JP2001001646A - Sensitizer for developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sensitizer for a specific developer which shows a superb coloring density and an outstanding storage stability of an uncolor developed part and a printed part by using the sensitizer, as shown by a specific structural formula, for the developer selected from the group of an isocyanate-state compound and an urea urethane compound. SOLUTION: The developer is a chemical compound which does not develop a color for itself but is capable of making a dye precursor develop a color through a chemical reaction with the dye precursor having a color developing ability. The developer to be used is the one selected from the group of an isocyanate compound and an urea urethane compound. The sensitizer has neither a practical color developing power nor a practical developing power itself but has a function to augment the color developing sensitivity of the dye precursor by using it with the dye precursor and the developer. The sensitizer for the specific developer to be used is the one as shown by a formula for this purpose. Thus it is possible to enhance the sensitivity and upgrade the keeping stability of the texture and the printed part.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive agent, a pressure-sensitive agent, and the like which develop color by heat, pressure, and the like, and a sensitizer which can be used for a recording material using the same. In particular, the present invention relates to a specific sensitizer for a color developer, which has improved coloration sensitivity, uncolored portion (background), and storage stability of a printed portion. The invention also relates to a thermosensitive recording material using the same.

[0002]

2. Description of the Related Art Heretofore, many chemical color developing systems using recording energy such as heat and pressure have been known. Among them, a color forming system composed of a two-component color forming system of a colorless or pale color dye precursor and a color developer which reacts with the dye precursor to form a color has been known for a long time and widely applied to recording materials. ing. For example, there are a pressure-sensitive recording material using pressure energy, a heat-sensitive recording material using heat energy, and a photosensitive recording material using light energy.

In recent years, for example, various information devices such as facsimile machines, printers, recorders, and the like have come to employ a heat-sensitive recording system in which recording is performed using thermal energy. These heat-sensitive recording materials have many excellent properties such as high whiteness, good appearance and feel close to plain paper, good recording suitability such as color sensitivity, and the like. It has the advantages of maintenance-free, no noise, etc., measurement recorder, facsimile, printer, computer terminal, label,
Its applications have been expanded to a wide range of fields such as automatic ticket vending machines such as tickets. The mainstream of these recording methods is to use a recording material in which a color-forming layer containing a two-component heat-sensitive agent is provided on a support, and to apply heat as recording energy thereto with a heat-sensitive head, a hot stamp, a laser beam, or the like. By
In this method, the heat-sensitive agent components are brought into contact with each other on a recording material to perform color recording. Above all, many use a colorless or light-colored electron-donating dye precursor (particularly a leuco dye) and an acidic developer such as a phenolic compound as the heat-sensitive agent. Recording materials using these leuco dyes are represented by, for example, heat-sensitive paper using crystal violet lactone and 4,4′-isopropylidenediphenol (bisphenol A) as heat-sensitive agents (see US Pat. No. 3,539,375). You.

As the dye precursor and the color developer used for these, an electron-donating compound and an electron-accepting compound are mainly used, respectively. This is because the reactivity of the dye precursor, which is the electron-donating compound, is high, and by contacting with the developer, which is the electron-accepting compound, a color-developed image having a high density can be obtained instantaneously. This is because they have excellent characteristics such as obtaining a close appearance and obtaining various color hues such as red, orange, yellow, green, blue and black. However, on the other hand, the obtained color-developed image has poor chemical resistance, so that it comes into contact with a plasticizer contained in a plastic sheet or an eraser or a chemical contained in food or cosmetics, and the record is easily lost, or , The light resistance of the recording part is inferior, so that the recording fades or disappears after a relatively short exposure to sunlight,
It has the disadvantage that the storage stability of the record is poor.

[0005] A heat-fusible substance (sensitizer) is generally used to accelerate the reaction between the dye precursor and the developer. The coloring sensitivity can be improved by using a heat-fusible substance in combination. However, on the other hand, the heat resistance of the uncolored portion (skin) of the obtained image is reduced, so that the background is colored and the storage stability of the record is maintained even in a temperature environment that can be exposed to daily use, such as a temperature in a private car in midsummer. At present, there is a certain restriction on the use of the device due to these disadvantages, and improvement thereof is strongly desired.

Japanese Patent Publication No. 4-6558 discloses a thermosensitive recording having a thermosensitive coloring layer containing a general color developing substance represented by a leuco dye and bisphenol A and a diphenyl sulfone compound as a thermofusible substance. Materials are disclosed. However, when a developer such as bisphenol A and a diphenyl sulfone compound are used in combination, not only the sensitivity of the heat-sensitive recording material is low, but also the heat resistance of the background is inferior and the storage stability of the recording is insufficient.

In addition, JP-A-9-207444 discloses a thermosensitive coloring layer containing a basic dye and a specific urea derivative or thiourea derivative as an organic developer, and containing a diphenyl sulfone compound as a sensitizer. There is disclosed a heat-sensitive recording material having: In addition, Japanese Patent Application Laid-Open No. 5-507
No. 66 discloses a heat-sensitive recording material having a heat-sensitive coloring layer containing a leuco dye, dihydroxydiphenylsulfones as a color developer, and a specific chlorinated diphenylsulfone-based compound as a sensitizer.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a specific sensitizer for a color developer which is excellent in color density, uncolored area (background) and storage stability of a printed area.
Another object is to provide a thermosensitive recording material using the same.

[0009]

Means for Solving the Problems As a result of intensive studies on sensitizers for various color developers, the present inventors have found that when a specific compound is combined with a specific color developer, the compound becomes a surprising sensitizer. The present inventors have found that excellent performance should be exhibited, and have completed the present invention. That is, the present invention is as follows. A first aspect of the present invention is a sensitizer represented by the following structural formula (I) for a developer selected from the group consisting of an isocyanate compound and a urea urethane compound.

[0010]

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(Where Y is -SO ₂ -,-(S) _n -,-
O -, - CO -, - CH (C 6 H 5) -, - C (CH 3) 2
-, - COCO -, - CO 3 -, - COCH 2 CO -, -
Shows any of NH-. n is 1 or 2. Further, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue. A second aspect of the invention is the sensitizer according to the first aspect, wherein the sensitizer is represented by the following structural formula (II).

[0012]

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(The hydrogen atom of the benzene ring in the formula may be substituted with an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue.) A third aspect of the present invention is the first aspect of the present invention. A heat-sensitive recording material comprising a support and a heat-sensitive color-developing layer containing the developer described in (1) and a sensitizer according to the first or second aspect of the invention for the color developer.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The color developer referred to in the present invention refers to a compound which does not form a color by itself, but can form a dye precursor by reacting with a dye precursor having a coloring ability, such as a leuco dye. It must be any color developer selected from the group consisting of isocyanate compounds and urea urethane compounds. In particular, it is preferable to use a urea urethane compound as a color developer because a recording material of high sensitivity and clear printing can be obtained and the printing storability is excellent.

The isocyanate compound which can be used as a color developer can be appropriately selected from colorless or pale-colored isocyanate compounds which are solid at normal temperature, and is not particularly limited. For example, one or more of the following isocyanate compounds are used. 2,6-dichlorophenyl isocyanate, p-chlorophenyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-dimethylbenzene-4,6-diisocyanate, 1,4 -Dimethylbenzene-2,5-diisocyanate, 1-methoxybenzene-2,4-diisocyanate, 1-methoxybenzene-2,5-diisocyanate, 1-ethoxybenzene-2,4-diisocyanate , 2,5-dimethoxybenzene-1,4-diisocyanate, 2,5-diethoxybenzene-1,4-
Diisocyanate, 2,5-dibutoxybenzene-1,
4-diisocyanate, azobenzene-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, naphthalene-1,4-diisocyanate,
Naphthalene-1,5-diisocyanate, naphthalene-
2,6-diisocyanate, naphthalene-2,7-diisocyanate,

3,3'-dimethyl-biphenyl-4,
4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, benzophenone-
3,3'-diisocyanate, fluorene-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, bilen-3,8-di Isocyanate, naphthalene-1,3,7-triisocyanate, biphenyl-
2,4,4'-triisocyanate, 4,4 ', 4 "-
Triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ', 4 "-triisocyanatotriphenylamine, 4,4'-diisocyanato-2,5dimethoxytriphenylamine, 4,4', 4" -Triisocyanato-2,5-diethoxytriphenylamine, p-dimethylaminophenylisocyanate, tris (4-phenylisocyanato) thiophosphate and the like. These isocyanates may optionally contain phenols,
It may be used in the form of a so-called block isocyanate, which is an addition compound with lactams, oximes and the like.

