or an electron-withdrawing group and m as an integer of 0 to 3 as a color developer can be recorded with a thermal head or the like. Both the recorded image portion and the background portion have heat resistance even at about 140 ° C. and heat resistance to a short-time heat treatment such as heat lamination, and exhibit characteristics that cannot be considered with conventional heat-sensitive recording paper.

The thiourea compound used in the thermosensitive recording medium of the present invention undergoes tautomerism from the thione type structure represented by the above general formula (1) or (2), and changes to a thiol type structure to develop color. It is considered to show. Therefore, in consideration of the stability of the recorded image against heat and oil, X in the above general formula (1) or (2) has a carbon number of 1 to 6 in order to stabilize a thiol type structure exhibiting a color developing ability. Although a lower alkyl group of the above can provide sufficient recorded image stability, an electron withdrawing group is more preferable. As the electron-withdrawing group, from the viewpoints of heat resistance, recording sensitivity, etc., a halogen atom and a carbon number of 1 to 1 are used.
6 is preferably an alkoxy group, a nitro group or a cyano group. From the viewpoint of industrial productivity and economy, X in the general formula (1) or (2) is more preferably an unsubstituted compound.

The general method for producing the thermosensitive recording medium of the present invention comprises a dye precursor and the above-mentioned general formula (1) as a color developer.
Alternatively, at least one compound represented by (2) is dispersed together with a binder, and if necessary, auxiliaries such as a filler, a lubricant, an ultraviolet absorber, a water-resistant agent, and an antifoaming agent are added, and the mixture is coated. In this method, a liquid is prepared, applied on a support by a usual method, and dried. It should be noted that a conventionally known color developing agent or a conventionally known sensitizer for forming a color of the dye precursor may be added to the above-mentioned coating solution as long as the desired effect on the above-mentioned problem is not impaired.

As the dye precursor used in the recording medium of the present invention, any of those known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, and there is no particular limitation. Compounds, fluoran compounds, fluorene compounds, divinyl compounds and the like are preferred. 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-methylfluoran 3-Diethylamino-6-methyl-7-anilinofluoran 3-Diethylamino-6-methyl-7- (o, p-dimethylanilino ) Fluoran 3-diethylamino-6-methyl-7-chlorofluoran 3-diethylamino-6-methyl-7- (m-trifluoromethylanilino) fluoran 3-diethylamino-6-methyl-7- (o-chloroanilino) Fluoran 3-diethylamino-6-methyl-7- (p-chloroanilino) fluoran 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluoran 3-diethylamino-6-methyl-7-n-octylaminofur Oran 3-diethylamino-6-methyl-7-benzylanilino Fluoran 3-diethylamino-6-methyl-7-dibenzylanilinofluoran 3-diethylamino-6-chloro-7-methylfluoran 3-diethylamino-6-chloro-7-anilinofluoran 3-diethylamino-6 Chloro-7-p-methylanilinofluoran 3-diethylamino-6-ethoxyethyl-7-anilinofluoran 3-diethylamino-7-methylfluoran 3-diethylamino-7-chlorofluorane 3-diethylamino-7- (M-trifluoromethylanilino) fluoran 3-diethylamino-7- (o-chloroanilino) fluoran 3-diethylamino-7- (p-chloroanilino) fluoran 3-diethylamino-benzo [a] fluoran 3-diethylamino-benzo [c ] Fluoran 3-jib Tylamino-6-methyl-fluoran 3-dibutylamino-6-methyl-7-anilinofluoran 3-dibutylamino-6-methyl-7- (o, p-dimethylanilino) fluoran 3-dibutylamino-6 Methyl-7- (o-chloroanilino) fluoran 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluoran 3-dibutylamino-6-methyl-7- (o-fluoroanilino) fluoran 3-dibutylamino -6-methyl-7- (m-trifluoromethylanilino) fluoran 3-dibutylamino-6-methyl-chlorofluoran 3-dibutylamino-6-ethoxyethyl-7-anilinofluoran 3-dibutylamino- 6-chloro-7-anilinofluoran 3-dibutylamino-6-methyl-7-p-methyla Nilinofluoran 3-dibutylamino-7- (o-chloroanilino) fluoran 3-n-dipentylamino-6-methyl-7-anilinofluoran 3-n-dipentylamino-6-methyl-7- (p-chloroanilino) fluoran 3-n-dipentylamino-6-chloro-7-anilinofluoran 3-n-dipentylamino-7- (p-chloroanilino) fluoran 3-pyrrolidino-6-methyl-7-anilinofluoran 3-piperidino- 6-methyl-7-anilinofluoran 3- (N-methyl-N-propylamino) -6-methyl-7-anilinofluoran 3- (N-methyl-N-cyclohexylamino) -6
Methyl-7-anilinofluoran 3- (N-ethyl-N-cyclohexylamino) -6
Methyl-7-anilinofluoran 3- (N-ethyl-N-xylamino) -6-methyl-
7- (p-chloroanilino) fluoran 3- (N-ethyl-p-toluidino) -6-methyl-
7-anilinofluoran 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran 3- (N-ethyl-N-isoamylamino) -6-chloro-7-anilino Fluoran 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluoran 3-cyclohexylamino-6-chlorofluoran 2- (4-oxahexyl) -3-dimethylamino -6
-Methyl-7-anilinofluoran 2- (4-oxahexyl) -3-diethylamino-6
-Methyl-7-anilinofluoran 2- (4-oxahexyl) -3-dipropylamino-
6-methyl-7-anilinofluoran 2-methyl-6-p- (p-dimethylaminophenyl)
Aminoanilinofluoran 2-methoxy-6-p- (p-dimethylaminophenyl) aminoanilinofluoran 2-chloro-3-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran 2 -Chloro-6-p- (p-dimethylaminophenyl)
Aminoanilinofluoran 2-nitro-6-p- (p-diethylaminophenyl)
Aminoanilinofluoran 2-amino-6-p- (p-diethylaminophenyl)
Aminoanilinofluoran 2-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluoran 2-phenyl-6-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran 2- Benzyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran 2-hydroxy-6-p- (p-phenylaminophenyl) aminoanilinofluoran 3-methyl-6-p- (p-dimethyl Aminophenyl)
Aminoanilinofluorane 3-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofluoran 3-diethylamino-6-p- (p-dibutylaminophenyl) aminoanilinofluoran

