JPH08300820A - Thermal recording material - Google Patents

Abstract

PURPOSE: To obtain a thermal recording material excellent in color forming sensitivity and the storage stability of an undeveloped color part and a developed color image by adding at least one kind of a compd. selected from a salicylic acid derivative represented by a specific formula and a metal salt thereof as an electron acceptive compd. CONSTITUTION: In a thermal recording material containing an electron donating color forming compd. and an electron acceptive compd., at least one kind of a compd. selected from a salicylic acid derivative represented by formula I and a metal salt thereof is added as the electron acceptive compd. and a compd. represented by formula II is added. In the formulae I, II, X1 and X2 are a hydrogen atom or an alkyl group, Y1 and Y2 an oxygen atom or a sulfur atom, R1 is a hydrogen atom and the others, R2 is an alkyl group and the others, X3 -X6 are a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an arylthio group or a halogen atom and R3 and R4 are an alkyl group or an aralkyl group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a heat-sensitive recording material.
More specifically, the present invention relates to a heat-sensitive recording material which is excellent in color development sensitivity and is excellent in storage stability of uncolored part (background) and color image.

[0002]

2. Description of the Related Art Conventionally, a heat-sensitive recording material utilizing a color reaction between an electron-donating color-forming compound and an electron-accepting compound (developing agent) is well known (for example, JP-B-43-4).
160, JP-B-45-14039). Thermosensitive recording materials are relatively inexpensive and have the advantages that the recording equipment is compact and maintenance-free, and are widely used in the fields of facsimiles, recorders and printers. In recent years, the fields of use of thermal recording materials have further expanded and diversified, and have expanded to applications (eg, labels, prepaid cards, etc.) under harsh environments. However, as is known in the art,
A heat-sensitive recording material containing 2,2-bis (4'-hydroxyphenyl) propane ["bisphenol A"], 4-hydroxybenzoic acid benzyl ester, etc. as an electron-accepting compound is used in a harsh environment (for example, oil or solvent). When exposed to a writing tool such as oil and fat or a fluorescent pen, or in a humid environment), there are drawbacks such that the uncolored part is significantly contaminated (ground stain), and the colored image is discolored.

As a means for improving such a defect,
A thermosensitive recording material has been proposed which uses a salicylic acid derivative substituted with a carbamate group or a metal salt (particularly a polyvalent metal salt) of the derivative as an electron-accepting compound (JP-A-6-7).
2984). Also known is a heat-sensitive recording material in which a salicylic acid derivative substituted with a carbamate group or a metal salt of the derivative is used as an electron-accepting compound, and an aliphatic amide compound having a molecular constitutional carbon number of 18 or more is used as a heat-fusible compound. (JP-A-6-143824). However, a heat-sensitive recording material using an aliphatic amide compound having a molecular number of carbon atoms of 18 or more (for example, stearic acid amide) as a heat-fusible compound requires further improvement in heat response. It has been found that when stored in a harsh environment for a long time, the stability of the uncolored part and the storage stability of the color image have some problems. At present, there is a demand for a heat-sensitive recording material which is excellent in thermal responsiveness (coloring sensitivity) and is further excellent in storage stability of uncolored portions and color images.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-sensitive recording material which is excellent in color developing sensitivity and storage stability of uncolored portion and color image.

[0005]

The inventors of the present invention have completed the present invention as a result of earnest studies on a heat-sensitive recording material in order to meet the above-mentioned demands. That is, the present invention is
In a heat-sensitive recording material containing an electron-donating color-forming compound and an electron-accepting compound, the electron-accepting compound is at least selected from salicylic acid derivatives represented by the general formula (1) (Formula 3) and metal salts of the derivatives. The present invention relates to a heat-sensitive recording material containing one kind and further containing a compound represented by the general formula (2) (formula 4).