In particular, it is preferable to use an isocyanate adduct compound having a melting point of 40 ° C. or higher as the isocyanate compound from the viewpoints of color sensitivity and storage stability. The isocyanate adduct compound is a colorless or pale color solid at room temperature, and preferably has a melting point of 40 ° C. or more and 500 ° C. or less. However, depending on the structure of the compound, it may be decomposed or deteriorated at a temperature lower than the melting point and show no melting point, but in this case, there is no problem in performance as long as the decomposing or changing temperature is 40 ° C. or higher. The melting point is preferably at least 50 ° C, more preferably at least 60 ° C. When the melting point of the adduct compound is less than 40 ° C., when it is used as a heat-sensitive agent, problems are likely to occur in heat resistance and moisture resistance, which are often not practically preferable.

The isocyanate adduct compound is obtained by reacting at least one isocyanate group of the isocyanate with a reactive group and dimerizing the isocyanate with water through a urea bond or a biuret bond to form a dimer or trimer.
A method for quantification, a method for derivatization to a corresponding substituted urea or a substituted biuret by an addition reaction with an amine compound, a method for dimerization by heat, or a method for derivatization to a substituted urethane or a substituted allohanate by an addition reaction with an OH group-containing compound Or an addition reaction with a compound having an active hydrogen. Further, an isocyanate adduct compound obtained by carrying out any of the above-mentioned reactions using an isocyanate adduct compound obtained by the above method such as carbodiimide-modified MDI or polyol-modified MDI as a starting material may be used.

The isocyanate as a starting material is not particularly limited as long as it has two or more isocyanate groups. For example, paraphenylene diisocyanate, 2,5-
Dimethoxybenzene-1,4-diisocyanate, 2,
4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o
-Tolidine diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,
3′-dimethyl-4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate 4,4 ′, 4 ″ -triisocyanatotriphenylamine, triphenylmethane triisocyanate, tris ( 4-phenylisocyanate) thiophosphate and the like.

Particularly, the isocyanate compound is represented by the following formula (II)
It is preferable to be an isocyanate adduct represented by I) or the following formula (IV) or an isocyanate compound represented by the following formulas (V) to (XIV).

[0021]

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(Where n represents an integer of 1 to 2. The hydrogen atom of the benzene ring may be substituted by an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent.)

[0023]

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(Wherein m is an integer of 0 to 5, n is 1 or 2. Further, the hydrogen atom of the benzene ring is substituted by an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent, and X ₁ and X ₂ are each independently -SO
_{2 -, - O -, -} (S) q -, - (CH 2) q -, - CO
-, - CONH -, - CH (C 6 H 5) -, - C (C
H ₃ ) ₂ — or none. q
Is 1 or 2. )

[0025]

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(Where R ₁ represents formula (a) or formula (b). The same applies to formulas (VI) to (XIV) below.

[0027]

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(Where n represents an integer of 1 to 2. The hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent.)

[0029]

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(Wherein m is an integer of 0 to 5, n is 1 or 2. The hydrogen atom of the benzene ring is substituted by an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue may have a substituent, and X ₁ and X ₂ are each independently -SO
_{2 -, - O -, -} (S) q -, - (CH 2) q -, - CO
-, - CONH -, - CH (C 6 H 5) -, - C (C
H ₃ ) ₂ — or none. q
Is 1 or 2. ))

[0031]

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[0032]

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(R ₂ represents an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Each residue may have a substituent. The following formula (VIII)
Same in (IX) and (X). )

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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(R ₃ represents an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue. Each residue may have a substituent.)

[0040]

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(R ₄ is an aromatic compound residue which may have a substituent, a heterocyclic compound residue which may have a substituent or an aliphatic compound residue or an inorganic compound residue which may have a substituent. Represents a group.)

[0042]

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(R ₅ and R ₆ each independently represent an aromatic compound, a heterocyclic compound, or an aliphatic compound residue. Each residue may have a substituent. R ₅ and R ₆ May form a cyclic structure with each other.) The adduct compound of an aromatic isocyanate represented by the above formula (III) refers to an isocyanate represented by the above formula (III), preferably toluene diisocyanate as a starting material Is an isocyanate compound having at least one isocyanate group obtained by performing an addition reaction using at least one isocyanate group of the toluene diisocyanate as a reactive group.

The toluene diisocyanate is 2,4
-Toluene diisocyanate and 2,6-toluene diisocyanate are generally commercially available, and can usually be obtained at low cost as a mixture thereof. However, these toluene diisocyanate isomer mixtures are liquid at room temperature (100% 2,4-toluene diisocyanate, melting point 19.5 ° C. to 21.5 ° C., 2,4-toluene diisocyanate 65%). / 35% mixture of 2,6-toluene diisocyanate at a melting point of 3.5 ° C. to 5.5 ° C.
° C), it is practically difficult to use this form as a heat-sensitive agent.

The isocyanate adduct compound represented by the above formula (IV) is an aromatic isocyanate represented by the above formula (IV) or polymethylene polyphenyl polyisocyanate (hereinafter referred to as cr.MDI) or A new isocyanate compound obtained by performing an addition reaction to diphenylmethane diisocyanate (hereinafter, MDI). The above cr. MDI or MDI is generally commercially available and can usually be obtained at low cost. However, for example, cr. MDI is a normal-temperature brown liquid, and MDI has a freezing point of 38 ° C. There is a practical problem in using MDI as it is as a heat-sensitive agent.

The isocyanate adduct compound is an isocyanate compound represented by the above formula (III), in particular, toluene diisocyanate, an aromatic isocyanate represented by the above formula (IV) or cr. It is an isocyanate compound containing at least one isocyanate group obtained by performing an addition reaction using at least one isocyanate group of an isocyanate such as MDI or MDI as a reactive group. That is, the isocyanate adduct compound that can be used in the present invention is an isocyanate compound represented by the above formula (III), particularly toluene diisocyanate, an aromatic isocyanate represented by the above formula (IV) or c
r. A method in which at least one isocyanate group of an isocyanate such as MDI or MDI is used as a reactive group, and the isocyanate is dimerized or trimerized through a urea bond or a biuret bond by reaction with water, or is added to an amine compound. A method of deriving to a corresponding substituted urea or substituted biuret by a reaction, a method of dimerization by heat, a method of deriving to a substituted urethane or a substituted allohanate by an addition reaction with an OH group-containing compound, or other active hydrogen It can be obtained by a method of addition reaction with a compound or the like. Further, an isocyanate adduct compound obtained by further performing any one of the above-mentioned reactions using the isocyanate adduct compound obtained by the above method as a starting material may be used. That is, by using this technology,
By increasing the melting point to 40 ° C. or higher by increasing the molecular weight, heat resistance, moisture resistance, etc. are improved, and there is no practical problem as a heat sensitive agent, and excellent performance can be exhibited.

