JPH11277909A - Thermal recording body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have heat resistance, and improve image preservability by containing at least two kinds of compounds having different sorts shown by a specific formula as a developer. SOLUTION: The thermal recording body is furnished on a carrier with a thermal recording layer containing an achromatic and hypochromic dye precursor by employing a developer as a main component, and the developer contains at least a kind of compound expressed by formula (l), and a kind of a component expressed by formula (2). In the formula, X shows an oxygen atom or a sulfur atom, and R shows a non-substituted or substituted phenyl group, a naphthyl group, an aralkyl group, a cycloalkyl group, or the like. Z shows a 1-6C lower alkyl group, or an electron attractive group, (n) shows integers of 0-4. In the formula (2), R1 , R2 , R3 , R4 can be the same or different, and show hydrogen atoms, 1-4C alkyl groups, and halogen atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to heat resistance, moisture resistance,
The present invention relates to a thermosensitive recording medium having excellent plasticizer 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 increase in recording speed, it is required to obtain a high-density and vivid color image even with a small amount of thermal energy. On the other hand, excellent storage stability such as heat resistance, water resistance, oil resistance and plasticizer resistance is required. A thermal recording sheet is required.

[0004] In recent years, as systems for recording on plain paper such as the electrophotographic system and the ink jet system have become widespread, there have been more opportunities to compare thermal recording with those on plain paper. For example, the stability of the image is the same quality as toner recording,
It is required that the stability of the non-recording area (blank paper or ground color) before and after recording (hereinafter referred to as ground color stability) be close to the quality of plain paper recording. Due to the use of heat-sensitive recording paper as a food label to be performed and the use of heat laminating for use in cards such as lift tickets, there is an increasing demand for ground color stability against heat of 100 ° C. or more.

Accordingly, the present inventors have previously proposed a heat-sensitive recording medium having heat resistance even at a high temperature of 100 ° C. or higher as disclosed in
JP-A-304727, JP-A-8-25810, JP-A-8-53407, JP-A-8-59603, JP-A-8-132939, JP-A-8-290
671, JP-A No. 8-310134 discloses or in JP-A 9-86049 and JP, proposes a heat-sensitive recording material to the amino benzenesulfonamide derivative having an amino sulfonyl group (-SO ₂ NH ₂₎ and developer doing.

When an aminobenzenesulfonamide derivative is used as a color developer, it has been confirmed that it has extremely high heat resistance even at a high temperature of 100 ° C. or more, and that the contrast between the ground color portion and the color-developed portion is high even when heat lamination is performed. Have been. However, since the image storability such as moisture resistance and plasticizer resistance is slightly weak, it was insufficient for long-term storage under severe environments.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-sensitive recording medium which has heat resistance to a certain extent capable of being heat-laminated and has excellent image storability such as moisture resistance and plasticizer resistance. To provide.

[0008]

Means for Solving the Problems The object of the present invention is to provide a thermosensitive recording medium comprising a support having thereon a thermosensitive recording layer containing a colorless or pale color dye precursor and a developer as main components.
This was achieved by including at least one compound represented by the following general formula (1) as the color developer and at least one compound represented by the following general formula (2).

[0009]

Embedded image (Wherein, X represents an oxygen atom or a sulfur atom;
Represents an unsubstituted or substituted phenyl group, naphthyl group, aralkyl group, lower alkyl group having 1 to 6 carbon atoms, cycloalkyl group, or lower alkenyl group having 2 to 6 carbon atoms. Z represents a lower alkyl group having 1 to 6 carbon atoms or an electron-withdrawing group. n represents the integer of 0-4. )

The compound represented by the general formula (1) used in the present invention undergoes a structural change from a neutral structure (a keto-type structure in the case of urea) represented by the general formula by heating to form an acidic structure (urea of urea). In this case, it is considered that the color developing ability is exhibited by changing to an phenolic structure. In the compound represented by the general formula (1), an aminosulfonyl group (-SO
_{It is} sufficient that an aromatic ring having (2NH ₂ ) exists, and it is considered that the aminosulfonyl group contributes to promotion of the color developing function and stabilization of the acidic structure.