[0006]

Embedded image (In the formula, X ₁ and X ₂ represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom, Y ₁ and Y ₂ represent an oxygen atom or a sulfur atom, R ₁ represents a hydrogen atom, Represents an alkyl group, an aralkyl group or an aryl group, and R ₂ represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group)

[Chemical 4] (In the formula, X _{3 to} X ₆ represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an arylthio group or a halogen atom, R ₃ and R ₄ represent an alkyl group or an aralkyl group, and Y is a single bond, Represents an oxygen atom or a sulfur atom, and n represents 0 or 1.)

In the salicylic acid derivative represented by the general formula (1) according to the present invention, X ₁ and X ₂ represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom, and preferably hydrogen. Atom, C1-C20 chain alkyl group, C5-C14 cyclic alkyl group, C1-C20 alkoxy group, C7-
20 aralkyl groups, phenyl groups, fluorine atoms, chlorine atoms or bromine atoms, more preferably hydrogen atoms,
It is a chain alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, an α-methylbenzyl group, a cumyl group, a phenyl group or a chlorine atom, and a hydrogen atom is particularly preferable. In the salicylic acid derivative represented by the general formula (1), Y ₁ and Y ₂ represent an oxygen atom or a sulfur atom, preferably Y ₁ is an oxygen atom, and more preferably Y ₁ and Y ₂ are oxygen atoms. Is.

In the salicylic acid derivative represented by the general formula (1), R ₁ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, preferably a hydrogen atom, a chain alkyl group having 1 to 20 carbon atoms, A cyclic alkyl group having 5 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and more preferably a hydrogen atom, a chain alkyl group having 1 to 8 carbon atoms, or a cyclopentyl group. , A cyclohexyl group, a cycloheptyl group, a benzyl group or a phenyl group, more preferably a hydrogen atom, a chain alkyl group having 1 to 4 carbon atoms or a phenyl group, and particularly preferably a hydrogen atom. General formula (1)
In the salicylic acid derivative represented by, R ₂ represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group, preferably a chain alkyl group which may have a substituent or a substituent which may have a substituent. Good cyclic alkyl group, chain alkenyl group optionally having substituent (s), cyclic alkenyl group optionally having substituent (s), aralkyl group optionally having substituent (s), having substituent (s) An optionally substituted phenyl group, an optionally substituted naphthyl group, or an optionally substituted heteroaromatic ring group.

The alkyl group and alkenyl group of R ₂ may have a substituent, and examples thereof include an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkoxy group having 2 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. Oxy group, carbon number 7-
An aralkyloxy group having 20 carbon atoms, an aralkyloxyalkoxy group having 8 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aryloxyalkoxy group having 7 to 20 carbon atoms,
Arylalkenyl group having 8 to 20 carbon atoms, 9 to 2 carbon atoms
0 aralkylalkenyl group, C1-20 alkylthio group, C2-20 alkoxyalkylthio group, C2-20 alkylthioalkylthio group, C2-20 alkenylthio group, C7-20 Aralkylthio group, C 8-20 aralkyloxyalkylthio group, C 8-20 aralkylthioalkylthio group, C 6-20 arylthio group, C 7
To 20 aryloxyalkylthio groups, having 7 to 2 carbon atoms
It may be mono- or poly-substituted with a substituent such as an arylthioalkylthio group of 0, a heteroalkyl-containing cyclic alkyl group, or a halogen atom. Further, the aryl group contained in these substituents further includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, It may be substituted with an aralkyloxy group having 7 to 10 carbon atoms, a hydroxyl group, a halogen atom or the like.