The aromatic isocyanate compound represented by the above formula (III) according to the present invention may be any compound having two or more NCO groups on the benzene ring.
-Phenylene diisocyanate, m-phenylene diisocyanate, toluene diisocyanate, 1,3-dimethylbenzene-4,6-diisocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1- Methoxybenzene-2,5-diisocyanate, 1-ethoxybenzene-2,4-diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,5-
Diethoxybenzene-1,4-diisocyanate, 2,
5-dibutoxybenzene-1,4-diisocyanate and the like. Particularly preferred is toluene diisocyanate, which may be 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or a mixture thereof.

The aromatic isocyanate represented by the above formula (IV) according to the present invention is, for example, dianisidine diisocyanate, diphenyl ether diisocyanate, orthotrizine diisocyanate, bis [4- (m
-Isocyanatophenoxy) phenyl] sulfone, bis [4- (p-isocyanatophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-isocyanatophenoxy) phenyl] sulfone, 3,3'-dimethoxy-
4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 2,2 '
-Dichloro-4,4'-diisocyanato-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diisocyanatobiphenyl, 2,4'-
Diisocyanato biphenyl, 2,2'-diisocyanato biphenyl, 4,4'-diisocyanato biphenyl,
2,2'-dichloro-4,4'-diisocyanatobiphenyl, 3,3'-dichloro-4,4'-diisocyanatobiphenyl, 2,2'-dimethyl-4,4'-diisocyanatobiphenyl 4,4'-diisocyanatodiphenyl ether, 3,3'-diisocyanatodiphenylether, 3,4'-diisocyanatodiphenylether,
3,4'-diisocyanatodiphenylmethane,

Bis (3-isocyanato-4-chlorophenyl) sulfone, bis (3,4-diisocyanatophenyl) sulfone, bis (4-isocyanatophenyl) sulfone, bis (3-isocyanatophenyl) sulfone,
3,4'-diisocyanatodiphenyl sulfone, 3,
3'-diisocyanatodiphenylmethane, 4,4'-diisocyanato-3,3'-dichlorodiphenylmethane,
1,4-bis (4-isocyanatophenoxy) benzene, 1,3-bis (4-isocyanatophenoxy) benzene, 1,3-bis (3-isocyanatophenoxy) benzene, 2,2-bis (4- Isocyanatophenoxyphenyl) propane, 4,4'-bis (4-isocyanatophenoxy) diphenyl, 3,3 ', 4,4'-tetraisocyanatodiphenyl ether, 3,3', 4,4 '
-Tetraisocyanatodiphenylsulfone and the like. These aromatic isocyanate or polymethylene polyphenyl polyisocyanate (cr.MDI) or diphenylmethane diisocyanate (MDI) may be used alone or in a mixture thereof.

As the reactant for forming these isocyanate adducts, for example, aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-
Dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol,
p-aminophenol, 2,3-xylysine, 2,4-
Xylidine, 3,4-xylidine, 2,6-xylidine, acetanilide, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N- Ethyl aniline, N-propyl aniline, N-
Butylaniline, acetoacetic anilide, trimethylphenylammonium bromide, 4,4'-diamino-3,
3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenylether, 3,3'-dichloro-4,
4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine,

Methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p-aminobenzoate
-Iso-propyl aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-
Aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p -(N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) Aniline, 2-methoxy-5- [N-
(2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy- 4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N
-Ethyl-N-phenylaminosulfonyl) aniline,
4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline,

Sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4 -N-
Phenylsulfamoylaniline, 2-methoxy-5
Benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl]
Sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, , 3'-Dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4 , 4'-diaminobiphenyl, ortho-tolidine sulfone, 2,
4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diamino Biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl,

4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4 '
-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4 '
-Diaminodiphenylmethane, bis (3-amino-4-
(Chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, 3,4′-
Diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4-diaminodiphenylamine,
4,4'-ethylenedianiline, 4,4'diamino-
2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone,
1,4-bis (4-aminophenoxy) benzene, 1,
3-bis (4-aminophenoxy) benzene, 1,3-
Bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4
-Aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, 3,3 ',
4,4'-tetraaminodiphenyl ether, 3,
3 ', 4,4'-tetraaminodiphenyl sulfone,
3,3'4,4'-tetraaminobenzophenone, 3-
Aminobenzonitrile, 4-phenoxyaniline, 3-
Phenoxyaniline, 4,4′-methylenebis-O-toluidine, 4,4 ′-(p-phenyleneisopropylidene) -bis- (2,6-xylidine),

O-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-
Amino-4-chlorophenol, o-nitroaniline,
m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine,
2-amino-5-nitrobenzonitrile, methol,
2,4-diaminophenol, p-hydroxyphenylglycine, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanylic acid, 4B
Acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,
4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3′-dichlorobenzidine,
4,4′-diaminostilbene-2,2′-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, tobias acid, H acid, J acid,
Phenyl J acid,

1,4-diamino-anthraquinone,
Aromatic amines such as 4-diamino-2,3-dichloroanthraquinone, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine,
-Aminopyridine, α-amino-ε-caprolactam,
Acetoguanamine, 2,4-diamino-6- [2′-methylimidazolyl- (1)] ethyl-S-triazine,
2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4
-Methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-
Heterocyclic compounds such as aminopropyl) morpholine amines, methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3
-(2-ethylhexyloxy) propylamine, 3-
Ethoxypropylamine, diisobutylamine, 3-
(Diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, t-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxy Propylamine, methylhydrazine, 1-methylbutylamine, methanediamine,
1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-
Propanol, 2-aminobutanol, 3-amino-
Aliphatic amines such as 1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol,

Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-
Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid-1,2,2,6,6-pentamethyl-4-piperidinol β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecanediethanol condensate,
3,4-butanetetracarboxylic acid ・ 2,2,6,6-tetramethyl-4-piperidinol ・ β, β, β ′, β ′
-Tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecanediethanol condensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino- 1,3,5-triazine-2,4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2,6,6-tetramethyl-4- Piperidyl) imino}], N, N'-bis (3-aminopropyl) ethylenediamine-2,4-
Bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,
3,5-triazine condensate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid-bis (1,2,2,6,6-pentamethyl-4 −
Hindered amine compounds such as piperidyl) and succinic acid-bis (2,2,6,6-tetramethyl-4-piperidienyl) ester.

Examples of the OH group-containing compound as a reactant for forming an adduct include phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-phenol. Octylphenol, 2-
Cyclohexylphenol, 2-allylphenol, 4
-Indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane,
2,2-bis (hydroxyphenyl) pentane, 2,2
-Bis (hydroxyphenyl) heptane, catechol,
3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone,
-Phenylphenol, p, p'-biphenol, 4-
Phenols such as cumylphenol (However, those having an amino group are not preferred in these phenols. When an amino group is present, the amino group reacts first because the reactivity with the isocyanate group is higher than that of the OH group. However, the desired adduct compound cannot be obtained.),

Methanol, ethanol, propanol,
Butanol, pentanol, hexanol, heptanol, octanol, isopropanol, 2-pentanol, 3-hexanol, tert-butanol, ter
t-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-
Methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, phenylcellosolve, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin , Alcohols such as glycerol, polypropylene glycol, polytetramethylene ether glycol,
Polyether polyols such as adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenolic polyol, amine modified polyol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2- Propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexaneglycol, 1,9-nonanediol, acrylic polyol, fluorine polyol , Polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, Pentaerythritol, castor oil-based polyol, polymer polyol, methyl pentanediol, halogen-containing polyols, phosphorus-containing polyols,
There are polyols such as ethylenediamine, α-methylglucoside, sorbitol, and souce.