<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) fluoran-γ- (3
'-Nitro) anilinolactam 3,6-bis (diethylamino) fluoran-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 types of conventionally known color developing agents that form a dye precursor are used as long as the desired effects on the above object are not impaired. Alternatively, it can be used in combination with the compound represented by (2). When producing a thermosensitive recording medium having extremely excellent heat resistance, it is better to avoid using a conventionally known color developer, but depending on the heat resistance temperature characteristics for the intended thermal environment, a conventionally known color developer may be 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 developer include, for example, JP-A-3-20768.
No. 8, Bisphenol A, 4-hydroxybenzoic acid esters,
Hydroxyphthalic acid diesters, phthalic acid monoesters, bis- (hydroxyphenyl) sulfides,
-Hydroxyphenylarylsulfones, 4-hydroxyphenylarylsulfonates, 1,3-di [2
-(Hydroxyphenyl) -2-propyl] -benzenes, 4-hydroxybenzoyloxybenzoic acid esters, and bisphenolsulfones. Specific examples of typical known color developers are shown below, but the present invention is not particularly limited thereto.

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

<4-Hydroxybenzoates> Benzyl 4-hydroxybenzoate Ethyl 4-hydroxybenzoate Propyl 4-hydroxybenzoate Isopropyl 4-hydroxybenzoate Butyl 4-hydroxybenzoate Isobutyl 4-hydroxybenzoate 4- Methyl benzyl hydroxybenzoate

<Diesters of 4-hydroxyphthalic acid> Dimethyl 4-hydroxyphthalate 4-Diisopropyl 4-hydroxyphthalate 4-Dibenzyl 4-hydroxyphthalate Dihexyl 4-hydroxyphthalate

<Monoesters of Phthalate> Monobenzyl phthalate Monocyclohexyl phthalate Monophenyl phthalate Monomethyl phenyl phthalate Monoethyl phenyl phthalate Monopropyl benzyl phthalate Monohalogen benzyl phthalate 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'-n-butyloxydiphenylsulfone4-hydroxy-4'-n-propoxydiphenylsulfone

<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-hydroxybenzoyloxybenzoate> Benzyl 4-hydroxybenzoyloxybenzoate Methyl 4-hydroxybenzoyloxybenzoate Ethyl 4-hydroxybenzoyloxybenzoate Propyl 4-hydroxybenzoyloxybenzoate 4-hydroxybenzoyloxy Butyl benzoate isopropyl 4-hydroxybenzoyloxybenzoate tert-butyl 4-hydroxybenzoyloxybenzoate hexyl 4-hydroxybenzoyloxybenzoate octyl 4-hydroxybenzoyloxybenzoate nonyl 4-hydroxybenzoyloxybenzoate 4-hydroxybenzoyloxy Cyclohexyl benzoate 4-hydroxybenzoyloxy benzoate β-phenethyl 4-hydroxybenzoyloxy Phenyl benzoate 4-hydroxy-benzoyloxy benzoate α- naphthyl 4-hydroxy-benzoyloxy benzoate β- naphthyl 4-hydroxy-benzoyloxy benzoate sec- butyl

<Bisphenolsulfones (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'-hydroxy Enirusuruhon 4-hydroxyphenyl-2'-isopropyl-4'
Hydroxyphenylsulfone 4-hydroxyphenyl-3'-isopropyl-4'-
Hydroxyphenylsulfone 4-hydroxyphenyl-3'-secbutyl-4'-
Hydroxyphenylsulfone 3-chloro-4-hydroxyphenyl-3'-isopropyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-aminophenyl -4'-hydroxyphenylsulfone 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-tert-butylphenyl-3'-isopropyl-4'-hydroxyphenylsulfone 2-hydroxy-5-tert-butylphenyl-2 '-Methyl-4'-hydroxyphenylsulfone

<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 novolak 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 on the above objects are not impaired. When manufacturing a heat-sensitive recording material having extremely excellent heat resistance, it is generally better not to use a sensitizer, but it is necessary to add an appropriate amount of the sensitizer according to the heat-resistant temperature characteristics of the target thermal environment. Can be.

Examples of such a sensitizer include fatty acid amides such as stearic acid amide and palmitic acid amide, ethylene bisamide, montanic acid wax, polyethylene wax, 1,2-di- (3-methylphenoxy) ethane, p
-Benzylbiphenyl, β-benzyloxynaphthalene, 4-biphenyl-p-tolylether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, di (oxachloro) benzyl, oxalate di ( 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-xylerin-bis-
Examples thereof include (phenyl ether) and 4- (m-methylphenoxymethyl) biphenyl, but are not particularly limited thereto. These sensitizers may be used alone or in combination of two or more.