The aralkyl group of R ₂ and the aryl group in the aryl group may have a substituent, and examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a carbon number. 7-20 aralkyl groups, 6 carbon atoms
To 20 aryl groups, C1 to C20 alkoxy groups,
Alkoxyalkyl group having 2 to 20 carbon atoms, 2 to 2 carbon atoms
0 alkoxyalkoxy group, C2-20 alkenyloxy group, C3-20 alkenyloxyalkyl group, C3-20 alkenyloxyalkoxy group, C7-20 aralkyloxy group, carbon number 8 ~
An aralkyloxyalkyl group having 20 carbon atoms, an aralkyloxyalkoxy group having 8 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aryloxyalkyl group having 7 to 20 carbon atoms, an aryloxyalkoxy group having 7 to 20 carbon atoms,
Alkylcarbonyl group having 2 to 20 carbon atoms, 3 to 2 carbon atoms
0 alkenylcarbonyl group, C8-20 aralkylcarbonyl group, C7-20 arylcarbonyl group, C2-20 alkoxycarbonyl group, C3-20 alkenyloxycarbonyl group, C8
~ 20 aralkyloxycarbonyl groups, 7 to 2 carbon atoms
0 aryloxycarbonyl group, C2-20 alkylcarbonyloxy group, C3-20 alkenylcarbonyloxy group, C8-20 aralkylcarbonyloxy group, C7-20 arylcarbonyloxy group An aralkyloxy aralkyl group having 14 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and 7 carbon atoms
It may be mono- or polysubstituted with a substituent such as an aralkylthio group having 20 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, a nitro group, a formyl group, a halogen atom, a hydroxyl group and a cyano group. Further, the aryl group contained in these substituents includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and a carbon atom. It may be substituted with an aralkyloxy group having a number of 7 to 10, a hydroxyl group, a halogen atom or the like.

Preferably, R ₂ is an alkyl group having 1 to 24 carbon atoms which may have a substituent, an alkenyl group having 2 to 24 carbon atoms which may have a substituent, or a substituent. It is an aralkyl group having a total of 7 to 24 carbon atoms which may be possessed or an aryl group having a total of 6 to 24 carbon atoms which may have a substituent, and particularly preferably it may have a substituent. An alkyl group having a total carbon number of 1 to 16, an aralkyl group having a total carbon number of 7 to 16 which may have a substituent, or an aryl group having a total carbon number of 6 to 16 which may have a substituent.

Specific examples of R ₂ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group and n-
Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n -Heptyl group, 1-methylhexyl group, n-octyl group, 1-methylheptyl group,
2-ethylhexyl group, n-nonyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-undecyl group, 1-methyldecyl group Group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, cyclopentyl group, cyclohexyl group,
4-methylcyclohexyl group, 3-methylcyclohexyl group, 2-methylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, 3-
tert-butylcyclohexyl group, 4-phenylcyclohexyl group, 2-phenylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclohexylmethyl group,
2-cyclohexylethyl group, bornel group, isobornel group, 2-norbornanemethyl group, 1-adamantylmethyl group,

Vinyl group, allyl group, 2-butenyl group, 3
-Butenyl group, 1-methyl-4-pentenyl group, 2-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group Group, 2-heptenyl group, 1
-Vinylhexyl group, 3-nonenyl group, 6-nonenyl group, 9-decenyl group, 10-undecenyl group, 1-cyclohexenyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group, 2-
n-hexyloxyethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2-n-
Decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-cyclohexyloxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-n-butoxypropyl group, 3 -N
-Hexyloxypropyl group, 3-n-octyloxypropyl group, 3-cyclohexyloxypropyl group, 4
-Ethoxybutyl group, 5-methoxypentyl group, 6-ethoxyhexyl group, 2-methoxyethoxyethyl group, 2
-Ethoxyethoxyethyl group, 2-n-butoxyethoxyethyl group, 3-ethoxyethoxypropyl group,

2-allyloxyethyl group, 2- (4'-
(Pentenyl) oxyethyl group, 3-allyloxypropyl group, 4-allyloxybutyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4 '
-Methylbenzyloxy) ethyl group, 2- (4'-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 4-benzyloxybutyl group, 2-benzyloxymethoxyethyl group, 2- (4'-methyl Benzyl)
Oxymethoxyethyl group, phenoxymethyl group, 2-phenoxyethyl group, 2- (4'-chlorophenyloxy) ethyl group, 2- (4'-methylphenyloxy) ethyl group, 2- (4'-methoxyphenyloxy) Ethyl group, 3-phenoxypropyl group, 4-phenoxybutyl group, 6- (2′-chlorophenyloxy) hexyl group,
2-phenoxyethoxyethyl group, 2- (1'-naphthyloxy) ethyl group, 2- (2'-naphthyloxy) ethyl group, 3- (2'-naphthyloxy) propyl group, cinnamyl group,