Other compounds having active hydrogen which reacts with isocyanate include dimethyl malonate, diethyl malonate, ethyl acetoacetate, butyl mercaptan, thiophenol, tert-dodecyl mercaptan, acetanisidide, acetate amide, benzamide, p-toluene sulfone Amide, o-toluenesulfonamide, p-chlorobenzenesulfonamide, benzenesulfonamide,
Hydrazine, hydroxylamine, succinimide, maleimide, acetanilide, imidazole, methyl ethyl ketoxime, acetoaldoxime, sodium bisulfite, urea, ammonia, 3-iminoisoindoline, imino compounds such as iminobenzophenone, piperidine, ethyleneimine And imine compounds such as piperazine.

In the production of the isocyanate adduct compound according to the present invention, the reaction can be carried out without solvent, but it is preferable to use a solvent. The solvent used is one that dissolves the isocyanate and dissolves the reactants to some extent. After mixing and reacting the reactant with the isocyanate in an organic solvent or in the absence of a solvent, the surplus isocyanate is removed by filtration or distillation under reduced pressure to obtain the desired product. A single or a plurality of reactants may be used depending on the purpose. The solvent may be any one that does not cause a reaction with the isocyanate group and the functional group of the reactant. Examples thereof include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and chlorinated aliphatic hydrocarbons. Organic solvents such as hydrogen, chlorinated aromatic hydrocarbons, and chlorinated alicyclic hydrocarbons are exemplified. Particularly, cyclohexane, ethylcyclohexane, toluene and the like, which dissolve the isocyanate and have low solubility of the product, are preferable.
The product obtained by the above reaction operation is not necessarily a single product, and a mixture of a compound having different substituent positions, a mixture of a substituted urea and a substituted biuret, a mixture of a substituted urethane and a substituted allohanate, and further addition reaction proceeds to increase the product. It may be obtained as a mixture of those having a molecular weight, but this is also acceptable. The target product can also be obtained by further reacting the reactants with the product obtained by the above reaction operation as a starting material.

The amount of the reactant used for the isocyanate varies greatly depending on the solubility of the reactant in the reaction solvent. Reactants that can dissolve the required amount in the reaction solvent
An amount of the reactant corresponding to the NCO group of the isocyanate may be used. However, in the case of a reactant having a low solubility in the reaction solvent, the reactant is excessively added to the solvent, and the reactant dissolved in the solvent is added. When the agent reacts with the isocyanate and is lost from the solvent, a new reactant may be dissolved in the solvent and contribute to the reaction. Therefore, the reactants in the solvent can be mixed in excess of the isocyanate.

The melting point of the isocyanate adduct compound thus obtained may be 40 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher. If the melting point of the adduct compound is less than 40 ° C., when it is used as a heat-sensitive agent, problems are likely to occur in heat resistance, moisture resistance and the like, which is not preferable in practical use. The upper limit of the melting point is 500
C. or less is preferred. However, depending on the structure of the compound,
In some cases, it decomposes or degrades at a temperature lower than the melting point and does not show a melting point, but in this case, there is no problem in performance as long as the temperature at which the decomposition or degeneration is at or above the lower limit of the melting point.

These isocyanate compounds may be added to phenols, lactams, oximes and the like, if necessary, to mask the isocyanate, and dissociate when heated to regenerate the isocyanate. It may be used in the form of isocyanate. The isocyanate compound, the isocyanate adduct compound or the isocyanate compound represented by the formulas (V) to (XIV) according to the present invention is a colorless or pale color solid at room temperature. In preparing the thermosensitive recording material, one type or a mixture of the isocyanate compound, the isocyanate adduct compound or the isocyanate compounds represented by the formulas (V) to (XIV) is used. You can also.

The isocyanate compounds represented by the formulas (V) to (XIV) can be obtained by subjecting the corresponding amine compound to a phosgene reaction to produce an isocyanate. It is possible. When used as an isocyanate adduct compound, it is preferable that 30% or more of the isocyanate is an adduct, and it is preferable that 50% or more of the isocyanate is an adduct. Further, it is preferable that 80% or more is an adduct body.

The urea urethane compound that can be used as a color developer may be any compound as long as it has a urea group (—NHCONH—) and a urethane group (—NHCOO—) in the molecule. It is preferably a heterocyclic compound. More preferably, the urea group (-
NHCONH-group) and urethane group (-NHCOO- group)
In addition, it is desirable that a sulfone group (—SO ₂ — group) or an anilide group (—NHCO— group) be present without directly bonding to a urea group.

The method for synthesizing the urea urethane compound according to the present invention is not particularly limited as long as a urea group (—NHCONH— group) and a urethane group (—NHCOO— group) can be formed. The method of making the compound by reaction with the compound and the amine compound is easy and preferable.
That is, the urea urethane compound according to the present invention is obtained by using an isocyanate having at least two or more isocyanate groups as a starting material, and excluding at least one isocyanate group of the isocyanate and an isocyanate group and an OH group-containing compound. React to form urethane groups,
Next, the remaining isocyanate group can be reacted with the amine compound to form a urea group. Alternatively, a urea group may be formed by reacting an isocyanate group with an amine compound, and then a urethane group may be formed by reacting the remaining isocyanate group with an OH group-containing compound.

The starting isocyanate is not particularly limited as long as it has two or more isocyanate groups. For example, paraphenylene diisocyanate, 2,5-
Dimethoxybenzene-1,4-diisocyanate, 2,
4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o
-Tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate,
Dianisidine diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3′-dimethyl-
4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate,
4,4 ′, 4 ″ -triisocyanato-2,5-dimethoxytriphenylamine, 4,4 ′, 4 ″ -triisocyanatotriphenylamine, metaxylylene diisocyanate, lysine diisocyanate, hexa Methylene diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl isocyanate,
Dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, and the like.

A diisocyanate dimer, for example, N, N ′ (4,
4'-dimethyl 3,3'-diphenyl diisocyanate) uretdione (trade name Desmodur TT) and trimers such as 4,4'4 "-trimethyl 3,3 ', 3"
-Triisocyanate 2,4.6-triphenyl cyanurate and the like. Water adduct isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-
(Methylphenyl) urea or a polyol adduct, for example, a trimethylolpropane adduct (trade name Desmodur L) of toluene diisocyanate, an amine adduct, or the like may be used. Further, the isocyanate compound and the isocyanate adduct compound described in Japanese Patent Application Nos. 8-225445 and 8-250623 may have two or more isocyanate groups.

A particularly preferred example is toluene diisocyanate. The toluene diisocyanate is preferably 2,4-toluene diisocyanate.
A mixture of 6-toluene diisocyanate is generally commercially available and can be obtained at low cost, but this is also acceptable. These toluene diisocyanate isomer mixtures are liquid at room temperature. The amine compound for forming a urea group by reacting with an isocyanate which is a starting material of a urea urethane compound may be any compound having an amino group, for example, aniline, o-toluidine, m-
Toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethyl-p-
Phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-
Aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine,
3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine,
2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o
-Chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N
-Propylaniline, N-butylaniline,

Acetoacetic anilide, trimethylphenylammonium bromide, 4,4'-diamino-3,3'-
Diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenylether, 3,3'-dichloro-4,4'-
Diaminodiphenylmethane, 3,3′-dimethyl-4,
4'-diaminodiphenylmethane, tolidine base, o
-Phenylenediamine, m-phenylenediamine, p-
Phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, p-
Ethyl aminobenzoate, n-propyl p-aminobenzoate, -iso-propyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, p
-Benzyl aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4 -Methylbenzamide,
3-amino-4-methoxybenzamide, 3-amino-
4-chlorobenzamide,

P- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl]
Aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N-
(2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy- 4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N
-Ethyl-N-phenylaminosulfonyl) aniline,
4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline,

Sulfathiazole, 4-aminodiphenylsulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4 -N-
Phenylsulfamoylaniline, 2-methoxy-5
Benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl]
Sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, , 3'-Dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4 , 4'-diaminobiphenyl, ortho-tolidine sulfone, 2,
4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diamino Biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl,