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 alcohol Modified polyvinyl alcohol such as alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as acetyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, polyvinyl chloride, polyvinyl acetate, polyacrylamide , Polyacrylate, polyvinyl butyral, polystyrene and copolymers thereof, polyamide resin, silicone Butter, petroleum resins, terpene resins, ketone resins, and coumarone resins. These polymeric substances include water, alcohol, ketones, esters,
In addition to being used by dissolving in a solvent such as a hydrocarbon, it can be used in a state of being emulsified or dispersed in water or another medium in the form of a paste, and used in combination depending on required quality.

Further, in the present invention, metal salts of p-nitrobenzoic acid (Ca, Zn), which are known stabilizers exhibiting an oil resistance effect of recorded images and the like, as long as the desired effects on the above-mentioned problems are not impaired, Alternatively, phthalic acid monobenzyl ester metal salt (Ca, Zn) can be added.

Fillers which can be used in the present invention include 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, releasing agents such as fatty acid metal salts, lubricants such as waxes, benzophenone-based and triazole-based ultraviolet absorbers, waterproofing agents such as glyoxal, dispersants, defoamers, antioxidants, fluorescent Dyes and the like can be used.

The amounts of the color developer and 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, with respect to 1 part of the dye precursor,
The developer of 1 to 8 parts of the present invention and the filler of 1 to 20 parts are used, and the binder is suitably used at 10 to 25% of the total solid content.

As the support, paper, synthetic paper, plastic film, non-woven fabric, metal foil and the like can be used, or a composite sheet combining these can be used. An intended thermosensitive recording medium can be obtained by applying a coating solution having the above composition to any of these supports.

For the purpose of further improving the storage stability, an overcoat layer of a polymer substance or the like can be provided on the thermosensitive coloring layer.

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

The above-mentioned developer, dye precursor, and optionally added materials are pulverized by a pulverizer such as a ball mill, an attritor, a sand grinder or an appropriate emulsifier to a particle size of several microns or less. A coating liquid is prepared by adding a binder and various additives depending on the purpose.

The thermosensitive recording medium of the present invention can be made into an optical recording medium by incorporating a light absorbing agent which absorbs light and converts it into heat in the thermosensitive recording layer or the like. The light absorbing agent for converting light into heat used in the recording medium 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 a light absorbing agent that converts light into heat include, for example, JP-A-2-206583 and Japanese Patent Application No. 5-30954. And a reaction product of a thiourea derivative and a copper compound described in JP-A-3-86580, graphite, copper sulfide, lead sulfide, molybdenum trisulfide, black titanium and the like described in JP-A-3-86580. Others
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 a visible wavelength region to a near infrared region is used. Examples of materials having an absorption corresponding to the oscillation wavelength thereof include JP-A-54-4142, JP-A-58-94494, and JP-A-58-209594.
JP-A-2-217287, JP-A-3-73814, and "Near-infrared absorbing dyes" (Chemical Industries 43, 198).
Polymethine dyes (cyanine dyes), azurenium dyes, pyrylium dyes, thiopyrylium dyes, squalilium dyes, croconium dyes, dithiol metal complex salt dyes, mercaptophenol metal complexes disclosed in Type dye, mercaptonnaphthol metal complex dye, phthalocyanine dye, naphthalocyanine dye, triallylmethane dye, immonium dye, diimmonium dye, naphthoquinone dye, anthraquinone dye, metal complex salt dye, etc. .

Specifically, examples of polymethine dyes (cyanine dyes) include indocyanine green (manufactured by Daiichi Pharmaceutical Co., Ltd.), NK-2014 (manufactured by Japan Photographic Dye Laboratories), and NK-2014. 2612 (manufactured by Japan Photographic Dye Laboratories), 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 the squarylium-based dye include, for example,
NK-2772 (manufactured by Japan Photographic Dye Laboratory). Examples of the dithiol metal complex salt dye include toluene dithiol nickel complex, 4-tertbutyl-1,2-benzenedithiol nickel complex, bisdithiobenzyl nickel complex, PA-1005 (manufactured by Mitsui Toatsu Dye Co., Ltd.), PA -1006 (manufactured by Mitsui Toatsu Dye Co., Ltd.), bis (4-ethyldithiobenzyl) nickel complex and bis (4-n-propyldithiobenzyl) nickel complex described in Japanese Patent Application No. 4-80646. No. As the immonium-based dye or diimmonium-based dye, IRG002 (Nippon Kayaku Co., Ltd.)
And IRG022 (produced by Nippon Kayaku Co., Ltd.). 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.). These light absorbers may be used alone or in combination of two or more.

The light absorbing agent used in the optical recording medium of the present invention comprises:
The light-absorbing agent may be preliminarily melted in the various materials of the optical recording medium of the present invention, as described in JP-A-2-217287. What was mixed and dissolved or dispersed can be used. Examples of various materials for dissolving or dispersing the light absorber by melting and mixing in advance include, for example, a sensitizer for thermal recording, a 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, and a composition of a heat-sensitive recording sensitizer and a dye precursor.

The light absorbing agent used in the optical recording medium of the present invention is obtained by previously dissolving or dispersing the various materials of the optical recording medium of the present invention and the light absorbing agent with a solvent, and dissolving or dissolving the various materials and the light absorbing agent. The dispersion mixture can also be used after separation from the solvent. Examples of the materials for dissolving or dispersing the light absorbing agent in the solvent include those similar to the examples of the materials for dissolving or dispersing the light absorbing agent by previously melting and mixing the light absorbing agent.