2-methylthioethyl group, 2-ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octylthioethyl group, 2
-N-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthiobutyl group, 4-n- Butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group,
8-methylthiooctyl group, 2-methoxyethylthioethyl group, 2-ethylthioethylthioethyl group, 2-allylthioethyl group, 2-benzylthioethyl group, 3-
(4'-methylbenzylthio) propyl group, 4-benzylthiobutyl group, 2-benzyloxyethylthioethyl group, 3-benzylthiopropylthiopropyl group, 2-phenylthioethyl group, 2- (4'-methoxy Phenylthio) ethyl group, 2-phenoxyethylthioethyl group, 3
-(2'-chlorophenylthio) ethylthiopropyl group, 2-tetrahydrofurfuryl group,

2-chloroethyl group, 3-chloropropyl group, 2,2,2-trichloroethyl group, 7-chloroheptyl group, 8-chlorooctyl group, 8-fluorooctyl group, benzyl group, α-methylbenzyl group , Α-ethylbenzyl group, phenethyl group, α-methylphenethyl group,
α, α-dimethylphenethyl group, 4-methylphenethyl group, 4-methylbenzyl group, 3-methylbenzyl group, 2
-Methylbenzyl group, 4-isopropylbenzyl group, 4
-Allylbenzyl group, 4-benzylbenzyl group, 4-phenethylbenzyl group, 4-phenylbenzyl group, 4-
(4'-methylphenyl) benzyl group, 4-methoxybenzyl group, 4-n-butoxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4
-Allyloxybenzyl group, 4-vinyloxymethylbenzyl group, 4-benzyloxybenzyl group, 4-phenethyloxybenzyl group, 4-phenoxybenzyl group, 3
-Phenoxybenzyl group, 4-hydroxybenzyl group,
3-hydroxybenzyl group, 2-hydroxybenzyl group, 4-hydroxy-3-methoxybenzyl group, 4-chlorobenzyl group, 3-chlorobenzyl group, 2-chlorobenzyl group, 2-furfuryl group, diphenylmethyl group, 1
-Naphthylmethyl group, 2-naphthylmethyl group,

Phenyl group, 1-naphthyl group, 2-naphthyl group, 3-freel group, 3-thienyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2
-Ethylphenyl group, 4-n-propylphenyl group, 4
-Isopropylphenyl group, 4-n-butylphenyl group, 4-sec-butylphenyl group, 4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-n-hexylphenyl group Group, 4-n
-Heptylphenyl group, 4-n-octylphenyl group,
4-tert-octylphenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4- Allylphenyl group, 2-allylphenyl group, 4
-Benzylphenyl group, 2-benzylphenyl group, 4-
Cumylphenyl group, 4- (4'-methoxycumyl) phenyl group, 4- (4'-benzyloxy) cumylphenyl group, 4- (4'-chlorobenzyl) phenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group,

4- (4'-methoxyphenyl) phenyl group, 4- (4'-n-butoxyphenyl) phenyl group,
2- (2'-methoxyphenyl) phenyl group, 4-
(4′-chlorophenyl) phenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 2-ethoxyphenyl group, 3-n-propoxyphenyl group, 4-iso Propoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 4-n-octyl Oxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2 -Methoxy-1-naphthyl group,
4-methoxy-1-naphthyl group, 4-n-butoxy-1
-Naphthyl group, 5-ethoxy-1-naphthyl group, 6-ethoxy-2-naphthyl group, 6-n-butoxy-2-naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7
-Methoxy-2-naphthyl group, 7-n-butoxy-2-
Naphthyl group,