4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4 '
-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4 '
-Diaminodiphenylmethane, bis (3-amino-4-
Chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 3,
4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3 ' -Diaminobenzophenone, 4,4'-diaminobenzophenone,
1,4-bis (4-aminophenoxy) benzene, 1,
3-bis (4-aminophenoxy) benzene, 1,3-
Bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4
-Aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, 3,3 ',
4,4'-tetraaminodiphenyl ether, 3,
3 ', 4,4'-tetraaminodiphenyl sulfone,
3,3'4,4'-tetraaminobenzophenone, 3-
Aminobenzonitrile, 4-phenoxyaniline, 3-
Phenoxyaniline, 4,4′-methylenebis-o-toluidine, 4,4 ′-(p-phenyleneisopropylidene) -bis- (2,6-xylidine),

O-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-
Amino-4-chlorophenol, o-nitroaniline,
m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine,
2-amino-5-nitrobenzonitrile, methol,
2,4-diaminophenol, p-hydroxyphenylglycine, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanylic acid, 4B
Acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,
4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3′-dichlorobenzidine,
4,4′-diaminostilbene-2,2′-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, tobias acid, H acid, J acid,
Phenyl J acid,

1,4-diamino-anthraquinone,
Aromatic amines such as 4-diamino-2,3-dichloroanthraquinone, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine,
-Aminopyridine, α-amino-ε-caprolactam,
Acetoguanamine, 2,4-diamino-6- [2′-methylimidazolyl- (1)] ethyl-S-triazine,
2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4
-Methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-
Heterocyclic compounds such as aminopropyl) morpholine amines, methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3
-(2-ethylhexyloxy) propylamine, 3-
Ethoxypropylamine, diisobutylamine, 3-
(Diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, t-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxy Propylamine, methylhydrazine, 1-methylbutylamine, methanediamine,
1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-
Propanol, 2-aminobutanol, 3-amino-
Aliphatic amines such as 1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol,

Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-
Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid-1,2,2,6,6-pentamethyl-4-piperidinol β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecanediethanol condensate,
3,4-butanetetracarboxylic acid ・ 2,2,6,6-tetramethyl-4-piperidinol ・ β, β, β ′, β ′
-Tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecanediethanol condensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino- 1,3,5-triazine-2,4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2,6,6-tetramethyl-4- Piperidyl) imino}], N, N'-bis (3-aminopropyl) ethylenediamine-2,4-
Bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,
3,5-triazine condensate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid-bis (1,2,2,6,6-pentamethyl-4 −
Hindered amine compounds such as piperidyl) and succinic acid-bis (2,2,6,6-tetramethyl-4-piperidienyl) ester.

Further, among the above amine compounds, an aniline derivative having at least one amino group represented by the following formula (XV) is particularly preferable.

[0078]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, halogen, an alkyl group, an alkoxy group or an amino group, and X ₁ and X ₂ represent an amino group or a formula (C)

[0080]

Embedded image

Y ₁ is —SO ₂ —, —O—, — (S) _n —,
— (CH ₂ ) _n —, —CO—, —CONH—, any one of formulas (d),

[0082]

Embedded image

Or, the case where it does not exist is shown. n is 1 or 2. ) Further, as the OH group-containing compound which reacts with isocyanate to form a urethane group, any compound having an OH group may be used. For example, phenol, cresol, xylenol, p-ethylphenol, o-
Isopropylphenol, resorcinol, p-tert-
Butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol,
p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane,
2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, bis ( 4-hydroxyphenyl) butyl acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-) (Hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenylsulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-isopropyl Oxyphenyl- 4'-hydroxyphenylsulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-isopropylphenyl-4'-hydroxyphenylsulfone, 4-hydroxy-4 '-Isopropoxydiphenyl sulfone, bis (2
-Methyl-3-tert. -Butyl-4-hydroxyphenyl) sulfide;

4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxydiphenylmethane 3,3′-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy) phenyl) sulfone, 2,4-dihydroxybenzophenone,
2,2 ′, 4,4′-tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxybenzoic acid (4′-chlorobenzyl), 1,2 -Ethyl bis (4'-hydroxybenzoate), 1,5-bis (4'-hydroxybenzoic acid) pentyl, 1,6-bis (4'-hydroxybenzoic acid) hexyl, dimethyl 3-hydroxyphthalate, gallic Stearyl acid, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyloxy) phenol,
-Hydroxybenzaldehyde and the like. Examples of salicylic acid derivatives include 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid,
Phenols such as -n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, and 4-n-octanoyloxycarbonylaminosalicylic acid; can give. (However,
Those having an amino group are not preferred among these phenols. When the amino group coexists, the reactivity with the isocyanate group is higher than the OH group, so the amino group reacts first,
In some cases, it is difficult to obtain the desired compound. )

Further, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, 2-pentanol, 3-hexanol, tert-butanol, t
ert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol,
2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, phenylcellosolve, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane ,
Alcohols such as glycerin and glycerol, polyether polyols such as polypropylene glycol, polytetramethylene ether glycol, adipate polyol, epoxy modified polyol, polyether ester polyol polycarbonate polyol, polycaprolactone diol, phenol polyol, and amine modified polyol , Ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 6-hexane glycol, 1,9-nonanediol, acrylic polyol, fluorine polyol, polybutadiene polyol, polyhydroxypoly Lumpur, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor oil-based polyol, polymer polyol, methyl pentanediol, halogen-containing polyols, phosphorus-containing polyols,
And polyols such as ethylenediamine, α-methylglucoside, sorbitol, and souce.

In order to obtain the urea urethane compound according to the present invention, the desired product can be obtained by mixing and reacting the isocyanate with the reactant in an organic solvent or without a solvent, and then removing the crystals by filtration. A single or a plurality of reactants may be used depending on the purpose. The solvent may be any solvent as long as it does not react with the isocyanate group and the functional group of the reactant, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatics. Examples include hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, and the like. In particular, methyl ethyl ketone, toluene, and the like, which dissolve the isocyanate and have low solubility of the product, are preferable. The product obtained by the above reaction operation is not necessarily a single product, and may be obtained as a mixture of compounds having different substituent positions, but may be used.

Among the urea urethane compounds thus obtained, urea urethane compounds of the following formulas (XVI) to (XXI) are preferred, and more preferred are those of the formula (X
VII) to (XXI), and particularly preferred are compounds of formulas (XX) to (XXI).

[0088]

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(Here, X, Y, and Z each represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Each residue may have a substituent.)

[0090]

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(X and Y each represent an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue. Each residue may have a substituent.)

[0092]

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(Wherein X and Y represent an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue. Α
Represents a residue having a valence of 2 or more, and n represents an integer of 2 or more. Further, each residue may have a substituent. )

[0094]

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(Where Z and Y each represent an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue. Β
Represents a residue having a valence of 2 or more, and n represents an integer of 2 or more. Further, each residue may have a substituent. )

[0096]

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(Here, the hydrogen atom of the benzene ring may be substituted by an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue has a substituent. Γ is -SO _2- , -O-,-(S)
_{n -, - (CH 2)} n -, - CO -, - CONH-, or of formula (d),

[0098]

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Or, the case where it does not exist is shown. n is 1 or 2. )

[0100]

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(Here, the hydrogen atom of the benzene ring may be substituted by an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. Each residue has a substituent. Δ is -SO _2- , -O-,-(S)
_{n -, - (CH 2)} n -, - CO -, - CONH -, - N
_{H -, - CH (COOR 1} ) -, - C (CF 3) 2 -, -
CR ₂ R ₃ — indicates either the absence or absence of CR ₂ R ₃ —.
R ₁ , R ₂ and R ₃ each independently represent an alkyl group, and n is 1 or 2. The urea urethane compound according to the present invention is a colorless or pale-colored compound which is usually a solid at room temperature. The molecular weight of the urea urethane compound is preferably 5,000 or less, more preferably 2,000 or less.