Further, the light absorbing agent used in the optical recording medium of the present invention may be used by being co-dispersed (simultaneously mixed and dispersed) with any one of a dye precursor, a color developer and a sensitizer. . Further, the light absorber may be co-dispersed (simultaneously mixed and dispersed) with a dye precursor and a sensitizer or a combination of a color developer and a sensitizer.

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

The amounts of the developer and the dye precursor and the types and amounts of other various components used in the optical recording medium of the present invention 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 for 1 part of the dye precursor, and the binder is suitably used in an amount of 10 to 25% based on the total solid content. The amount of the light absorbing agent to be added is determined according to the light absorbing performance and the like.

Further, in the optical recording medium of the present invention, an overcoat layer of a polymer substance or the like is provided on the recording layer of the optical recording medium for the purpose of enhancing the storability and sensitivity similarly to the thermosensitive recording medium 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. The light absorbing agent may be added to these overcoat layers and undercoat layers.

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

As a light source for performing optical recording on the optical recording medium of the present invention, for example, 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, 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 medium of the present invention. Furthermore, using a mirror etc.
Optical scanning recording may be performed.

Since the heat-sensitive recording medium and the optical recording medium of the present invention have excellent heat resistance and extremely high thermal stability of ground color, a strong protective film can be provided by heat lamination of a plastic film. Therefore, before or after recording with heat or light, etc., by using a plastic film for thermal lamination and a commercially available laminator,
A card protected by a plastic film and having excellent heat resistance and various stability can be easily produced. Especially,
In the case of the optical recording medium of the present invention, additional recording with light is possible from above the laminated plastic film. Examples of the base material of the plastic film for heat lamination include polyethylene terephthalate (PET) and polypropylene (PP). Examples of the heat sealant for the plastic film for heat lamination include low-density polyethylene and ethylene / vinyl acetate. A thermoplastic resin such as a copolymer (EVA), an ethylene / ethyl acrylate copolymer (EEA), an ethylene / methyl methacrylate copolymer (EMAA), and an ethylene / methacrylic acid copolymer (EMAA) can be used.

In addition, the heat-sensitive recording material and the optical recording material of the present invention can be subjected to extrusion coating treatment using an extrusion-coatable resin. Examples of the resin for extrusion coating include various thermoplastic resins useful as the heat sealant and polypropylene (P).
P) and polyethylene terephthalate (PET).

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

[0068]

The reason why the thiourea compound represented by the general formula (1) or (2) of the present invention functions as a developer for a dye precursor used in a thermosensitive recording medium or an optical recording medium, and the dye precursor And the reason why the thermosensitive recording medium composed of the developer of the present invention exhibits extremely high heat resistance, is also an optical recording medium composed of the dye precursor, the developer of the present invention, and the light absorbing agent. Although the reason for the extremely high heat resistance is not clearly understood, it can be considered as follows.

In the aminobenzenesulfonamide derivative of the present invention, a structural change (tautomerism) as shown below may occur depending on conditions. It is considered that these compounds need to have a thiol type structure in order to function as a color developer, and a high temperature is required to cause tautomerism from a thione type to a thiol type.

[0070]

Embedded image

In the case of the thermal recording, since the temperature of the thermal head is instantaneously raised to 200 to 300 ° C. or higher, the general formula (1) or (1) contained in the recording layer of the thermal recording medium which comes into contact with the thermal head. The compound which can be represented by 2) causes tautomerism, becomes a thiol type, and develops a color developing function. Thereby, it is considered that the lactone ring of the dye precursor is cleaved and color is formed. Furthermore, the aminosulfonyl group (—S) of one aromatic ring of the diphenylthiourea skeleton
O ₂ NH ₂ ) is considered to contribute to the promotion of the color developing function and the stabilization of the thiol-type structure. Therefore, it is presumed that dark recording image density and thermal stability of the image and the ground color can be obtained. Is done.

On the other hand, in the case of the optical recording, since the light absorbing agent is present 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 instantaneously rises to 200 to 300 ° C. or higher, the compound of the general formula (1) or (2) contained in the recording layer causes tautomerism similarly to the thermosensitive recording, and the thiol type And a color developing function is developed. Thereby, it is considered that the lactone ring of the dye precursor is cleaved and color is formed.

Further, the compound of the above general formula (1) or (2) does not exhibit a color developer function and does not react with a dye precursor until the temperature changes to a thiol 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 thiolated is considered to be higher than the temperature required for thermal lamination, and therefore, even in a high-temperature thermal environment such as a thermal lamination treatment, the development of the ground color occurs. Never get up.

Further, in the case of the optical recording medium having the above-mentioned structure subjected to the heat lamination, the light emitted from the recording light source is
Since the light passes through the plastic film existing on the optical recording layer, reaches the light absorbing agent in the optical recording layer and is converted into heat, additional recording is possible even after lamination.

[0075]

【Example】

<Production of thermosensitive recording medium; Examples 1 to 18, Comparative Examples 1 to 6>
Hereinafter, the thermosensitive recording medium of the present invention will be described with reference to examples.
In the description, parts and% indicate parts by weight and% by weight, respectively.

