JPH0516526A - Thermal recording material - Google Patents

Abstract

PURPOSE:To obtain a thermal recording material having excellent image preservability and high thermal response. CONSTITUTION:In the thermal recording material wherein a thermal recording layer containing an aromatic isocyanate and an imino compound is carried on a support, at least one kind of condensated polycyclic compound or a derivative thereof, wherein three single rings are condensated and at least one of them is a five-membered ring, is added. Dibenzofuran, dibezothiophene, carbazole, fluorene and their derivatives are especially preferable as the condensated polycyclic compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive recording material which has excellent image storability and good thermal response.

[0002]

2. Description of the Related Art In recent years, heat-sensitive recording materials for recording with heat energy have been used in a wide range of fields such as printers and recorders for various measuring instruments, printers for labels, printers for POS, and automatic ticket vending machines such as tickets. It started to come. However, the heat-sensitive recording material using the conventional electron-donating colorless dye precursor and the electron-accepting color developer has excellent appearance, good feel, high color density, and various colored hues. While having characteristics,
When the recorded image area (thermosensitive coloring area) comes into contact with plastic such as polyvinyl chloride and disappears due to the plasticizers and additives contained in the plastic, or comes into contact with chemicals contained in foods and cosmetics. There is a drawback that the storage stability of the record is inferior such that it easily disappears or is easily faded by exposure to sunlight for a short time. In view of this point, JP-A-58-387 discloses a heat-sensitive recording material which reacts when two components are heated to obtain a recorded image with good storage stability.
33, JP-A-58-54085, and JP-A-5-54085.
JP-A 8-104959 discloses a heat-sensitive recording material whose two components include an isocyanate compound and an imino compound. In order to improve the thermal responsiveness (sensitivity) of the heat-sensitive recording material containing the imino compound and the isocyanate compound,
Various sensitizers have been investigated. For example, Japanese Patent Application No. 1-3
40349, Japanese Patent Application 1-343375, Japanese Patent Application 1-
Although disclosed in Japanese Patent No. 344669, the thermal response is still insufficient.

[0003]

An object of the present invention is to improve the thermal responsiveness (sensitivity) of a thermal recording material containing an imino compound and an isocyanate compound which are excellent in image storability.

[0004]

In a heat-sensitive recording material in which a heat-sensitive recording layer containing an aromatic isocyanate compound and an imino compound is provided on a support, three monocycles are condensed and one of the monocycles is condensed. By incorporating at least one fused polycyclic compound having a 5-membered ring or a derivative thereof, a heat-sensitive recording material excellent in thermal response could be obtained.

Among the fused polycyclic compounds according to the present invention, the 5-membered ring portion preferably has a skeleton represented by the Markush formula of the following chemical formula 1.

[0006]

[Chemical 1]

(X in the chemical formula 1 represents a hetero atom or a methylene chain, and when X is a nitrogen or methylene chain, it may or may not have a substituent.)

Further, the condensed form is preferably represented by the Markush formula of the following chemical formula 2. (X in the chemical formula 2 represents a hetero atom or a methylene chain, and when X is a nitrogen or a methylene chain, it may or may not have a substituent.)

[0009]

[Chemical 2]

Among the condensed polycyclic compounds represented by the condensed form of Chemical formula 2, particularly preferred are the dibenzofuran, dibenzothiophene, carbazole, fluorene and their derivatives represented by Chemical formula 3.

[0011]

[Chemical 3]

(X in the chemical formula 3 represents an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted methylene chain, and R represents an ether bond, an ester bond, a carbonyl group, a hydroxy group, a halogen, etc. Represents a group having 0 or more and 20 or less carbon atoms, which may or may not include.

In the chemical formula 3, when X is a substituted methylene chain, X is an alkyl group, an alkenyl group, an acyl group, a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkoxycarbonyl group, A methylene chain substituted with any of an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkylcarboxy group, an aralkylcarboxy group, an arylcarboxy group, an aryl group, an aralkyl group, a hydroxyalkyl group and a hydroxyalkoxy group is preferable. When X is a substituted nitrogen atom, X is a nitrogen atom substituted with any one of an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a hydroxyalkyl group, an alkoxyalkyl group and an alooloxyalkyl group. Is preferred.

Specific preferred examples of the substituent R in the chemical formula 3 are represented by the following chemical formula 4.

[0015]

[Chemical 4]

(Wherein n and m are integers of 0 or 1, l is an integer of 0 or more and 3 or less, R ¹ is an alkylene chain having 0 or more and 6 or less carbon atoms, R ² is hydrogen, An alkyl group, a substituted or unsubstituted aralkyl group and an aryl group are shown. When 1 is 2 or more, R ¹ 's may be different from each other or the same.)

Specific examples of the compound in the present invention include:
For example, the following are listed, but the present invention is not limited thereto.