In the heat-sensitive recording material, a compound having a melting point is preferable, and the melting point is preferably from 40 ° C. to 5 ° C.
The temperature is preferably 00 ° C, particularly preferably in the range of 60 ° C to 300 ° C. The total number of urea groups and urethane groups in the urea urethane compound is preferably 20 or less, and more preferably 10 or less. The ratio of the urea group to the urethane group is preferably from 1: 3 to 3: 1, and particularly preferably from 1: 2 to 2: 1.

As the color developer, a phenol derivative, an aromatic carboxylic acid derivative or a metal salt thereof, a salicylic acid derivative or a metal salt thereof, a sulfonylurea derivative, or the like can be used in combination, if necessary, as long as the effects of the present invention are not impaired. . Next, the sensitizer according to the present invention has neither practical color developing ability nor color developing ability by itself, but increases the color developing sensitivity of the dye precursor by using it together with the dye precursor and the color developing agent. It has the function of exercising. The specific sensitizer for a developer according to the present invention has the following structural formula (I).

[0104]

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(Where Y is -SO ₂ -,-(S) _n -,-
O -, - CO -, - CH (C 6 H 5) -, - C (CH 3) 2
-, - COCO -, - CO 3 -, - COCH 2 CO -, -
Shows any of NH-. n is 1 or 2. Further, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue. The use of a developer composition obtained by combining the above-mentioned specific developer and the sensitizer represented by the above formula (I) in a heat-sensitive recording material improves the sensitivity, and improves the background and printing. The storage stability of the part can be improved.

The sensitizer for a heat-sensitive color former represented by the above formula (I) preferably has a melting point of 60 ° C. to 180 ° C.
Particularly, those having a melting point of 80 ° C to 140 ° C are preferable.
Representative examples of the sensitizer for a thermal color former represented by the above formula (I) include 4,4'-dimethoxybenzophenone, diphenylsulfone, diphenyldisulfide, diphenylamine, 2-methyl-4-methoxydiphenylamine, N , N'-diphenyl-p-phenylenediamine,
1- (N-phenylamino) naphthalene, benzyl,
1,3-diphenyl-1,3-propanedione and the like can be mentioned. Of these, compounds represented by the following structural formula (II) are preferred, and diphenyl sulfone is particularly preferred.

[0107]

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(The hydrogen atom of the benzene ring in the formula may be substituted with an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue.) In particular, the compound represented by the structural formula (II) Has excellent functions as a sensitizer when a urea urethane compound is used as a developer. The specific sensitizer for a developer represented by the above formula (I) may be used alone or in combination of two or more.

The specific sensitizer for a developer represented by the above formula (I) is preferably used in an amount of 10 to 1000% by weight, more preferably 40 to 500% by weight, based on the developer. 10% by weight or more of a specific sensitizer for a color developer is sufficient to improve sensitivity, and the color density is high. When the sensitizer is 1000% by weight or less, an excessive sensitizer hardly remains, which is economically advantageous and preferable. In the heat-sensitive recording material using the sensitizer of the present invention, any one of the above-described specific developers, the sensitizer for the developer, and a colorless or A light-colored dye precursor is used. By using a colorless or light-colored dye precursor and a specific color developer that reacts with the color developer at the time of heating to form a color and a sensitizer for the color developer in the heat-sensitive recording material, the sensitivity is improved, In addition, the background and the storage stability of printing can be improved.

The colorless or light-colored dye precursor according to the present invention is a compound already known as a heat-sensitive color former, and is not particularly limited. Examples thereof include the following. (1) Triarylmethane compound 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3- ( p-dimethylaminophenyl) -3-
(1,2-dimethylindol-3-yl) phthalide,
3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindole-
3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole-3-
Yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5 -Dimethylaminophthalide, 3-p
-Dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide and the like.

(2) Diphenylmethane compounds 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, N-halophenylleucouramine, N-2,4,5-trichlorophenylleucouramine and the like.

(3) Xanthene compounds rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-octylaminofluoran, 3- Diethylamino-7-phenylfluoran, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-chloro-7-methylfluoran, 3-diethylamino-7- (3,4-dichloroanilino) fluoran, 3 -Diethylamino-7
-(2-chloroanilino) fluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- (N
-Ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino-6 Methyl-7-phenethylfluoran, 3-diethylamino-7- (4-nitroanilino) fluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-propyl) amino-
6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-cyclohexyl) amino-6 Methyl-7-anilinofluoran, 3
-(N-ethyl-N-tetrahydrofuryl) amino-6
-Methyl-7-anilinofluoran and the like.

(4) Thiazine compounds Benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue and the like. (5) Spiro compound 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3-methoxybenzo) Spiropyran, 3-propylspirobenzopyran and the like.

Further, 3,6-bis (dimethylamino) fluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3′- (6′-dimethylaminophthalide), 3,6-bis (diethylamino) fluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9- Spiro-3 ′-(6′-dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluorene-9-spiro-3 ′-(6′-dimethylaminophthalide), 3,6-bis (dimethylamino) ) Fluorene-9-spiro-3 '-(6'-diethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3'-(6'-di Butylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3 ′-(6′-diethylaminophthalide), 3,6-bis (diethylamino) fluorene-9-spiro-3′- (6′-diethylaminophthalide), 3,6-bis (dimethylamino) fluorene-9
-Spiro-3 '-(6'-dibutylaminophthalide),
3-dibutylamino-6-diethylaminofluorene-
9-spiro-3 '-(6'-diethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3'-(6'-dibutylaminophthalide), 3,3-bis [2 -(4-Dimethylaminophenyl) -2- (4-methoxyphenyl) ethenyl]-
Compounds having an absorption region in the near infrared, such as 4,5,6,7, -tetrachlorophthalide.

Among these dye precursors, the leuco dye represented by the following formula (XXII) is particularly preferred because of its excellent color developing sensitivity and storage stability of the background.

[0116]

Embedded image

(Wherein, Y ₁ and Y _{2 each} represent an alkyl group or an alkoxyalkyl group having 2 or more carbon atoms. Y ₃ represents any one of an alkyl group, an alkoxyalkyl group, hydrogen, and a halogen atom. Y ₄ , Y ₅ is a hydrogen atom, a halogen atom,
Shows any of an alkyl group, an alkoxy group and a halogenated carbon group. The colorless or light-colored dye precursors may be used alone or in combination of two or more.

The colorless or pale color dye precursor is preferably used in an amount of 20 to 2,000% by weight, more preferably 30 to 500% by weight, based on the developer. When the colorless or pale color dye precursor is 20% by weight or more, it reacts with the developer and is sufficient to improve the sensitivity, and the coloring density is high. Also,
When the amount of the dye precursor is 2000% by weight or less, an excessive amount of the dye precursor hardly remains, which is economically advantageous and preferable.

Further, in order to improve the background fogging and the heat responsiveness, N-stearyl-N ′-(2-hydroxyphenyl) urea, N-stearyl-N ′-(3-hydroxyphenyl) urea, N-stearyl-N ′-(3-hydroxyphenyl) urea Stearyl-N ′-(4-hydroxyphenyl) urea, p-stearoylaminophenol, o-stearoylaminophenol, p-lauroylaminophenol, p-butyrylaminophenol, m-acetylaminophenol, o-acetylaminophenol, p-acetylaminophenol, o-butylaminocarbonylphenol, o-stearylaminocarbonylphenol, p-stearylaminocarbonylphenol, 1,1,3-tris (3-tert.
-Butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tris (3-tert.-butyl-4)
-Hydroxy-6-ethylphenyl) butane, 1,1,
3-tris (3,5-di-tert.-butyl-4-hydroxyphenyl) butane, 1,1,3-tris (3-
tert. -Butyl-4-hydroxy-6-methylphenyl) propane, 1,2,3-tris (3-tert.
-Butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tris (3-phenyl-4-hydroxyphenyl) butane, 1,1,3-tris (3-cyclohexyl-4-hydroxy-5) -Methylphenyl) butane, 1,1,3-tris (3-cyclohexyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-
Tetra (3-phenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetra (3-cyclohexyl-
4-hydroxy-6-methylphenyl) propane, 1,
1-bis (3-tert.-butyl-4-hydroxy-
It is also possible to add phenol compounds such as 6-methylphenyl) butane and 1,1-bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) butane.