[Examples 1 to 10] In Examples 1 to 10, the compound (A-1) was used as a developer in the heat-sensitive recording material of the present invention.
(A-2), (A-4), (A-7), (A-8),
(A-10), any one of (A-12) to (A-15), in which 3-diethylamino-6-methyl-7-anilinofluoran (ODB) is used as a dye precursor. The developer dispersion (solution A) and the dye precursor dispersion (solution B) having the following composition were separately wet-ground using a sand grinder until the average particle diameter became 1 μm. Solution A (Developer dispersion) Developer 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts Water 11.2 parts Solution B (Dye precursor dispersion) 3-Diethylamino-6-methyl-7-ani Linofluoran (ODB) 2.0 parts 10% aqueous solution of polyvinyl alcohol 4.6 parts Water 2.6 parts Next, the dispersion liquid was mixed at the following ratio to obtain a coating liquid. Solution A (Developer dispersion) 36.0 parts Solution B (Dye precursor [ODB] dispersion) 9.2 parts Kaolin clay (50% dispersion) 12.0 parts 50 g / m ^{2 of} each of the above coating solutions After applying to one side of the base paper,
After drying, the sheet is treated with a super calender so that the smoothness is 500 to 600 seconds, and the coating amount is 6.0.
g / m ² was obtained.

[Examples 11 to 14] Examples 11 to 14
Is an example using the compound (A-10) as a color developer and the following dye precursor other than ODB as a dye precursor. (Dye precursor) ODB-2; 3-dibutylamino-6-methyl-7-anilinofluoran Green 40; 3-diethylamino-7- (o-chloroanilino) fluoran PSD-150; 3- (N-cyclohexyl-N -Methylamino) -6-methyl-7-anilinofluoran CVL; 3,3-bis (p-dimethylaminophenyl)
Dye precursor dispersion liquids (liquid C) other than -6-dimethylaminophthalide ODB were separately wet-ground with a sand grinder until the average particle diameter became 1 μm. Solution C (Dye precursor dispersion other than ODB) The above-mentioned dye precursor 2.0 parts 10% aqueous polyvinyl alcohol solution 4.6 parts Water 2.6 parts Next, the dispersion liquid was mixed at the following ratio to obtain a coating liquid. . Solution A (A-10 developer dispersion) 36.0 parts Solution C (dye precursor dispersion other than ODB) 9.2 parts Kaolin clay (50% dispersion) 12.0 parts 50 g of each of the above coating solutions / M ² on one side of the base paper,
After drying, the sheet is treated with a super calender so that the smoothness is 500 to 600 seconds, and the coating amount is 6.0.
g / m ² was obtained.

[Examples 15 and 16] In Example 15, the compound (A-10) was used as a developer, and O was used as a dye precursor.
This is an example using DB and PSD-150. Example 1
And OD, and OD
The dispersion B (liquid B) was treated, and the PSD-150 dispersion (liquid C) was treated in the same manner as in Examples 11 to 14. Liquid A (developer [A-1] dispersion) 36.0 parts Liquid B (dye precursor [ODB] dispersion) 4.6 parts Liquid C (dye precursor [PSD-150] dispersion) 6 parts Kaolin clay (50% dispersion) 12.0 parts After applying each of the above coating liquids to one side of a 50 g / m ² base paper,
After drying, the sheet is treated with a super calender so that the smoothness is 500 to 600 seconds, and the coating amount is 6.0.
g / m ² was obtained. Example 16 shows compound (A-10) as a developer and ODB as a dye precursor.
-2 and PSD-150. Example 1
In the same manner as in Examples 10 to 14, the developer dispersion (Solution A) was treated with the ODB-2 dispersion (Solution C) and the PSD-150 dispersion (Solution C) in the same manner as in Examples 11 to 14. . Solution A (Developer [A-1] dispersion) 36.0 parts Solution C (Dye precursor [ODB-2] dispersion) 4.6 parts Solution C (Dye precursor [PSD-150] dispersion) 4.6 parts Kaolin clay (50% dispersion) 12.0 parts After applying each of the above coating liquids to one side of a 50 g / m ² base paper,
After drying, the sheet is treated with a super calender so that the smoothness is 500 to 600 seconds, and the coating amount is 6.0.
g / m ² was obtained.

[Examples 17 and 18] In Example 11, compounds (A-1) and (A-10) were used as developers.
This is an example in which ODB is used as a dye precursor. In the same manner as in Examples 1 to 10, compound (A-1) and compound (A
-10) The developer dispersion (solution A) and the ODB dispersion (solution B) were treated. Liquid A (developer [A-1] dispersion) 18.0 parts Liquid A (developer [A-10] 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 liquids to one side of a 50 g / m ² base paper,
After drying, the sheet is treated with a super calender so that the smoothness is 500 to 600 seconds, and the coating amount is 6.0.
g / m ² was obtained. Example 18 is an example in which compound (A-10) and bisphenol A (hereinafter, referred to as BPA) were used as a color developer, and ODB was used as a dye precursor (color developer mixture). A developer dispersion (solution A) and an ODB dispersion (solution B) of the compound (A-10) were treated in the same manner as in Examples 1 to 10. Further, a BPA dispersion liquid (D liquid), which is a known developer, was wet-ground by a sand grinder until the average particle diameter became 1 μm. Liquid D (known developer [BPA] dispersion) Bisphenol A (BPA) 6.0 parts 10% aqueous solution of polyvinyl alcohol 18.8 parts Water 11.2 parts Then, the dispersion liquid is mixed in the following ratio to form a coating liquid. And 8. Liquid A (developer [A-10] dispersion) 30.0 parts Liquid D (known developer [BPA] dispersion) 6.0 parts Liquid B (dye precursor [ODB] dispersion) 2 parts Kaolin clay (50% dispersion) 12.0 parts After applying each of the above coating liquids to one side of a 50 g / m ² base paper,
After drying, the sheet is treated with a super calender so that the smoothness is 500 to 600 seconds, and the coating amount is 6.0.
g / m ² was obtained.