Accordingly, R in the general formula (1) is not particularly limited as long as it does not impair the color developing ability and stability. For example, unsubstituted or substituted phenyl, naphthyl, aralkyl, carbon atoms And lower alkyl groups, cycloalkyl groups and lower alkenyl groups having 2-6 carbon atoms. Further, R in the general formula (1) may contain a substituent that does not impair the color development and heat resistance. Examples of the substituent include a lower alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group, a lower alkenyl group such as an isopropenyl group, and an electron-withdrawing group such as fluorine, chlorine, bromine, and a nitro group. . Further, Z in the general formula (1) may be any substituent that does not impair color development and heat resistance. Examples of such a substituent include a lower alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group, or fluorine, chlorine, bromine,
Examples thereof include an electron-withdrawing group such as a nitro group.

[0012]

Embedded image

In the formula, R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different and include a hydrogen atom, a C ₁ -C ₄ alkyl group,
Indicates a halogen atom. As the C ₁ -C ₄ alkyl group,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
Or a tert-butyl group, and examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Among them, a hydrogen atom or a methyl group is preferable, and among them, a hydrogen atom is particularly preferable.

Furthermore, R ₁ and R ₂ or R ₃ and R ₄ may form an aromatic ring bonded to each other, For example, R ₁ and R ₂
Alternatively, a naphthalene ring may be formed together with a benzene ring to which R ₃ and R ₄ are bonded.

X and Y may be the same or different;
Represents an oxygen atom or a sulfur atom. That is, when X is an oxygen atom and Y is also an oxygen atom, when X is an oxygen atom and Y is a sulfur atom, when X is a sulfur atom and Y is an oxygen atom, X is a sulfur atom and Y is also a sulfur atom. Is the case.

Among the compounds represented by the general formula (1), the compound represented by the following general formula (3) has a heat resistance effect,
It is preferably used in view of the availability of synthetic raw materials, economy, reactivity (yield) and the like.

[0017]

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

A thermosensitive recording medium using the compound represented by the general formula (1) as a color developer can be recorded with a thermal head or the like.
It exhibits the characteristic that the ground color is less developed even in a high heat environment of about ° C. The reason why high heat resistance is obtained is not clear, but it is believed that the temperature at which the structural change from the neutral type to the acidic type required to function as a color developer occurs is higher than the temperature used for thermal lamination. Therefore, it is considered that the ground color does not occur even in a high-temperature heat environment such as a heat lamination process. Similarly, even when the toner comes into contact with the heat fixing portion of the toner of the electrophotographic copying machine, the coloring does not occur on the ground. Thermal recording can be performed before or after toner recording by the electrophotographic copying machine.

However, on the other hand, the thermal recording medium using the compound represented by the general formula (1) tends to be decolorized and unstable when exposed to water or moisture. Although the reason for this is not clear, the compound has an aminosulfonyl group and a phenyl (thio) urea group and has a highly polar structure. It is considered that the structural change to the neutral type is likely to occur.

Therefore, the present inventors have conducted intensive studies, and by further containing the compound represented by the general formula (2) in the heat-sensitive recording layer, the resistance to water and moisture can be improved without impairing high heat resistance. The present invention has been found to provide a thermosensitive recording medium having excellent image storability, in which the resistance to a plasticizer and the like is improved as well as the image is not discolored even when it comes into contact with them. . Since the compound represented by the general formula (2) has a plurality of so-called acidified nitrogen atoms having a reduced electron density adjacent to the electron-withdrawing group in the molecule, the chemical bonding force of acid / base increases, As a result, while exhibiting the color developing ability of coloring the dye precursor by the heat melting reaction, it exhibits the effect of stabilizing the recorded image. When the compound represented by the general formula (1) is contained in the heat-sensitive recording layer at the same time as the compound represented by the general formula (1), a fused image of the dye precursor, the developer of the general formula (1) and the compound of the general formula (2) is formed as a recorded image. By forming a charge transfer complex as a complex, a structural change from an acidic type to a neutral type in the compound of the general formula (1) or (3) upon contact with water or a plasticizer is suppressed, It is assumed that the stability of the recorded image is maintained.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to obtain a thermosensitive recording medium of the present invention,
For example, a dispersion in which a dye precursor, an organic developer represented by the general formula (1), and a compound represented by the general formula (2) are respectively dispersed together with a binder is mixed, and a filler, a binder, and other necessary additives are mixed. The heat-sensitive recording layer can be produced by adjusting the coating solution of the heat-sensitive recording layer by adding an agent, coating and drying on a support to form a heat-sensitive recording layer.