A heat-sensitive composition containing these dye precursor, a specific color developer and the specific sensitizer for a color developer represented by the above formula (I) of the present invention is subjected to some methods such as coating. By forming a heat-sensitive layer on the body, a heat-sensitive recording material can be obtained. Specifically, a color developer selected from the group consisting of a colorless or light-colored dye precursor such as the above-mentioned leuco dye, an isocyanate compound, and a urea urethane compound; It is necessary to apply the sensitizer in the form of a dispersion to a support together with other necessary components to form a heat-sensitive recording layer. The dispersion can be prepared by finely pulverizing one or more of these compounds in an aqueous solution containing a compound having a dispersing ability such as a water-soluble polymer or a surfactant using a sand grinder or the like. . The particle diameter of each dispersion is preferably 0.1 to 10 μm, particularly preferably about 1 μm.

In addition, the thermosensitive recording layer contains diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin and the like as pigments. You can also. In addition, for the purpose of preventing head abrasion and sticking, zinc stearate, higher fatty acid metal salts such as calcium stearate, paraffin,
Waxes such as paraffin oxide, polyethylene, polyethylene oxide, stearic acid amide, caster wax, etc .; dispersants such as dioctyl sodium sulfosuccinate; ultraviolet absorbers such as benzophenone and benzotriazole; surfactants and fluorescent dyes Etc. can be contained as needed.

Examples of the binder that can be used for forming the heat-sensitive recording layer include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, acrylamide / acrylic acid. Water-soluble binders such as ester copolymers, acrylamide / acrylate / methacrylic acid terpolymers, styrene / maleic anhydride copolymer alkali salts, ethylene / maleic anhydride copolymer alkali salts, and styrene Latex-based water-insoluble binders such as styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, and methyl acrylate / butadiene copolymer.

As the support for the heat-sensitive recording layer, paper is mainly used. In addition to paper, various woven fabrics, nonwoven fabrics, synthetic resin films, laminated paper, synthetic paper, metal foil, or composite sheets obtained by combining these are used. It can be used arbitrarily according to the purpose. The thermal recording layer may be composed of a single layer or a plurality of layers. For example, each color forming component may be contained one layer at a time to form a multilayer structure. Further, a protective layer composed of one layer or a plurality of layers may be provided on the heat-sensitive recording layer, or a protective layer may be provided between the support and the heat-sensitive recording layer.
A layer or an intermediate layer composed of a plurality of layers may be provided. This heat-sensitive recording layer can be obtained by mixing each aqueous dispersion obtained by finely pulverizing each color-forming component or other components, a binder and the like, applying the mixture on a support, and drying. The coating amount is 1 to 15 g /
m ² is preferred.

Further, the heat-sensitive recording material according to the present invention may contain a hindered phenol compound or an ultraviolet absorber in the recording layer. For example, 1,1,3-tris (3′-cyclohexyl-4′hydroxyphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′- Thiobis (3-methyl-6-tert-butylphenol),
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, p-octylphenyl salicylate, 2
-(2'-hydroxy-5'-methylphenyl) benzotriazole, ethyl-2-cyano-3,3'-diphenylacrylate, tetra (2,2,6,6-tetramethyl-4-piperidyl) 1,2 , 3,4-butanetetracarboate and the like.

Hereinafter, the present invention will be described in more detail by way of examples.
I will tell. In addition, each physical property was evaluated by the following methods. <Color sensitivity of thermal paper>
The head uses Kyocera's KJT-256-8MGF1
24 V applied voltage and 1.5 msec pulse width
It was measured with an optical densitometer. <Heat resistance (skin preservability)> Thermal recording of color development sensitivity
4kg / cm hot stamp heated to 90 ° C ^Twoof
Press for 4 seconds under pressure to visually check the density of background coloring on the recording material
Evaluated, those with little coloring have good heat resistance (skin preservability)
And <Plasticizer resistance (print storage stability)>
Scissors with rulap, 300g / cm from above^TwoThe load of
And leave it at 40 ° C for 24 hours.
Is visually evaluated, and those with less decoloration of print density are printed and stored.
Good performance.

[0126]

Example 1 2,4-Toluene diisocyanate 100
g of toluene as a solvent, and water 30
g was added and reacted at 30 ° C. for 7 hours. The precipitated white solid was recovered by filtration, washed with hexane, and dried in vacuo overnight to obtain 90 g of a white crystalline compound. The melting point and infrared absorption spectrum of this compound were measured. Melting point is 190 ° C
Met. The infrared absorption spectrum was 1590, 165
A characteristic sharp peak was observed at around 0,2290 cm-1.

Next, 6 g of the compound developer thus synthesized was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 24 g of a 2.5% by weight aqueous solution of polyvinyl alcohol to obtain a dispersion. Also, 70 g of 3-dibutylamino-6-methyl-7-anilinofluoran as a dye precursor
Was ground and dispersed together with 130 g of a 4.3% by weight aqueous solution of polyvinyl alcohol in a sand grinder (vessel capacity: 400 ml, manufactured by IMEX Co., Ltd.) for 3 hours at a rotation speed of 2000 rpm to obtain a dispersion.

The sensitizer diphenyl sulfone 7
0 g of a 5.4% by weight aqueous solution of polyvinyl alcohol 130
g with sand grinder (vessel capacity 400m
l, manufactured by Imex Co., Ltd.) and crushed and dispersed at a rotation speed of 2000 rpm for 3 hours to obtain a dispersion. Further, 10 g of calcium carbonate was mixed with 30 g of water, and the mixture was stirred and dispersed with a stirrer to obtain a dispersion.

These dispersions were combined with 50 parts by weight of the dry solids of the compound developer dispersion and 15 parts by weight of the dry solids of 3-dibutylamino-6-methyl-7-anilinofluoran dispersion.
Parts by weight, 30 parts by weight of dry solids of diphenyl sulfone dispersion, 20 parts by weight of dry solids of calcium carbonate dispersion,
Further, a coating liquid was obtained by stirring and mixing at a ratio of 10 parts by weight of a dry solid content of a zinc stearate dispersion having a solid content concentration of 16% by weight and 7 parts by weight of a dry solid content of 15% by weight of polyvinyl alcohol (dry basis). Was.

This coating solution was applied on a base paper having a weighing of 50 g / m 2 with a rod number 10 of a bacoater, dried and treated with a super calender to obtain a heat-sensitive recording material. The evaluation result of the sensitivity was as good as the optical density of 1.3. The evaluation result of the degree of discoloration (heat resistance) of the background due to heat was good with little discoloration. The preservability of the wrap of the printed portion with respect to the plasticizer was good with little fading. The results are summarized in Table 1.

[0131]

Example 2 2,4-Toluene diisocyanate 882
1240 g of methyl ethyl ketone as a solvent and N, N
-150 g of dimethylformamide,
63 g of 4'-diaminodiphenyl sulfone was mixed with 250 g of methyl ethyl ketone and N, N-dimethylformamide 30.
g, and the mixture was added dropwise over 30 minutes, and further reacted at 25 ° C. for 8 hours. After the reaction, methyl ethyl ketone was concentrated and removed, and then toluene was added. The precipitated white solid was collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 100 g of a white crystalline compound. Next, take 85 g of this compound,
1760 g of methyl ethyl ketone was added as a solvent, and 330 g of phenol and 0.08 g of triethylamine were further added.
After the addition, the mixture was reacted at 25 ° C. for 7 hours. After the reaction, toluene was added, and the precipitated crystals were collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 100 g of a white crystalline compound.