(1) Hydrocarbon-based condensed polycyclic compound: fluorene, 9-fluorenone, acenaphthene, 1-methylfluorene, 1-benzylfluorene, 1-phenethylfluorene, 1-p-chlorobenzylfluorene, 2-
Hydroxyfluorene, 2-methoxyfluorene, 2-
Ethoxyfluorene, 2-benzyloxyfluorene,
3-benzyloxyfluorene, 4-benzyloxyfluorene, 2-p-tolylmethoxyfluorene, 2-phenoxyfluorene, 2-p-toluoxyfluorene,
2-fluorene carboxaldehyde, 4-fluorene carboxaldehyde, 2-acetylfluorene, 4-
Acetylfluorene, 2-benzoylfluorene, 2-
Hydroxyethylfluorene, 4-hydroxyethylfluorene, 2- (2-ethoxyethyl) fluorene, 2
-(2-phenoxyethyl) fluorene, 2- (2-p
-Chlorophenoxyethyl) fluorene, 2-benzyloxymethylfluorene, 2-acetoxyfluorene,
Methyl 1-fluorenecarboxylate, benzyl 1-fluorenecarboxylate, 2-benzoyloxyfluorene, 4
-Benzoyloxyfluorene, 2- (2-hydroxyethoxy) fluorene, 2- (2-hydroxyethoxyethoxy) fluorene, 2- (2-methoxyethoxy)
Fluorene, 2- (2-methoxypropoxy) fluorene, 2- (2-methoxyethyl) carbonylfluorene, 2-benzyloxyethylcarbonyloxyfluorene, 9-methylfluorene, 9-propylfluorene, 9-fluorenecarboxaldehyde, 9- Acetylfluorene, 9-benzoylfluorene, 9-bromofluorene, 9-allylfluorene, 9-hydroxyfluorene, 9-methoxyfluorene, 9-benzyloxyfluorene, 9-phenylfluorene, 9-phenoxyfluorene, 9-p-toluoxy Fluorene, 9-fluorenemethanol, 9-hydroxyethoxyfluorene and the like.

(2) Oxygen-containing heterocyclic condensed polycyclic compound:
Dibenzofuran, 1-benzyloxydibenzofuran,
1- (4-methylbenzyloxy) dibenzofuran, 1
-(M-chlorobenzyloxy) dibenzofuran, 1-
(4-Methoxybenzyloxy) dibenzofuran, 1-
(1-phenoxyethoxy) dibenzofuran, 1- (2
-Phenoxyethoxy) dibenzofuran, 1-isopropyldibenzofuran, 1-methyldibenzofuran, 1-
Benzyldibenzofuran, 1-phenethyldibenzofuran, 1-p-chlorobenzyldibenzofuran, 1-isopropoxydibenzofuran, 1-phenoxydibenzofuran, 1-p-chlorophenoxydibenzofuran, 1-
m-chlorophenoxydibenzofuran, 1-o-chlorophenoxydibenzofuran, 2-benzyloxydibenzofuran, 2-phenethyloxydibenzofuran, 2-
(4-Methylbenzyloxy) dibenzofuran, 2-
(4-chlorobenzyloxy) dibenzofuran, 2-
(4-Methoxybenzyloxy) dibenzofuran, 2-
(2,4-dimethylbenzyloxy) dibenzofuran,
2- (2-phenoxyethoxy) dibenzofuran, 2-
(3-phenoxypropoxy) dibenzofuran, 2-
(5-phenoxypentyloxy) dibenzofuran, 2
-(2- (4-tolyloxy) ethoxy) dibenzofuran, 2- (2- (4-chlorophenyl) ethoxy) dibenzofuran, 2- (2- (3-chlorophenyl) ethoxy) dibenzofuran, 2-hydroxydibenzofuran,
2-methoxydibenzofuran, 2-isopropoxydibenzofuran, 2-p-toluoxydibenzofuran, 2-
Benzyldibenzofuran, 3-phenoxydibenzofuran, 3-p-toluoxydibenzofuran, 3-benzyloxydibenzofuran, 3-phenethyloxydibenzofuran, 3- (4-chlorobenzyloxy) dibenzofuran, 3- (4-methylbenzyloxy) dibenzofuran, 3- (4-t-butylbenzyloxy) dibenzofuran, 3- (4-ethylbenzyloxy) dibenzofuran, 3- (3-methoxybenzyloxy) dibenzofuran, 3- (2-phenoxyethoxy) dibenzofuran,
3- (3-phenoxypropoxy) dibenzofuran, 3
-(2-naphthyl) methyloxydibenzofuran, 3-
(4-Ethylbenzyloxy) dibenzofuran, 3-
(1-phenoxyethoxy) dibenzofuran, 3- (2
-(3-methoxyphenyl) ethoxy) dibenzofuran, 3- (2- (3-ethoxyphenyl) ethoxy) dibenzofuran, 3- (2-ethoxyethyl) dibenzofuran, 3- (2-phenoxyethyl) dibenzofuran,
3- (2-p-chlorophenoxyethyl) dibenzofuran, 3-methyldibenzofuran, 3-benzyldibenzofuran, 3-phenethyldibenzofuran, 3-p-chlorobenzyldibenzofuran, 3-hydroxydibenzofuran, 3-methoxydibenzofuran, 3-ethoxydibenzofuran , 3-isopropoxydibenzofuran, 3-
Formyldibenzofuran, 3-acetyldibenzofuran, 3-benzoyldibenzofuran, 3-hydroxyethyldibenzofuran, 3-benzyloxymethyldibenzofuran, 3-acetoxydibenzofuran, methyl 3-dibenzofuranate, benzyl 3-dibenzofuranate 3,
-Benzoyloxydibenzofuran, 3- (2-hydroxyethoxy) dibenzofuran, 3- (2-hydroxyethoxyethoxy) dibenzofuran, 3- (2-methoxyethoxy) dibenzofuran, 3- (3-ethoxypropoxy) dibenzofuran, 3- (2 -Methoxyethyl)
Carbonyldibenzofuran, 3-benzyloxyethyl carbonyloxydibenzofuran, 4-benzyloxydibenzofuran, 4- (4-methylbenzyloxy) dibenzofuran, 4- (4-isopropylbenzyloxy) dibenzofuran, 4- (4-chlorobenzyloxy) dibenzofuran , 4- (2-phenoxyethoxy)
Dibenzofuran, 4-methyldibenzofuran, 4-benzyldibenzofuran, 4-phenethyldibenzofuran,
4-p-chlorobenzyldibenzofuran, 4-methoxydibenzofuran, 4-phenoxydibenzofuran, 4-
p-chlorophenoxydibenzofuran, 4-benzyloxyethylcarbonyloxydibenzofuran and the like.