The aminobenzenesulfonamide derivative represented by the general formula (1) of the present invention is as disclosed in detail by the present inventors in the above-mentioned JP-A-7-304727, etc. For example, as a synthesis method, it can be produced by reacting an aminobenzenesulfonamide with an isocyanate or an isothiocyanate. That is, in the reaction, 1 mole of aminobenzenesulfonamide is added with 1 to 1 part of an isocyanate or an isothiocyanate.
Add 2.5 moles. The solvent to be used may be any solvent that dissolves aminobenzenesulfonamides, isocyanates, or isothiocyanates, such as aromatic hydrocarbons such as benzene, toluene, and xylene, chloroform, dichloromethane, and chlorobenzene. Such as halogenated 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, dimethylformamide, dimethyl sulfoxide and the like Non-proton-donating polar solvent, alcohols such as methanol and ethanol, or a mixed solvent thereof. Reaction temperature is 0-15
0 ° C, preferably in the range of 20-100 ° C.

Specific examples of the compounds represented by the general formula (1) or (3) used as the organic color developer in the heat-sensitive recording layer are shown below as (A-1) to (A).
-54) or (B-1) to (B-18), but is not limited thereto. Particularly, the compounds represented by the general formula (3) include (A-1) to (A-
8), (A-10) to (A-17), (A-19)
This corresponds to (A-25) or (A-27).

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

The compound represented by the general formula (2) of the present invention can be synthesized by reacting 3-aminobenzenesulfonamide with an isocyanate compound or an isothiocyanate compound. For example, it can be easily obtained by reacting 3-aminobenzenesulfonamide represented by the formula (4) with an isocyanate compound represented by the general formula (5) or an isothiocyanate compound represented by the general formula (6).

[0033]

Embedded image

[0034]

Embedded image R ₅ -NCO (5) (wherein, R ₅ is an unsubstituted monocyclic aromatic ring or a condensed polycyclic aromatic ring (e.g., benzene, naphthalene, etc.), an alkyl group or a halogen C ₁ -C ₄ Represents a monocyclic aromatic ring or a condensed polycyclic aromatic ring substituted with 1 to 2 (see the above).)

[0035]

Embedded image R ₅ -NCS (6) (wherein, R ₅ is an unsubstituted monocyclic aromatic ring or a condensed polycyclic aromatic ring (the foregoing is referenced), or an alkyl group of C ₁ -C ₄ Represents a monocyclic aromatic ring or a condensed polycyclic aromatic ring substituted with 1 to 2 halogen atoms (see the above).

That is, 3-aminobenzenesulfonamide is reacted with an isocyanate compound or an isothiocyanate compound in an organic solvent or a water-containing solvent at a reaction temperature of -10 ° C. to 60 ° C. under neutral conditions to give 3-sulfamoyl (thio). This produces carbanilide compounds. Generated 3-
Without isolating the sulfamoyl (thio) carbanilide compound, an aqueous alkali hydroxide solution was added according to the method described in French Patent No. 994465 to form an alkali metal salt of a 3-sulfamoyl (thio) carbanilide compound, and further, It can be easily produced by reacting with a corresponding isocyanate compound or isothiocyanate compound.

Examples of the isocyanate compound include phenyl isocyanate, toluene isocyanate, diisopropylphenyl isocyanate, chlorophenyl isocyanate, bromophenyl isocyanate, and naphthalene isocyanate. On the other hand, examples of the isothiocyanate compound include phenyl isothiocyanate, toluene isothiocyanate, chlorophenyl isothiocyanate, and the like. Bromophenyl isothiocyanate, naphthalene isothiocyanate and the like can be mentioned.