[Comparative Examples 1 to 6] Comparative Examples 1 to 6 are examples in which the following known color developers and the various dye precursors shown in Examples 1 to 14 were used as color developers. (Known developer) BPA: Bisphenol A D-8: 4-hydroxy-4'-isopropoxydiphenyl sulfone A thermosensitive recording medium for a comparative example was prepared in the same manner as in Examples 1 to 14. The BPA dispersion (solution D) was treated in the same manner as in Example 18, and the D-8 dispersion (solution D ') was further treated.
Was subjected to wet grinding using a sand grinder until the average particle diameter became 1 μm. D 'solution (known developer [D-8] dispersion) D-8 6.0 parts 10% aqueous solution of polyvinyl alcohol 18.8 parts Water 11.2 parts Then, the dispersions are mixed and applied at the following ratio and coated. Liquid. D solution or D 'solution (known developer dispersion) 36.0 parts B or C solution (dye precursor dispersion) 9.2 parts Kaolin clay (50% dispersion) 12.0 parts After applying each coating solution to one side of a 50 g / m ² base paper,
After drying, the sheet is treated with a super calender so that the smoothness is 500 to 600 seconds, and the coating amount is 6.0.
g / m ² was obtained.

<Evaluation of Thermosensitive Recording Material; Examples 1 to 18, Comparative Examples 1 to 6> The thermosensitive recording materials of Examples 1 to 18 and Comparative Examples 1 to 6 were subjected to a thermal recording test and a thermal stability of ground color. Tests were performed (Table 1 "Recording density and ground color heat stability of heat-sensitive recording materials of Examples 1 to 18" and Table 2 "Recording density and ground color heat stability of heat-sensitive recording materials of Comparative Examples 1 to 6""reference).

[Thermal Recording Test (Dynamic Color Density)] Personal Word Processor Rupo-90FII (manufactured by Toshiba Corporation)
The thermal recording was performed on the thermal recording media of Examples 1 to 18 and Comparative Examples 1 to 6 at the maximum applied energy (the same conditions were used for the thermal recording described below).
The recording density of the recording unit was measured using a Macbeth densitometer (RD-914,
The measurement was carried out under the same conditions using an amber filter. Examples 1 to 18 in which the compound of the present invention was used as a developer
In the heat-sensitive recording medium, a sufficient recording density was obtained by the printer. In Examples using a dye precursor other than black, the value was low because the recording density measurement filter was amber.

[Ground Thermal Stability Test] Using a gear type aging tester (Toyo Seiki Seisaku-sho, Ltd.) at a test temperature of 10
Heat resistance tests at 0 ° C., 120 ° C., and 140 ° C. for 30 minutes each were performed on the thermosensitive recording media of Examples 1 to 18 and Comparative Examples 1 to 6. After the heat resistance test, the density of the ground color was measured with a Macbeth densitometer. In this case, the smaller the value of the Macbeth density, the less the ground color is developed, and the higher the thermal stability of the ground color. Example 1 using the compound of the present invention as a developer
Comparative Examples 1 to 18 have no background recording densities of 0.4 or more after heating at 140 ° C. for 30 minutes and no background color densities of 0.2 or more after heating at 120 ° C. for 30 minutes. All the thermal papers using the phenolic developers of Nos. To 5 already exceeded 0.5 at 100 ° C. for 30 minutes. It can be said that the heat-sensitive recording materials of Examples 1 to 18 have high contrast between the recorded image and the ground color even after 30 minutes at 140 ° C., and exhibit extremely high heat stability.

[0084]

[Table 1]

[Table 2]

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

[Heat Lamination Test] A simple laminating apparatus (MS Pouch H-140, Meiko Shokai) and a laminate film (MS Pouch Film MP10-609)
5) was used. The heat-sensitive recording materials of Examples 1, 4, 6 to 8, 11, 16 to 18, or Comparative Examples 1, 2, and 4 in which the heat-sensitive recording was already performed under the above-described conditions were sandwiched between the laminate films, and the feeding speed was changed. Laminated thermosensitive recording media having a thermosensitive recording section were produced at 20 mm / sec (Examples 19 to 27, Comparative Examples 7 to 9). After the heat laminating treatment, through the laminated film of the laminated heat-sensitive recording material, the color-developed portion by the heat-sensitive recording, and the ground color portion,
It was measured with a Macbeth densitometer (the value is high because it is measured through the film). As for the ground color, the smaller the Macbeth density value, the more stable the ground color. The contrast between the color-developed portion and the ground color of the laminated thermosensitive recording medium due to thermal recording was evaluated as follows. …: There is no ground color development or almost no (thermal lamination possible) △: There is ground color development X: There is remarkable ground color development Reading was difficult, and thermal lamination was practically impossible (Comparative Examples 7 to 9). On the other hand, Examples 19 to 2
With regard to 7, the contrast evaluation was good (）),
Thermal lamination was possible.

[Toner Recording Test Using Electrophotographic Copying Machine] The heat-sensitive recording materials of Examples 1, 4, 6 to 8, 11, 16 to 18 or Comparative Examples 1, 2, and 4 were transferred to an electrophotographic copying machine (Vision 400 Fuji Toner recording was performed on paper (Xerox Co., Ltd.). Based on the degree of ground color development, the potential as an electronic copier paper was evaluated (evaluation of the ground color was the same as the "thermal lamination test"). The thermosensitive recording medium of the present invention (Examples 1, 4, 6 to 8, 11, 16 to 18)
There was almost no ground color, and it could be used as electrophotographic copier paper (Examples 19 to 27).