(2) Sulfur-containing heterocyclic condensed polycyclic compound:
Dibenzothiophene, 1-benzyloxydibenzothiophene, 1- (4-methylbenzyloxy) dibenzothiophene, 1- (m-chlorobenzyloxy) dibenzothiophene, 1- (4-methoxybenzyloxy) dibenzothiophene, 1- (1 -Phenoxyethoxy) dibenzothiophene, 1- (2-phenoxyethoxy) dibenzothiophene, 1-isopropyldibenzothiophene, 1-methyldibenzothiophene, 1-benzyldibenzothiophene, 1-phenethyldibenzothiophene,
1-p-chlorobenzyldibenzothiophene, 1-isopropoxydibenzothiophene, 1-phenoxydibenzothiophene, 1-p-chlorophenoxydibenzothiophene, 1-m-chlorophenoxydibenzothiophene, 1-o-chlorophenoxydibenzothiophene, 2
-Benzyloxydibenzothiophene, 2-phenethyloxydibenzothiophene, 2- (4-methylbenzyloxy) dibenzothiophene, 2- (4-chlorobenzyloxy) dibenzothiophene, 2- (4-methoxybenzyloxy) dibenzothiophene, 2 -(2,4-dimethylbenzyloxy) dibenzothiophene, 2- (2
-Phenoxyethoxy) dibenzothiophene, 2- (3
-Phenoxypropoxy) dibenzothiophene, 2-
(5-phenoxypentyloxy) dibenzothiophene, 2- (2- (4-tolyloxy) ethoxy) dibenzothiophene, 2- (2- (4-chlorophenyl) ethoxy) dibenzothiophene, 2-hydroxydibenzothiophene, 2-methoxydibenzo Thiophene, 2-isopropoxydibenzothiophene, 2-p-toluoxydibenzothiophene, 2-benzyldibenzothiophene,
3-phenoxydibenzothiophene, 3-p-toluoxydibenzothiophene, 3-benzyloxydibenzothiophene, 3-phenethyloxydibenzothiophene,
3- (4-chlorobenzyloxy) dibenzothiophene, 3- (4-methylbenzyloxy) dibenzothiophene, 3- (4-ethylbenzyloxy) dibenzothiophene, 3- (3-methoxybenzyloxy) dibenzothiophene, 3- (2-phenoxyethoxy) dibenzothiophene, 3- (3-phenoxypropoxy) dibenzothiophene, 3- (2-naphthyl) methyloxydibenzothiophene, 3- (4-ethylbenzyloxy) dibenzothiophene, 3- (1-phenoxy) Ethoxy) dibenzothiophene, 3- (2- (3-methoxyphenyl) ethoxy) dibenzothiophene, 3- (2- (3-
Ethoxyphenyl) ethoxy) dibenzothiophene, 3
-(2-Ethoxyethyl) dibenzothiophene, 3-
(2-phenoxyethyl) dibenzothiophene, 3-
(2-p-chlorophenoxyethyl) dibenzothiophene, 3-methyldibenzothiophene, 3-benzyldibenzothiophene, 3-phenethyldibenzothiophene,
3-p-chlorobenzyldibenzothiophene, 3-hydroxydibenzothiophene, 3-methoxydibenzothiophene, 3-ethoxydibenzothiophene, 3-isopropoxydibenzothiophene, 3-formyldibenzothiophene, 3-acetyldibenzothiophene, 3-benzoyldibenzo Thiophene, 3-hydroxyethyldibenzothiophene, 3-benzyloxymethyldibenzothiophene, 3-acetoxydibenzothiophene, methyl 3-dibenzothiophenate, benzyl 3-dibenzothiophenate, 3-benzoyloxydibenzothiophene,
3- (2-hydroxyethoxy) dibenzothiophene,
3- (2-hydroxyethoxyethoxy) dibenzothiophene, 3- (2-methoxyethoxy) dibenzothiophene, 3- (2-methoxypropoxy) dibenzothiophene, 3- (3-ethoxypropoxy) dibenzothiophene, 3- (2- Methoxyethyl) carbonyldibenzothiophene, 3-benzyloxyethylcarbonyloxydibenzothiophene, 4-benzyloxydibenzothiophene, 4- (4-methylbenzyloxy) dibenzothiophene, 4- (4-chlorobenzyloxy) dibenzothiophene, 4- (2-phenoxyethoxy) dibenzothiophene, 4-methyldibenzothiophene, 4-benzyldibenzothiophene, 4-phenethyldibenzothiophene, 4-p-chlorobenzyldibenzothiophene, 4-methoxydi Nzochiofen, 4-phenoxyphenyl dibenzothiophene, 4-benzyloxycarbonyl-ethyl carbonyloxy dibenzothiophene.