The organic solvent used in the reaction is acetone, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, dimethylformamide, dimethylsulfoxide, ethyl acetate, methanol and ethanol, preferably acetone, acetonitrile, dimethylformamide and dimethylsulfoxide.

Examples of the alkali hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide.

Specific examples of the compound represented by formula (2) of the present invention include the following compounds, and these compounds may be used alone or in combination of two or more as necessary.

3- (phenylcarbamoylsulfamoyl) carbanilide, 3- (phenylcarbamoylsulfamoyl) thiocarbanilide, 3- (phenylthiocarbamoylsulfamoyl) carbanilide, 3- (phenylthiocarbamoylsulfamoyl) thiocarbanilide, 3 -(P-tolylcarbamoylsulfamoyl) carbanilide, 3- (p-tolylcarbamoylsulfamoyl) thiocarbanilide, 3- (p-tolylthiocarbamoylsulfamoyl) carbanilide, 3- (p-tolylthiocarbamoylsulfamoyl) carbanilide ) Thiocarbanilide, 3- (m-tolylcarbamoylsulfamoyl) carbanilide, 3- (m-tolylcarbamoylsulfamoyl) thiocarbanilide, 3- (m-tolylthiocarbamoylsulfamoyl) ) Carbanilide, 3- (m-tolylthiocarbamoylsulfamoyl) thiocarbanilide, 4-methyl-3 ′-(phenylcarbamoylsulfamoyl) carbanilide, 3-methyl-3 ′-(phenylcarbamoylsulfamoyl) carbanilide, 4 -Methyl-3 '-(phenylthiocarbamoylsulfamoyl) carbanilide, 3-methyl-3'-(phenylthiocarbamoylsulfamoyl) carbanilide, 4-methyl-3 '-(phenylcarbamoylsulfamoyl) thiocarbanilide, 3 -Methyl-3 '-(phenylcarbamoylsulfamoyl) thiocarbanilide, 4-methyl-3'-(phenylthiocarbamoylsulfamoyl)
Thiocarbanilide, 3-methyl-3 ′-(phenylthiocarbamoylsulfamoyl) thiocarbanilide, 3
-(P-chlorophenylcarbamoylsulfamoyl)
Carbanilide, 3- (m-chlorophenylcarbamoylsulfamoyl) carbanilide, 3- (p-chlorophenylthiocarbamoylsulfamoyl) carbanilide,
3- (m-chlorophenylcarbamoylsulfamoyl) thiocarbanilide, 4-chloro-3 ′-(phenylcarbamoylsulfamoyl) carbanilide, 3-chloro-3 ′-(phenylcarbamoylsulfamoyl) carbanilide, 4-bromo-3 '-(Phenylcarbamoylsulfamoyl) carbanilide, 4-chloro-3'-
(P-chlorophenylcarbamoylsulfamoyl) carbanilide, 4-chloro-3 ′-(phenylcarbamoylsulfamoyl) thiocarbanilide, 4-chloro-
3 ′-(phenylthiocarbamoylsulfamoyl) thiocarbanilide, 3- (α-naphthylcarbamoylsulfamoyl) carbanilide, 3- (β-naphthylcarbamoylsulfamoyl) carbanilide, 1- (α-
Naphthyl) -3- (m-phenylcarbamoylsulfamoylphenyl) urea, 3- (α-naphthylthiocarbamoylsulfamoyl) carbanilide, 3- (β-naphthylthiocarbamoylsulfamoyl) carbanilide, 1- (α- Naphthyl) -3- (m-phenylcarbamoylsulfamoylphenyl) thiourea, 1- (β-
Naphthyl) -3- (m-phenylcarbamoylsulfamoylphenyl) thiourea, 1- (α-naphthyl) -3
-(M-α-naphthylcarbamoylsulfamoylphenyl) urea and 1- (α-naphthyl) -3- (m-α-naphthylcarbamoylsulfamoylphenyl) thiourea.