4-methoxymethylphenyl group, 4-ethoxymethylphenyl group, 4-n-butoxymethylphenyl group, 3-methoxymethylphenyl group, 4- (2'-methoxyethyl) phenyl group, 4- (2 ' -Ethoxyethyloxy) phenyl group, 4- (2'-n-butoxyethyloxy) phenyl group, 4- (3'-ethoxypropyloxy) phenyl group, 4-vinyloxyphenyl group, 4
-Allyloxyphenyl group, 3-allyloxyphenyl group, 4- (4'-pentenyloxy) phenyl group, 4-
Allyloxy-1-naphthyl group, 4-allyloxymethylphenyl group, 4- (2'-allyloxyethyloxy) phenyl group, 4-benzyloxyphenyl group, 2-
Benzyloxyphenyl group, 4-phenethyloxyphenyl group, 4- (4'-chlorobenzyloxy) phenyl group, 4- (4'-methylbenzyloxy) phenyl group,
4- (4'-methoxybenzyloxy) phenyl group, 4
-(3'-ethoxybenzyloxy) phenyl group, 4-
Benzyloxy-1-naphthyl group, 5- (4′-methylbenzyloxy) -1-naphthyl group, 6-benzyloxy-2-naphthyl group, 7-benzyloxy-2-naphthyl group,

4- (benzyloxymethyl) phenyl group, 4- (2'-benzyloxyethyloxy) phenyl group, 4-phenoxyphenyl group, 3-phenoxyphenyl group, 2-phenoxyphenyl group, 4- (4 ' -Methylphenoxy) phenyl group, 4- (4'-methoxyphenoxy) phenyl group, 4- (4'-chlorophenoxy)
Phenyl group, 4-phenoxy-1-naphthyl group, 6-phenoxy-2-naphthyl group, 4-phenoxymethylphenyl group, 4- (2'-phenoxyethyloxy) phenyl group, 4- [2 '-(4' -Methylphenyl) oxyethyloxy] phenyl group, 4- [2 '-(4'-methoxyphenyl) oxyethyloxy] phenyl group, 4-
[2 ′-(4′-chlorophenyl) oxyethyloxy] phenyl group, 4-acetylphenyl group, 3-acetylphenyl group, 2-acetylphenyl group, 4-ethylcarbonylphenyl group, 4-n-butylcarbonylphenyl group , 4-n-hexylcarbonylphenyl group, 4-n
-Octylcarbonylphenyl group, 4-cyclohexylcarbonylphenyl group, 4-acetyl-1-naphthyl group, 6-acetyl-2-naphthyl group, 6-n-butylcarbonyl-2-naphthyl group, 4-allylcarbonylphenyl group, 4-benzylcarbonylphenyl group, 4-
(4'-methylbenzyl) carbonylphenyl group, 4-
Phenylcarbonylphenyl group, 4- (4'-methylphenyl) carbonylphenyl group, 4- (4'-chlorophenyl) carbonylphenyl group, 4-phenylcarbonyl-1-naphthyl group, 4-methoxycarbonylphenyl group, 2-methoxy Carbonylphenyl group, 4-ethoxycarbonylphenyl group, 3-ethoxycarbonylphenyl group, 4-n-propoxycarbonylphenyl group, 4-
n-butoxycarbonylphenyl group, 4-n-hexyloxycarbonylphenyl group, 4-n-decyloxycarbonylphenyl group, 4-cyclohexyloxycarbonylphenyl group, 4-ethoxycarbonyl-1-naphthyl group, 6-methoxycarbonyl- 2-naphthyl group, 6-
n-butoxycarbonyl-2-naphthyl group, 4-allyloxycarbonylphenyl group, 4-benzyloxycarbonylphenyl group, 4- (4'-chlorobenzyl) oxycarbonylphenyl group, 4-phenethyloxycarbonylphenyl group, 6- Benzyloxycarbonyl-2-
Naphthyl group, 4-phenyloxycarbonylphenyl group, 4- (4'-ethylphenyl) oxycarbonylphenyl group, 4- (4'-chlorophenyl) oxycarbonylphenyl group, 4- (4'-ethoxyphenyl) oxycarbonylphenyl group Group, 6-phenyloxycarbonyl-2-naphthyl group,