(3) Nitrogen-containing heterocyclic condensed polycyclic compound:
Carbazole, 9-methylcarbazole, 9-ethylcarbazole, 9-vinylcarbazole, 9-phenylcarbazole, 9-ethyl-3-carbazolecarboxaldehyde, 9- (2-phenoxyethyl) carbazole, 9- (2-ethoxyethyl) ) Carbazole, 9-
(Methoxyethyl) carbazole, 1-benzyloxycarbazole, 1- (4-methylbenzyloxy) carbazole, 1- (m-chlorobenzyloxy) carbazole, 1- (1-phenoxyethoxy) carbazole,
1-isopropylcarbazole, 1-methylcarbazole, 1-benzylcarbazole, 1-p-chlorobenzylcarbazole, 1-p-chlorophenoxycarbazole, 2-benzyloxycarbazole, 2-phenethyloxycarbazole, 2- (4-methylbenzyl) (Oxy) carbazole, 2- (2,4-dimethylbenzyloxy) carbazole, 2-hydroxycarbazole, 2
-Methoxycarbazole, 2-p-toluoxycarbazole, 2-benzylcarbazole, 3-phenoxycarbazole, 3-p-toluoxycarbazole, 3-benzyloxycarbazole, 3-phenethyloxycarbazole, 3- (4-methylbenzyloxy) ) Carbazole, 3- (2-naphthyl) methyloxycarbazole,
3- (4-ethylbenzyloxy) carbazole, 3-
(1-phenoxyethoxy) carbazole, 3- (2-
Ethoxyethyl) carbazole, 3- (2-phenoxyethyl) carbazole, 3- (2-p-chlorophenoxyethyl) carbazole, 3-methylcarbazole, 3
-Benzylcarbazole, 3-phenethylcarbazole, 3-p-chlorobenzylcarbazole, 3-hydroxycarbazole, 3-methoxycarbazole, 3-ethoxycarbazole, 3-formylcarbazole, 3-
Acetylcarbazole, 3-benzoylcarbazole,
3-hydroxyethylcarbazole, 3-benzyloxymethylcarbazole, 3-acetoxycarbazole,
Benzyl 3-carbazolate, 3- (2-hydroxyethoxyethoxy) carbazole, 3- (2-methoxypropoxy) carbazole, 4-benzyloxycarbazole, 4- (4-methylbenzyloxy) carbazole, 4-methylcarbazole, 4 -Benzylcarbazole, 4-phenethylcarbazole, 4-p-chlorobenzylcarbazole, 4-phenoxycarbazole and the like.

The compound in the present invention can be easily synthesized by a known method. There are also commercially available compounds. Specific synthetic examples of the compound in the present invention are shown below, but the present invention is not limited to these.

(Synthesis Example 1) Synthesis of 3-benzyloxydibenzofuran 3-hydroxydibenzofuran (18.4 g) was added to N, N
-Dissolved in dimethylformamide (100 ml), potassium carbonate (11.9 g) was added to this solution and dispersed. Benzyl chloride (12.7 g) was added dropwise over 30 minutes, and after completion of the addition, the mixture was heated to 100 ° C. and reacted for 1 hour. After completion of the reaction, the reaction mixture was poured into 1 liter of water, and the precipitated white solid was collected by filtration, dried and recrystallized from isopropyl alcohol to give 3-benzyloxydibenzofuran 2
2.5 g was obtained. (Melting point 92 ° C)