As the dye precursor to be used in the heat-sensitive recording material of the present invention, any known dye precursor in the field of pressure-sensitive or heat-sensitive recording paper can be used, and is not particularly limited. Compounds, fluorane 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 Malachite green lactone] <Fluoran leuco dye> 3-Diethylamino-6-methylfluoran 3-Diethylamino-6-methyl-7-anilinofluoran 3-Diethylamino-6-methyl-7- (o, p-dimethyl Anilino) fluorane 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 Le-7- (p-chloroanilino) fluoran 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluoran 3-diethylamino-6-methyl-7-n-octylanilinofluoran 3-diethylamino-6 -Methyl-7-n-octylaminofluoran 3-diethylamino-6-methyl-7-benzylanilinofluoran 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-anilinofur Oran 3-diethylamino-7-methylfluoran 3-diethylamino- -Chlorofluoran 3-diethylamino-7- (m-trifluoromethylanilino) fluoran 3-diethylamino-7- (o-chloroanilino) fluoran 3-diethylamino-7- (p-chloroanilino) fluoran 3-diethylamino-7- (O-fluoroanilino) fluoran 3-diethylamino-benzo [a] fluoran 3-diethylamino-benzo [c] fluoran 3-dibutylamino-6-methyl-fluoran 3-dibutylamino-6-methyl-7-anilinofur Oran 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-dibutyl Amino-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-methylanilinofluoran 3- Dibutylamino-7- (o-chloroanilino) fluoran 3-dibutylamino-7- (o-fluoroanilino) fluoran 3-n-dipentylamino-6-methyl-7-anilinofluoran 3-n-dipentylamino- 6-methyl-7- (p-chloroanilino) fluoran 3-n-dipentylamino-6-chloro-7-ani Linofluoran 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- (N-ethyl-N-isobutylamino) -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)
Aminoanilinofluoran 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 which form a dye precursor can be replaced by the general formula (1) or It can be used in combination with the compound represented by (3). 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. Examples of such a developer include, for example, JP-A-3-207688.
, 4-hydroxybenzoic acid esters, 4-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 4-Isopropyl benzoate 4 -Butyl hydroxybenzoate 4-Isobutyl 4-hydroxybenzoate Methylbenzyl 4-hydroxybenzoate <Dimethyl 4-hydroxyphthalates> Dimethyl 4-hydroxyphthalate 4-Diisopropyl 4-hydroxyphthalate 4-Dibenzyl 4-hydroxyphthalate 4-hydro Dihexyl phthalate <monoesters of phthalic acid> 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'-propoxydiphenylsulfone4-hydroxy-4'-n-butyloxydiphenylsulfone 4- 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-hydroxy Phenyl-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 Butyl 4-hydroxybenzoyloxybenzoate Isopropyl 4-hydroxybenzoyloxybenzoate tert-butyl 4-hydroxybenzoyloxybenzoate hexyl 4-hydroxybenzoyloxybenzoate octyl 4-hydroxybenzoyloxybenzoate 4-h Nonyl roxybenzoyloxybenzoate Cyclohexyl 4-hydroxybenzoyloxybenzoate β-phenethyl 4-hydroxybenzoyloxybenzoate Phenyl 4-hydroxybenzoyloxybenzoate α-Naphthyl 4-hydroxybenzoyloxybenzoate β-Hydroxybenzoyloxybenzoate β -Naphthyl sec-butyl 4-hydroxybenzoyloxybenzoate <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'-hydroxyphenylsulfone 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<Bisphenolsulfones(II)>4,4'-Sulfonyldiphenol2,4'-Sulfonyldiphenol3,3'-Dichloro-4,4'-sulfonyldiphenol 3, 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-tolyl ether, m-terphenyl, 1,2-diphenoxyethane, dibenzyl oxalate, di (p-chlorobenzyl) oxalate, di (p-methylbenzyl) oxalate, Dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, phenyl-α-naphthyl carbonate, 1,4-diethoxynaphthalene, 1
-Hydroxy-2-naphthoic acid phenyl ester, o-
Xylerin-bis- (phenyl ether), 4- (m-
Examples thereof include, but are not particularly limited to, methylphenoxymethyl) biphenyl. These sensitizers may be used alone or in combination of two or more.