[0088]

[Table 3]

<Manufacture of Optical Recording Medium; Examples 28 to 32, Comparative Example 10> The optical recording medium of the present invention will be described below with reference to examples. In the description, parts and% indicate parts by weight and% by weight, respectively.

[Examples 28 to 32] Examples 28 to 32
Are compounds (A-1), (A-4), or (A-10) to (A) as a developer in the optical recording medium of the present invention.
-12), bis (1-methyl-3,4-dithiophenolate) nickel tetra-n- as a light absorber
This is an example in which 3-diethylamino-6-methyl-7-anilinofluoran (ODB) is used as a hot melt of butylammonium and a sensitizer, and a dye precursor. Examples 1-4
The developer dispersion (solution A), the dye precursor dispersion (solution B), and the light absorber dispersion (solution E) having the following composition used in
Each was separately wet-ground with a sand grinder until the average particle size became 1 micron. E liquid (light absorber dispersion) 6 parts of bis (1-methyl-3,4-dithiophenolate) nickel tetra-n-butylammonium was added to 94 parts of 4-biphenyl-p-tolyl ether, and 100 parts
The mixture was heated to 150 ° C., melt-mixed, and pulverized to obtain a light absorber. Light absorber 4.0 parts 10% aqueous solution of polyvinyl alcohol 10.0 parts Water 6.0 parts Then, the following dispersions were mixed to form a coating liquid. 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 coating liquids to one side of a 50 g / m ² base paper,
Drying was performed to obtain an optical recording medium having a coating amount of 6.0 g / m ² .

[Comparative Example 10] Comparative Example 10 was a comparative example of bisphenol A (BP) shown in Comparative Examples 1 to 3 as a known developer.
A) Hot melt of bis (1-methyl-3,4-dithiophenolate) nickel tetra-n-butylammonium as light absorber and sensitizer, Example 1 as dye precursor
7 is a comparative example for the optical recording medium of the present invention using ODBs shown in FIGS. A developer dispersion liquid (BPA; D liquid) was prepared in the same manner as in Example 18, and a light absorber dispersion liquid (E liquid) was prepared in the same manner as in Examples 28 to 32. Dye precursor dispersions were prepared in the same manner as in Nos. 1 to 10, and mixed at the following ratios to obtain coating liquids. 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 coating liquid to one surface of a 50 g / m ² base paper,
Drying was performed to obtain an optical recording medium having a coating amount of 6.0 g / m ² .

<Evaluation of Optical Recording Material; Examples 28 to 32 and Comparative Example 10> The optical recording materials of Examples 28 to 32 and Comparative Example 10 were subjected to an optical recording test and a thermal stability test of the ground color ( (See Table 4 "Optical recording density and ground color thermal stability of optical recording media of Examples 28 to 32 and Comparative Example 10").

[Optical Recording Test 1] The optical recording mediums of Examples 28 to 32 or Comparative Example 10 were applied to JP-A-3-23959.
Using a laser plotter described in Japanese Patent Publication No. 8 (1994), laser recording was performed by the following method. As a light source for optical recording,
Semiconductor laser L with oscillation wavelength of 830 nm and output of 30 mW
T015MD (manufactured by Sharp Corporation) was used, and two AP4545 (manufactured by Konica), an aspherical plastic lens having a numerical aperture of 0.45 and a focal length of 4.5 mm, were used as the condenser lens. A laser recording head composed of these semiconductor lasers and lenses is applied at a recording speed of 50 mm / sec.
c, By scanning at a recording line interval of 50 microns, a solid color image of 1 cm square was obtained. The density of the 1 cm square color image was measured with a Macbeth densitometer (RD-914, using an amber filter). This value is shown in “optical recording density 1” in Table 4. In the optical recording media of Examples 28 to 32 using the compound of the present invention as a developer, a sufficient recording density was obtained by the above laser recording.

[Optical Recording Test 2] Optical recording using strobe flash light was performed on the optical recording media of Examples 28 to 32 or Comparative Example 10 by the following method. As an optical recording method, a strobe flash auto4330 for a camera is used.
Light emission was performed by narrowing the emission window (manufactured by Sunpac) to 5%. This color image is converted to a Macbeth densitometer (RD-
914, using an amber filter). This value is shown in “optical recording density 2” in Table 4. In the optical recording media of Examples 28 to 32 in which the compound of the present invention was used as a developer, a sufficient recording density was obtained by the above strobe flash recording.

[Ground Thermal Stability Test (Optical Recording Material)] Similarly to the thermal stability test of the heat-sensitive recording material, a gear aging tester (Toyo Seiki Seisakusho Co., Ltd.) was used at a test temperature of 100.
A heat resistance test at 30 ° C., 120 ° C., and 140 ° C. for 30 minutes was performed on the optical recording media of Examples 28 to 32 and Comparative Example 10. After the heat resistance test, the density of the ground color was measured with a Macbeth densitometer. In this case, the smaller the value of the Macbeth density, the less the ground color is developed, and the higher the thermal stability of the ground color. Example 28 using the compound of the present invention as a developer
The optical recording materials No. to No. 32 do not have a ground color density of 0.4 after 30 minutes at 140 ° C. and a density of 0.25 after 30 minutes of 120 ° C. The optical recording medium using the phenol-based developer of No. 1 already far exceeds 0.4 at 100 ° C. for 30 minutes. The optical recording media of Examples 28 to 32 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.