(Synthesis Example 2) Synthesis of 3-benzyldibenzothiophene Dibenzothiophene (9.2 g) was added to 1,1,2,2,-
It was dissolved in tetrachloroethane (100 ml). Anhydrous aluminum chloride (7.3 g) and benzoyl chloride (7.0 g) were added, and the mixture was stirred at 10 ° C for 5 hr. After completion of the reaction, 2N hydrochloric acid aqueous solution (30 ml) was added. The organic layer was extracted and the solvent was evaporated under reduced pressure to give a pale yellow solid. This was recrystallized from ethanol to obtain 3-benzoyldibenzothiophene (10.1 g). Next, this benzoyl compound was added to 140 ml of ethylene glycol, followed by potassium hydroxide (2.6 g) and hydrazine hydrate (7.0 g), and the mixture was heated to 150 ° C.
Heating was continued for 2 hours while distilling water off, and after cooling, the reaction mixture was poured into 400 ml of water, the precipitated solid was collected by filtration, dried and recrystallized from ethanol to give 3-benzyldibenzothiophene. 9 g was obtained. (Melting point 130
℃)

The amount of the condensed polycyclic compound used in the present invention is 5 to 400% by weight, preferably 10 to 300% by weight, based on the aromatic isocyanate compound. 5% by weight
In the following, good thermal response cannot be obtained, and in the case of 400% by weight or more, a diluting effect occurs, and similarly good thermal response cannot be obtained.

The aromatic isocyanate compound used in the present invention refers to a colorless or light-colored aromatic isocyanate compound or heterocyclic isocyanate compound which is solid at room temperature, and for example, one or more of the following may be 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, diphenyl ether-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, pyrene-3,8-di Isocyanate, naphthalene-1,3,7-triisocyanate, biphenyl-
2,4,4'-triisocyanate, 4,4 ', 4 "-
Triisocyanate-2,5-dimethoxytriphenylamine, p-dimethylaminophenylisocyanate,
Examples include tris (4-phenylisocyanate) thiophosphate. These isocyanate compounds may be used in the form of so-called block isocyanate, which is an addition compound with phenols, lactams, oximes, etc., if necessary, and a diisocyanate dimer,
For example, it may be used in the form of isocyanurate, which is a dimer or trimer of 1-methylbenzene-2,4-diisocyanate, or used as a polyisocyanate adducted with various polyols. Is also possible.

The imino compound used in the present invention is a compound represented by the general formula 5 (φ is an aromatic compound residue capable of forming a conjugated system with an adjacent C═N), and it is solid at room temperature. It is a colorless or pale compound.

[0029]

[Chemical 5]

As specific examples, (1) 1,3-diiminoisoindolines: 1,3-diiminoisoindoline, 1,3-diimino-4,5,6,7-tetrachloroiso Indoline, 1,3-Diimino-6-methoxyisoindoline, 1,3-Diimino-6-cyanoisoindoline, 1,3-Diimino-4,7-dithia-5,5,5
6,6-Tetrahydroisoindoline, 1-phenylimino-3-iminoisoindoline, 1- (3'-chlorophenylimino) -3-iminoisoindoline, 1-
(2 ', 5'-Dichlorophenylimino) -3-iminoisoindoline, 1- (2', 4 ', 5'trichlorophenylimino) -3-iminoisoindoline, 1-
(2'-Cyano-4'-nitrophenylimino) -3-
Iminoisoindoline, 1- (2'-chloro-5'-cyanophenylimino) -3-iminoisoindoline, 1
-(2 ', 6'-Dichloro-4'-nitrophenylimino) -3-iminoisoindoline, 1- (2', 5'-
Dimethoxyphenylimino) -3-iminoisoindoline, 1- (2 ', 5'-diethoxyphenylimino)-
3-iminoisoindoline, 1- (2'-methyl-4 '
-Nitrophenylimino) -3-iminoisoindoline, 1- (5'-chloro-2'-phenoxyphenylimino) -3-iminoisoindoline, 1- (4'-N,
N-dimethylaminophenylimino) -3-iminoisoindoline, 1- (3′-N, N-dimethylamino-
4'-methoxyphenylimino) -3-iminoisoindoline, 1- (2'-methoxy-5'-N-phenylcarbamoylphenylimino) -3-iminoisoindoline, 1- (2'-chloro-5'- Trifluoromethylphenylimino) -3-iminoisoindoline, 1-
(5 ', 6'-dichlorobenzothiazolyl-2'-imino) -3-iminoisoindoline, 1- (6'-methylbenzothiazolyl-2'-imino) -3-iminoisoindoline, 1 -(4'-phenylaminophenylimino) -3-iminoisoindoline, 1- (p-phenylazophenylimino) -3-iminoisoindoline, 1
-(Naphtyl-1'-imino) -3-iminoisoindoline, 1- (anthraquinone-1'-imino) -3-iminoisoindoline, 1- (5'-chloroanthraquinone-1'-imino)- 3-iminoisoindoline, 1-
(N-ethylcarbazolyl-3′-imino) -3-iminosoindoline, 1- (naphthoquinone-1′-imino)
-3-iminoisoindoline, 1- (pyridyl-4'-
Imino) -3-iminoisoindoline, 1- (benzimidazolone-6'-imino) -3-iminoisoindoline, 1- (1'-methylbenzimidazolone-6'-imino) -3-iminoisoindoline , 1- (7'-chlorobenzimidazolone-5'-imino) -3-iminoisoindoline, 1- (benzimidazolyl-2'-imino) -3-iminoisoindoline, 1- (benzimidazolyl-2 ' -Imino) -3-imino-4,5,6,7
-Tetrachloroisoindoline, 1- (2 ', 4'-dinitrophenylhydrazone) -3-iminoisoindoline, 1- (indazolyl-3'-imino) -3-iminoisoindoline, 1- (indazolyl-3' -Imino)
-3-Imino-4,5,6,7-tetrabromoisoindoline, 1- (indazolyl-3'-imino) -3-imino-4,5,6,7-tetrafluoroisoindoline, 1- (benz Imidazolyl-2'-imino) -3-
Imino-4,7-dithiatetrahydroisoindoline,
1- (4 ', 5'-dicyanoimidazolyl-2'-imino) -3-imino-5,6-dimethyl-4,7-pyradiisoindoline and the like,