As the binder used in the heat-sensitive recording layer of the present invention, completely saponified polyvinyl alcohol having a polymerization degree of 200 to 1900, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol Alcohol, modified polyvinyl alcohol such as butyral modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as acetyl cellulose, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, polyvinyl chloride, poly (vinyl chloride) Vinyl acetate, polyacrylamide, polyacrylate,
Examples thereof include polyvinyl butyral, polystyrene and copolymers thereof, polyamide resin, silicone resin, petroleum resin, terpene resin, ketone resin, and cumarone resin. These high-molecular substances can be used by dissolving them in solvents such as water, alcohols, ketones, esters, and hydrocarbons.Also, they can be used in emulsified or paste-like form in water or other media. You can also.

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

The fillers that can be used in the heat-sensitive recording layer of the present invention include silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide,
Examples include inorganic or organic fillers such as zinc oxide, aluminum hydroxide, polystyrene resin, urea-formalin resin, styrene-methacrylic acid copolymer, styrene-butadiene copolymer, and hollow plastic pigment.

In addition, release agents such as fatty acid metal salts, lubricants such as waxes, 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 layer 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,
1 to 8 parts of the developer represented by the general formula (1), and the general formula (2)
0.25 to 3 parts of a compound represented by the formula (1) and a filler of 1 to 20 parts are used, and an appropriate binder is 10 to 25% of the total solid content. In particular, when the compound of the general formula (2) is used in an amount of from 0.08 part to less than 1 part with respect to 1 part of the compound represented by the general formula (1), the heat resistance and the effect of stabilizing the image area are preferably high.

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.

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. A desired heat-sensitive recording medium can be obtained by applying a coating solution for a heat-sensitive recording layer having the above composition to any of these supports. The coating amount of the heat-sensitive recording layer coating liquid is ² to 12 g / m ² , preferably 3 to 10 g in dry weight.
It is adjusted in the range of about g / m ² . Further, an undercoat layer may be provided for the purpose of improving color sensitivity, and a protective layer may be provided for the purpose of improving storability.

[0054]

EXAMPLES <Synthesis example of compound represented by general formula (2)> [Synthesis example 1] Synthesis of 3- (phenylcarbamoylsulfamoyl) carbanilide 500 ml of 4- (4) equipped with a stirrer, a cooler and a thermometer. 17.2 g of 3-aminobenzenesulfonamide and 200 ml of acetonitrile were charged into a flask with stirring and dissolved. Next, 11.9 g of phenyl isocyanate dissolved in 50 ml of acetonitrile was added dropwise over 1 hour while maintaining the liquid temperature at 20 ° C. Thereafter, the reaction was carried out for 6 hours to produce 3-sulfamoylcarbanilide. Without isolating the formed 3-sulfamoylcarbanilide, 42 g of a 10% aqueous sodium hydroxide solution was added to the reaction solution, and the mixture was stirred for 1 hour. Then, 11.9 g of phenyl isocyanate dissolved in 50 ml of acetonitrile was added dropwise over 1 hour. Then, the reaction was carried out for 6 hours. After completion of the reaction, acetonitrile was distilled off under reduced pressure, and 200 g of water and 100 ml of ethyl acetate were added to the concentrated residue to extract unreacted substances, and the aqueous layer was separated. When the aqueous solution was acidified with hydrochloric acid, white crystals were precipitated. The crystals were collected by filtration and recrystallized from ethyl acetate to obtain 34 g of white crystals having a melting point of 197 to 199 ° C. It was confirmed from infrared spectroscopy, mass spectrometry and elemental analysis that the white crystals were 3- (phenylcarbamoylsulfamoyl) carbanilide.

Synthesis Example 2 Synthesis of 3- (phenylcarbamoylsulfamoyl) thiocarbanilide In the reaction between 3-aminobenzenesulfonamide and phenylisocyanate in Synthesis Example 1, 13.5 g of phenylisothiocyanate was used instead of phenylisocyanate. A melting point of 170 to 17
25 g of 2 ° C. white crystals were obtained. From infrared spectroscopy, mass spectrometry and elemental analysis, it was confirmed that the white crystal was 3- (phenylcarbamoylsulfamoyl) thiocarbanilide.