[0096]

[Table 4] <Thermal lamination and toner recording test; Examples 33 to 3>
7, Comparative Example 11> Next, the optical recording medium of the present invention was subjected to a heat lamination test and a toner recording test with an electrophotographic copying machine as various heat treatment tests (see Table 5, "Examples 28 to 32, Comparative Examples 10) Various heat treatment tests (heat lamination and heat fixing treatment of toner) of the optical recording medium.

[Thermal Lamination Test] A simple laminating apparatus (MS Pouch H-140, Meiko Shokai) and a laminate film (MS Pouch Film MP10-609)
5) was used. Optical recording media of Examples 28 to 32 or Comparative Example 10 in which optical recording (see [Optical Recording Test 1] or [Optical Recording Test 2]) was already performed under the conditions described above, were sandwiched between the laminate films. , Feed speed 20m
At m / sec, laminated optical recording media having an optical recording section were produced (Examples 33 to 37, Comparative Example 11). After the heat laminating treatment, the color-developed portion and the ground-colored portion by the optical recording were measured with a Macbeth densitometer over the laminated film of the laminated optical recording medium. As for the ground color, the smaller the Macbeth density value, the more stable the ground color. The contrast between the colored portion and the ground color of the laminated optical recording medium by optical recording was evaluated as follows. ○…: No background color development, almost no background color (thermal lamination possible) が あ る: Base color development X: ... Significant ground color development Laminated optical recording whose contrast evaluation was × The body was difficult to read and virtually impossible to heat laminate (Comparative Example 11). On the other hand, Examples 33 to
As for No. 37, the contrast evaluation was good (（), and thermal lamination was possible.

[Toner Recording Test with Electrophotographic Copying Machine] Toner recording was performed using the optical recording medium of Examples 28 to 32 or Comparative Example 10 as paper of an electrophotographic copying machine (Vision 400 manufactured by Fuji Xerox Co., Ltd.). Was. Possibility as an electrophotographic copying machine paper was evaluated based on the degree of ground color development (evaluation of the ground color was the same as the "thermal lamination test"). The optical recording medium of the present invention could be used as electrophotographic copying machine paper without causing color development (Examples 33 to 37).

[0099]

[Table 5]

<Optical Additional Recording Test; Examples 38 to 42> [Optical Additional Recording Test (See Table 5)] The laminated optical recording media shown in Examples 33 to 37 were evaluated in terms of optical recording media. "Optical recording test 1" and "optical recording test 2" were performed (Examples 38 to 42). The color image obtained by the optical additional recording was measured for density using a Macbeth densitometer (RD-914, using an amber filter). This value
The results are shown in Table 6 under “Optical additional recording density of laminated optical recording materials of Examples 33 to 37”. All of the laminated optical recording media shown in Examples 33 to 37 can perform laser recording (optical recording test 1) and strobe flash recording (optical recording test 2) through a laminated film, and have a sufficient recording density. Obtained.

[0101]

[Table 6]

[0102]

As described above, the general formula (1)
Alternatively, the heat-sensitive recording material and the optical recording material of the present invention using the compound represented by (2) as a color developer may have 120 to 1
Up to a temperature environment of about 40 ° C., practically sufficient image recording density can be obtained by a thermal recording device such as a thermal head or an optical recording device using a laser or a strobe flash, even though there is almost no fogging of the ground 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.) which could not be used until now. (2) Since the laminator can perform thermal lamination on a recorded thermosensitive recording medium or optical recording medium, a thermosensitive recording card or an optical recording card can be easily manufactured. (3) Optical recording can be further performed on the laminated optical recording medium. (4) Since the ground color is stable even after passing through a heat roll, a thermosensitive recording medium or an optical recording medium can be used as electrophotographic copying machine paper.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Toshiaki Minami 1-30-6 Kamiochiai, Shinjuku-ku, Tokyo Nihon Paper Industries Co., Ltd. Product Development Laboratory (56) References JP-A-6-262856 (JP, A) JP-A-61-27287 (JP, A) JP-A-64-26492 (JP, A) JP-A-2-217287 (JP, A) JP-A-8-59603 (JP, A) JP-B-3-26675 (JP, B2) (58) Field surveyed (Int. Cl. ⁶ , DB name) B41M 5/28-5/34 CA (STN)

Claims (7)

(57) [Claims] 1. A thermosensitive recording medium having a recording layer containing, as a main component, a colorless or pale-colored dye precursor and a color developer which reacts with the dye precursor to form a color on a support. Wherein the developer comprises at least one compound 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. The heat-sensitive recording material according to claim 1, wherein the recording surface or the entire recording material is laminated with a plastic film after the heat-sensitive recording is performed. 3. The optical recording medium according to claim 1, wherein the recording layer of the thermosensitive recording medium contains a light absorbing agent that absorbs light and converts it into heat. 4. An optical recording medium according to claim 3, wherein the recording surface of the optical recording medium or the entire recording medium is laminated with a plastic film. 5. An optical recording medium according to claim 3, wherein said recording surface or said entire recording medium is laminated with a plastic film after thermal recording or optical recording on said optical recording medium. 6. An optical recording method, wherein additional recording is performed on the optical recording medium according to claim 4 with a strobe flash light or a laser light. 7. The heat-sensitive recording medium according to claim 1, or claim 3.
Sheet for an electrophotographic copying machine using the optical recording medium.