(2) 3-iminoisoindoline-1-ones: 3-iminoisoindoline-1-one, 3-imino-4,5,6,7-tetrachloroisoindoline-1
-One, 3-imino-4,5,6,7-tetrabromoisoindoline-1-one, 3-imino-4,5,6,7
-Tetrafluoroisoindoline-1-one, 3-imino-5,6-dichloroisoindoline-1-one, 3-
Imino-4,5,7-trichloro-6-methoxyisoindoline-1-one, 3-imino-4,5,7-trichloro-6-methoxyisoindoline-1-one, 3-imino-4,5,5 7-Trichloro-6-methylmercaptoisoindoline-1-one, 3-imino-6-nitroisoindoline-1-one, 1-iminonaphthalimide, 1-iminodiphenimide, 3-iminoisoindoline-1-spiro -Dioxolane, 1,1-dimethoxy-3-iminoisoindoline, 1,1-diethoxy-
3-imino-4,5,6,7-tetrachloroisoindoline, 1-ethoxy-3-iminoisoindoline, 3-
Imino-2-methyl-4,5,6,7-tetrachloroisoindoline-1-one, 1- (cyanocarbomethoxymethylene) -3-iminoisoindoline, 1- (cyanocarboethoxymethylene) -3-imino Isoindoline, 7-amino-2,3-dimethyl-5-oxopyrrolo [3,4b] pyrazine, 7-amino-2,3-diphenyl-5-oxopyrrolo [3,4b] pyrazine, and the like,

(3) 3-iminoisoindolines: 1-
(Cyanobenzoylmethylene) -3-iminoisoindoline, 1- (cyanocarbamidomethylene) -3-iminoisoindoline, 1- (cyano-N-phenylcarbamoylmethylene) -3-iminoisoindoline, 1- [cyano-N -(3'-Methylphenyl) carbamoylmethylene] -3-iminoisoindoline, 1- [cyano-N
-(4'-chlorophenyl) carbamoylmethylene]-
3-iminoisoindoline, 1- [cyano-N- (4 '
-Methoxyphenyl) -carbamoylmethylene] -3-
Iminoisoindoline, 1- [cyano-N- (3'-chloro-4'-methylphenyl) -carbamoylmethylene] -3-iminoisoindoline, 1- (cyano-p-
Nitrophenylmethylene) -3-iminoisoindoline, 1- (dicyanomethylene) -3-iminoisoindoline, 1- (cyano-1 ′, 2 ′, 4′-triazolyl- (3 ′)-carbamoylmethylene) -3 -Iminoisoindoline, 1- (cyanothiazoyl- (2 ')-carbamoylmethylene) -3-iminoisoindoline, 1-
(Cyanobenzimidazolyl- (2 ')-carbamoylmethylene-3-iminoisoindoline, 1- (cyanobenzothiazolyl- (2')-carbamoylmethylene)-
3-iminoisoindoline, 1-[(cyanobenzimidazolyl-2 ')-methylene] -3-iminoisoindoline, 1-[(cyanobenzimidazolyl-2') methylene] -3-imino-4,5,6 , 7-Tetrachloroisoindoline, 1-[(cyanobenzimidazolyl-
2 ')-methylene] -3-imino-5-methoxyisoindoline, 1-[(cyanobenzimidazolyl-2')
-Methylene] -3-imino-6-chloroisoindoline, 1-[(1'-phenyl-3'-methyl-5-oxo) -pyrazolidene-4 ']-3-iminoisoindoline, 1-[(cyano Benzimidazolyl-2 ')-methylene] -3-imino-4,7-dithiatetrahydroisoindoline, 1-[(cyanobenzimidazolyl-
2 ')-Methylene] -3-imino-5,6-dimethyl-
4,7-pyradiisoindoline, 1-[(1'-methyl-3'-n-butyl) -barbituric acid-5 ']-3-iminoisoindoline and the like,