Synthesis Example 3 Synthesis of 3- (phenylthiocarbamoylsulfamoyl) carbanilide The same reaction as in Synthesis Example 1 was performed to produce 3-sulfamoylcarbanilide, and then phenylisocyane was used instead of phenylisocyanate. The same operation as in Synthesis Example 1 was performed except that 13.5 g of thiocyanate was used, to obtain 25 g of white crystals having a melting point of 165 to 168 ° C. From infrared spectroscopy, mass spectrometry and elemental analysis, it was confirmed that the white crystal was 3- (phenylthiocarbamoylsulfamoyl) carbanilide.

<Manufacture of Thermal Recording Medium> Examples 1 to 5 and Comparative Examples 1 to 7 Hereinafter, the thermal 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.
The developers used in the thermosensitive recording materials of the present example and the comparative example include compounds (A-1), (A-10) and (A-1).
9), bisphenol A or 4-hydroxy-4′-isopropoxydiphenyl sulfone. or,
Examples of the stabilizer used in the thermosensitive recording materials of the present example and the comparative example include the compounds shown in the above Synthesis Examples 1 to 3, and N- (p
-Toluenesulfonyl) -N '-(p-tolyl) urea;
N- (p-methoxybenzenesulfonyl) -N′-phenylurea.

A developer dispersion (solution A), a dye precursor dispersion (solution B), and a stabilizer dispersion (solution C) each having the following composition were separately prepared by a sand grinder to an average particle diameter of 1 μm. Wet grinding was carried out until complete. Liquid A (Developer dispersion liquid) Developer 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts Water 11.2 parts Liquid B (Dye precursor dispersion liquid) 3- (N-ethyl-N-isoamylamino) ) -6-Methyl-7-anilinofluoran 2.0 parts 10% aqueous polyvinyl alcohol solution 4.6 parts water 2.6 parts Liquid C (stabilizer dispersion) Stabilizer 2.0 parts 10% aqueous polyvinyl alcohol solution 2 .5 parts water 1.5 parts

[Examples 1 to 5] Dispersions were mixed at the following ratios to obtain coating liquids. Liquid A (see Table 1) 36.0 parts Liquid B 9.2 parts Liquid C (see Table 1) 6.0 parts Kaolin clay (50% dispersion) 12.0 parts The above coating liquid was used at a base of 50 g / m ² . 6.0 g on one side of paper
/ M ² and dried, and this sheet was treated with a super calender so that the smoothness was 500 to 600 seconds to produce a thermosensitive recording medium.

[Comparative Examples 1 to 3] The heat-sensitive recording materials of Examples 1 to 5 were prepared in the same manner as in Examples 1 to 5, except that a dispersion was mixed at the following ratio to form a coating solution. Obtained. Liquid A (see Table 2) 36.0 parts Liquid B 9.2 parts Kaolin clay (50% dispersion) 12.0 parts

[Comparative Examples 4 to 7] The heat-sensitive recording materials of Examples 1 to 5 were prepared in the same manner as in Examples 1 to 5, except that dispersions were mixed at the following ratios to form coating liquids. Obtained. Liquid A (see Table 2) 36.0 parts Liquid B 9.2 parts Liquid C (see Table 2) 6.0 parts Kaolin clay (50% dispersion) 12.0 parts

<Evaluation of Thermosensitive Recording Materials; Examples 1 to 5, Comparative Examples 1 to 7> The thermal recording properties of Examples 1 to 5 and Comparative Examples 1 to 7 Moisture resistance and plasticizer resistance tests were performed (see Tables 1-4).

[Thermal Recording Test (Dynamic Color Density)] Using an Okura Electric Co., Ltd. TH-PMD (thermal recording paper printing tester, equipped with a Kyocera thermal head), at an applied energy of 0.41 mj / dot. Thermal recording was performed on the produced thermal recording medium (the same conditions were used for the following thermal recordings).
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. In the thermosensitive recording materials of Examples 1 to 5 of the present invention, a sufficient recording density was obtained by a printer. In addition, the same measurement was performed on the uncolored portion.