Next, 2 g of the compound developer thus synthesized was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5% by weight aqueous solution of polyvinyl alcohol to obtain a dispersion. Subsequently, a thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the dispersion of the compound developer described above was used instead of the dispersion of the compound developer synthesized in Example 1. . The results are summarized in Table 1.

[0133]

Example 3 61 g of 2,4-toluene diisocyanate
To this was added 450 g of toluene as a solvent, and 26 g of aniline dissolved in 150 g of toluene was added dropwise over 6 hours, and the mixture was reacted at 5 ° C. for 7 hours. After the reaction, the precipitated white solid was collected by filtration, washed with toluene, and dried in vacuo overnight to obtain 70 g of a white crystalline compound. Next, 30 g of this compound was taken, 365 g of toluene was added as a solvent, 12.2 g of 2,2-bis (4-hydroxyphenyl) propane and 0.3 mg of triethylamine were added, and the mixture was stirred at 60 ° C. for 4 hours, followed by 4 hours. The reaction was performed at 70 ° C. for 3 hours, and further heated at 80 ° C. for 3 hours. After the reaction, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with toluene, and dried under vacuum overnight to obtain 42 g of a white crystalline compound.

Next, 2 g of the compound developer thus synthesized was taken and crushed and dispersed with a paint shaker for 6 hours together with 8 g of a 2.5% by weight aqueous solution of polyvinyl alcohol.
A dispersion was obtained. In addition, 70 g of benzyl, which is a sensitizer, was pulverized together with 130 g of a 5.4% by weight aqueous solution of polyvinyl alcohol in a sand grinder (vessel capacity: 400 ml, manufactured by Imex Co.) for 3 hours at a rotation speed of 2000 rpm.
Dispersion gave a dispersion. Subsequently, the same as Example 1 except that the dispersion of the compound developer was used in place of the dispersion of the compound developer synthesized in Example 1, and the benzyl dispersion was used instead of the diphenylsulfone dispersion. Then, a heat-sensitive recording material was prepared and evaluated. The results are summarized in Table 1.

[0135]

Example 4 30 g of 2,4-toluene diisocyanate
To the mixture was added 30 g of toluene as a solvent, 3.24 g of phenol was added thereto, and the mixture was reacted at 100 ° C. for 1 hour and 30 minutes. After the reaction, the toluene was concentrated and removed, and then hexane was added.
The precipitated white solid was collected by filtration, washed with hexane, and dried in vacuo overnight to obtain 6.9 g of a compound as white crystals. Next, 5.0 g of this compound was taken, 100 g of toluene was added as a solvent, and 3.50 g of aniline was added thereto.
The reaction mixture was reacted for 3 hours, and the precipitated crystals were collected by filtration, washed with hexane, and dried in vacuo overnight to obtain a white crystalline compound 5.5.
g was obtained.

Next, 2 g of the compound developer thus synthesized was taken and pulverized and dispersed for 45 minutes with a paint shaker together with 8 g of a 2.5% by weight aqueous solution of polyvinyl alcohol to obtain a dispersion. Further, 70 g of 4,4'-dimethoxybenzophenone as a sensitizer was pulverized, dispersed and dispersed at a rotation speed of 2,000 rpm for 3 hours with a sand grinder (Vessel capacity: 400 ml, manufactured by Imex Co.) together with 130 g of a 5.4 wt% aqueous solution of polyvinyl alcohol. A liquid was obtained. Subsequently, a dispersion of the compound developer was used in place of the dispersion of the compound developer synthesized in Example 1, and a 4,4′-dimethoxybenzophenone dispersion was used instead of the diphenylsulfone dispersion. A thermosensitive recording material was prepared and evaluated in the same manner as in Example 1. The results are summarized in Table 1.

[0137]

Example 5 17 g of 2,4-toluene diisocyanate
To the mixture was added 40 g of methyl ethyl ketone as a solvent, 3.8 g of methanol was added dropwise, and the mixture was reacted at 60 ° C. for 5 hours with stirring. Next, 9.9 g of 4,4′-diaminodiphenylsulfone was added, and reacted at 60 ° C. for 4 hours with stirring. After the reaction, the reaction solution was cooled to room temperature, poured into 800 g of acetonitrile, and the precipitated crystals were collected by filtration, washed with hexane, and vacuum-dried overnight to obtain 15 g of a white crystalline compound.

Next, 2 g of the compound developer thus synthesized was taken and crushed and dispersed with a paint shaker for 6 hours together with 8 g of a 2.5% by weight aqueous solution of polyvinyl alcohol.
A dispersion was obtained. Also, diphenyl carbonate 70 as a sensitizer is used.
g of 5.4 wt% polyvinyl alcohol aqueous solution 130 g
With sand grinder (vessel capacity 400ml,
The mixture was pulverized and dispersed at 2,000 rpm for 3 hours to obtain a dispersion. Subsequently, Example 1 was repeated except that the dispersion of the compound developer was used in place of the dispersion of the compound developer synthesized in Example 1, and the diphenyl carbonate dispersion was used instead of the diphenylsulfone dispersion. In the same manner, a heat-sensitive recording material was prepared and evaluated. The results are summarized in Table 1.

[0139]

Examples 6 to 8 In place of diphenyl sulfone which is a sensitizer used in Example 2, 4,4'-dimethoxydiphenyl sulfone (Example 6), 4,4'-dibutoxydiphenyl sulfone (Example 7) Example 2) except that 4,4'-diallyloxydiphenyl sulfone (Example 8) was used.
A heat-sensitive recording material was prepared and evaluated in the same manner as described above. The results are summarized in Table 1.

[0140]

Example 9 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that diphenyl carbonate was used instead of diphenylsulfone used in Example 1. The results are summarized in Table 1.

[0141]

Comparative Examples 1-2 The compounds synthesized in Example 1 were replaced with 2,2-bis (4-hydroxyphenyl) propane (Comparative Example 1) and bis (4-hydroxyphenyl) sulfone (Comparative Example 2) A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that (1) was used. The results are summarized in Table 1.

[0142]

Comparative Example 3 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 1 except that parabenzylbiphenyl was used instead of diphenylsulfone used in Example 1.
The results are summarized in Table 1.

[0143]

Comparative Example 4 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 3 except that parabenzylbiphenyl was used instead of benzyl used in Example 3. The results are summarized in Table 1.

[0144]

[Table 1]

[0145]

According to the present invention, a recording material excellent in background, print preservability, and color sensitivity, particularly a heat-sensitive agent and a heat-sensitive recording material can be obtained.

Claims (3)

[Claims] 1. A sensitizer represented by the following structural formula (I) for a developer selected from the group consisting of an isocyanate compound and a urea urethane compound. Embedded image (Wherein, Y is _{-SO 2 -, - (S)} n -, - O -, - CO
_{-, - CH (C 6 H} 5) -, - C (CH 3) 2 -, - COC
_{O -, - CO 3 -,} - COCH 2 CO -, - NH- represents any. n is 1 or 2. Further, the hydrogen atom of the benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue. ) 2. The sensitizer according to claim 1, wherein the sensitizer is represented by the following structural formula (II). Embedded image (The hydrogen atom of the benzene ring in the formula is an aromatic compound residue,
It may be substituted by an aliphatic compound residue or a heterocyclic compound residue. ) 3. A heat-sensitive recording material comprising a support according to claim 1 and a thermosensitive coloring layer containing the sensitizer according to claim 1 for the developer. .