(4) 3-imino-1-sulfobenzoic acid imides: 3-imino-1-sulfobenzoic acid imide, 3-
Imino-1-sulfo-6-chlorobenzoic acid imide, 3-
Imino-1-sulfo-5,6-dichlorobenzoic acid imide, 3-imino-1-sulfo-4,5,6,7-tetrachlorobenzoic acid imide, 3-imino-1-sulfo-4,
5,6,7-Tetrabromobenzoic acid imide, 3-imino-1-sulfo-4,5,6,7-tetrafluorobenzoic acid imide, 3-imino-1-sulfo-6-nitrobenzoic acid imide, 3- Imino-1-sulfo-6-methoxybenzoic acid imide, 3-imino-1-sulfo-4,5,7-trichloro-6-methylmercaptobenzoic acid imide, 3-
Imino-1-sulfonaphthoic acid imide, 3-imino-1
-Sulfo-5-bromonaphthoic acid imide, etc., and two or more kinds of imino compounds can be used in combination depending on the purpose.

The amount of the aromatic isocyanate compound used is not particularly limited as long as it reacts with the imino compound and a color image is obtained, but it is preferably contained in an amount of 1% by weight or more based on the imino compound. Preferably 5 to 1
It is 000% by weight.

Paper is mainly used as a support for the heat-sensitive recording material of the present invention. In addition to paper, various non-woven fabrics, woven fabrics, synthetic resin films, laminated papers, synthetic papers, metal foils, and the like, or these A composite sheet obtained by combining the above can be arbitrarily used according to the purpose.

The layer structure of the heat-sensitive recording layer may be a single layer or a multi-layer structure. In the case of multiple layers, an intermediate layer may be interposed between each layer, and the intermediate layer may be composed of a plurality of layers. A protective layer may be provided on the heat-sensitive recording layer, or an intermediate layer may be provided between the heat-sensitive recording layer and the support. In this case, each of the protective layer and the intermediate layer may be composed of a single layer or a plurality of layers of two layers or three layers or more. Further, a back coat layer may be provided on the surface of the support opposite to the surface on which the heat-sensitive recording layer is provided for the purpose of preventing curling and charging.

The heat-sensitive recording layer can be obtained by mixing the respective aqueous dispersions obtained by finely pulverizing the respective color-forming components, the binder and the like, coating on a support and drying. In this case, for example, each color-forming component may be contained in one layer to form a multilayer structure.

In the heat-sensitive recording material of the present invention, other heat-fusible substances can be used alone or in combination.
Those having a melting point of 60 ° C. to 180 ° C. are preferable, and those having a melting point of 80 ° C. to 140 ° C. are particularly preferable. For example, benzyl p-benzyloxybenzoate, stearic acid amide, palmitic acid amide, N-methylol stearic acid amide, β-naphthylbenzyl ether, N-stearyl urea, N, N′-distearyl urea, β-
Naphthoic acid phenyl ester, β-naphthol (p-methylbenzyl) ether, 1,4-dimethoxynaphthalene, 1-methoxy-4-benzyloxynaphthalene, N
-Stearoyl urea, 4-benzyl biphenyl, 1,
2-di (m-methylphenoxy) ethane, 1-phenoxy-2- (4-chlorophenoxy) ethane, 1,4-butanediol phenyl ether, dimethyl terephthalate and the like can be mentioned.

Further, the heat-sensitive recording material of the present invention may contain an aniline derivative having at least one amino group, which is shown in the international application PCT / JP81 / 00300 by the applicant of the present invention. More effective.

As specific examples, (1) monoanilines: methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, p-aminobenzoic acid-iso- Propyl, 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 and the like,

(2) Bisanilines: 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, 3,3'-dimethyl- 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ',
5,5'-Tetrachloro-4,4'-diaminobiphenyl, ortho-sortidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-
Diaminobiphenyl, 2,2'-dichloro-4,4'-
Diaminobiphenyl, 3,3'-dichloro-4,4'-
Diaminobiphenyl, 2,2'-dimethyl-4,4'-
Diaminobiphenyl, 4,4'-thiodianiline, 2,
2'-dithiodianiline, 4,4'-dithiodianiline, 3,4'-diaminodiphenyl ether, 4,4 '
-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-
Amino-4-chlorophenyl) sulfone, bis (4-aminophenyl) sulfone, bis (3-aminophenyl)
Sulfone, 3,4'-diaminodiphenyl sulfone,
3,3′-diaminodiphenylmethane, 4,4′-ethylenedianiline, 4,4′-diamino-2,2′-dimethyldibenzyl, 4,4′-diamino-3,3′-dichlorodiphenylmethane, 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, etc.

(3) Phenylenediamines: Bis (3,
4-diaminophenyl) sulfone, 3,3 ′, 4,4 ′
-Tetraaminodiphenyl ether, 3,3 ', 4,
4'-tetraaminodiphenyl sulfone, 3,3 ',
4,4'-tetraaminobenzophenone and the like can be mentioned.