[Background Thermal Stability Test] Using a gear type aging tester (Toyo Seiki Seisakusho), a test temperature of 10
Heat resistance tests at 0 ° C. and 120 ° C. for 30 minutes each were performed on the heat-sensitive recording media of Examples 1 to 5 and Comparative Examples 1 to 7. 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. Actual thermal lamination is usually 100-140 ° C, feed rate 1-10
Since it is performed at 0 mm / sec, Examples 1 to 5 of the present invention
It is shown that the heat-sensitive recording material of Example 1 has sufficiently high contrast between the recorded image and the ground color even after the heat lamination process.

[Moisture Resistance Test] The printer (0.4
1 mj / dot) at 40 ° C. 9
After leaving for 24 hours in an environment of 0% RH, the Macbeth density of the image area and the ground color area was measured. Examples 1 to 5 of the present invention
In the heat-sensitive recording material of No. 4, decolorization of the recorded image was hardly recognized.

[Plasticizer resistance test] A vinyl chloride wrap (Hi-wrap KMA manufactured by Mitsui Toatsu) was wrapped around a paper tube in a single layer, and a thermosensitive recording medium recorded by the printer (0.41 mj / dot) was pasted thereon. Further, a layer obtained by winding PVC wrap three times thereon was left at 40 ° C. for 72 hours, and then the Macbeth density of the image area was measured. In the heat-sensitive recording materials of Examples 1 to 5 of the present invention, the recorded images almost remained.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

[0070]

[Table 4]

[0071]

As described above, the heat-sensitive recording material of the present invention has almost no ground color fog even under a high temperature environment of about 120 ° C., and has excellent storage stability of the image area such as moisture resistance and plasticizer resistance. And an image recording density sufficient for practical use with a thermal recording apparatus such as a thermal head. The effects of the present invention include the following. (1) A thermosensitive recording medium can be used under severe temperature conditions (for example, 100 to 120 ° C.). (2) Thermal lamination can be performed by a laminator. (3) Since the ground color is stable even after passing through a heat roll, it can be used as electrophotographic copying machine paper. (4) Decoloring of an image hardly occurs even after long-term storage.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Kaoru Hamada 1-30-6 Kamiochiai, Shinjuku-ku, Tokyo Japan Paper Manufacturing Co., Ltd.

Claims (3)

[Claims] 1. A thermosensitive recording medium comprising a support and a thermosensitive recording layer containing a colorless or pale-colored dye precursor and a developer as main components, wherein the developer has the following general formula (1): A thermosensitive recording medium comprising at least one compound represented by the following formula (1) and at least one compound represented by the following general formula (2). Embedded image (Wherein, X represents an oxygen atom or a sulfur atom;
Represents an unsubstituted or substituted phenyl group, naphthyl group, aralkyl group, lower alkyl group having 1 to 6 carbon atoms, cycloalkyl group, or lower alkenyl group having 2 to 6 carbon atoms. Z represents a lower alkyl group having 1 to 6 carbon atoms or an electron-withdrawing group. n represents the integer of 0-4. ) (Wherein, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and represent a hydrogen atom, a C ₁ -C ₄ alkyl group, a halogen atom, and R ₁ and R ₂ or R ₃ And R ₄ may combine with each other to form an aromatic ring; X and Y may be the same or different and each represent an oxygen atom or a sulfur atom.) 2. The heat-sensitive recording material according to claim 1, wherein said developer contains at least one compound represented by the following general formula (3). Embedded image (In the formula, Y represents a lower alkyl group having 1 to 6 carbon atoms or an electron-withdrawing group. M represents an integer of 0 to 3.) 3. The thermosensitive recording layer according to claim 1, wherein the general formula (2)
The compound represented by the formula (1) is used as a stabilizer in an amount of from 0.08 part by weight to 1 part of the compound represented by the formula (1) or (3).
The thermosensitive recording medium according to claim 1, wherein the thermosensitive recording medium contains less than 10 parts by weight.