Further, in the heat-sensitive recording layer, pigments such as diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin, and others. For the purpose of preventing head wear, sticking, etc., higher fatty acid metal salts such as zinc stearate and calcium stearate, waxes such as paraffin, oxidized paraffin, polyethylene, oxidized polyethylene, stearic acid amide and castor wax, and dioctylsulfosuccinic acid A dispersant such as sodium acid salt, a benzophenone-based or benzotriazole-based ultraviolet absorber, a surfactant, a fluorescent dye, and the like may be contained.

[0044]

The present invention will be described in more detail with reference to the following examples.

Example 1 15 g of 1,3-diimino-4,5,6,7-tetrachloroisoindoline was added to a 1% aqueous solution of polyvinyl alcohol 6
Grind with 0g in a ball mill for 24 hours, and
10 g of 4 ', 4 "-triisocyanato-2,5-dimethoxytriphenylamine was crushed with 40 g of a 1% aqueous solution of polyvinyl alcohol in a ball mill for 24 hours to obtain a dispersion liquid. Further, 25 g of fluorene (melting point: 115 ° C) was added to 1 g.
% Polyvinyl alcohol aqueous solution and similarly dispersed to obtain a dispersion liquid. After mixing these three types of dispersions, 125 g of 40% aqueous dispersion of calcium carbonate, 50 g of 30% aqueous dispersion of zinc stearate and 10% polyvinyl alcohol
Solution (135 g) and water (90 g) were added and sufficiently stirred to obtain a coating liquid. This coating solution was applied onto a base paper having a basis weight of 50 g / m ² so as to obtain a coating amount of 5.2 g / m ² in terms of solid content, dried and then treated with a super calendar to obtain a heat-sensitive recording material. Obtained.

Examples 2 to 16 Instead of the fluorene used in Example 1, dibenzothiophene (Example 2, melting point 98 ° C.), 9-phenoxyfluorene (Example 3, melting point 80 ° C.), 9-fluorenemethanol, respectively. (Example 4, melting point 106 ° C), 3-benzyloxydibenzofuran (Example 5, melting point 92 ° C),
3- (4-chlorobenzyloxy) dibenzofuran (Example 6, melting point 94 ° C), 3- (4-methylbenzyloxy) dibenzofuran (Example 7, melting point 100 ° C), 3-
(2-phenoxyethoxy) dibenzofuran (Example 8, melting point 123 ° C), 3- (3-phenoxypropoxy) dibenzofuran (Example 9, melting point 82 ° C), 3-benzyldibenzofuran (Example 10, melting point 89 ° C), Three
-Benzyldibenzothiophene (Example 11, melting point 13
0 ° C.), 3-acetoxydibenzofuran (Example 12,
Melting point 114 ° C.), 3-hydroxyethoxydibenzofuran (Example 13, melting point 122 ° C.), 9-methylcarbazole (Example 14, melting point 90 ° C.), 9-ethyl-3-carbazole carboxaldehyde (Example 15, melting point). 85
C.), 9-phenylcarbazole (Example 16, melting point 9)
A thermosensitive recording material was obtained in the same manner as in Example 1 except that (5 ° C.) was used.

Comparative Example 1 A thermosensitive recording material was obtained in the same manner as in Example 1 except that fluorene of Example 1 was not used.

Test 1 (color density = thermal response) The thermal recording materials obtained in Examples 1 to 16 and Comparative Example 1 were
An applied voltage of 22 ms and an applied voltage of 1.2 ms for 1.75 ms using a thermal facsimile printing tester, respectively.
Printing was performed under the condition of 00 V, and the density of the obtained color image was measured using a densitometer Macbeth RD918. The results are shown in Table 1.

Test 2 (Plasticizer resistance = image storability) The thermal recording materials obtained in Examples 1 to 16 and Comparative Example 1 were
After overlaying each with a vinyl chloride sheet and applying a load of 300 g / m ² and storing in an atmosphere of 40 ° C. for 24 hours,
In the same manner as in Test 1, the density of the colored portion was measured. The image residual rate was calculated according to the following formula 1. As a result, the image residual rates of the thermal recording materials obtained in Examples 1 to 16 and Comparative Example 1 were all 100%.

[0050]

[Equation 1] A = (B / C) × 100 A: Image residual ratio (%) B: Density of image area after test C: Density of image area before test

[0051]

[Table 1]

[0052]

By using the compound according to the present invention, a heat-sensitive recording material having excellent image storability and thermal responsiveness can be obtained.

Claims (1)

Claim: What is claimed is: 1. A heat-sensitive recording material comprising a support and a heat-sensitive recording layer containing an aromatic isocyanate compound and an imino compound, wherein three monocycles are condensed and one of them is condensed. A heat-sensitive recording material comprising at least one fused polycyclic compound having a 5-membered single ring or a derivative thereof.