4-acetyloxyphenyl group, 3-acetyloxyphenyl group, 4-ethylcarbonyloxyphenyl group, 2-ethylcarbonyloxyphenyl group, 4
-N-propylcarbonyloxyphenyl group, 4-n-
Pentylcarbonyloxyphenyl group, 4-n-octylcarbonyloxyphenyl group, 4-cyclohexylcarbonyloxyphenyl group, 4-acetyloxy-1-
Naphthyl group, 4-n-butylcarbonyloxy-1-naphthyl group, 5-acetyloxy-1-naphthyl group, 6-
Ethylcarbonyloxy-2-naphthyl group, 7-acetyloxy-2-naphthyl group, 4-allylcarbonyloxyphenyl group, 4-benzylcarbonyloxyphenyl group, 4-phenethylcarbonyloxyphenyl group, 6-
Benzylcarbonyloxy-2-naphthyl group, 4-phenylcarbonyloxyphenyl group, 4- (4'-methylphenyl) carbonyloxyphenyl group, 4- (2'-
Methylphenyl) carbonyloxyphenyl group, 4-
(4'-chlorophenyl) carbonyloxyphenyl group, 4- (2'-chlorophenyl) carbonyloxyphenyl group, 4-phenylcarbonyloxy-1-naphthyl group, 6-phenylcarbonyloxy-2-naphthyl group,
7-phenylcarbonyloxy-2-naphthyl group, 4-
Methylthiophenyl group, 2-methylthiophenyl group, 4
-Ethylthiophenyl group, 3-ethylthiophenyl group,
4-n-propylthiophenyl group, 4-n-butylthiophenyl group, 4-n-hexylthiophenyl group, 4-n
-Octylthiophenyl group, 4-cyclohexylthiophenyl group, 4-benzylthiophenyl group, 3-benzylthiophenyl group, 4- (4'-chlorobenzylthio) phenyl group, 4-phenylthiophenyl, 3-phenylthio Phenyl group, 4- (4'-methylphenylthio) phenyl group, 4- (4'-methoxyphenylthio) phenyl group, 4- (4'-chlorophenylthio) phenyl group, 2
-Ethylthio-1-naphthyl group, 4-methylthio-1-
Naphthyl group, 6-ethylthio-2-naphthyl group, 6-phenylthio-2-naphthyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2
-Chlorophenyl group, 4-bromophenyl group, 4-chloro-1-naphthyl group, 4-chloro-2-naphthyl group, 6
-Bromo-2-naphthyl group, 4-nitrophenyl group, 3
-Nitrophenyl group, 4-formylphenyl group, 3-formylphenyl group, 2-formylphenyl group, 4-formyl-1-naphthyl group, 1-formyl-2-naphthyl group,

4-hydroxyphenyl group, 3-hydroxyphenyl group, 2-hydroxyphenyl group, 4-hydroxy-1-naphthyl group, 6-hydroxy-2-naphthyl group, 4-cyanophenyl group, 2-cyanophenyl group Four
-Cyano-1-naphthyl group, 6-cyano-2-naphthyl group, 2-chloro-4-nitrophenyl group, 4-chloro-
2-nitrophenyl group, 6-chloro-3-methylphenyl group, 2-chloro-6-methylphenyl group, 4-chloro-2-methylphenyl group, 4-chloro-3-methylphenyl group, 2,4- Dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-
Dimethylphenyl group, 2,6-dimethylphenyl group,
2,4-diethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,
4,6-trimethylphenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-
Dichlorophenyl group, 3,5-dichlorophenyl group,
2,4,6-trichlorophenyl group, 2-methoxy-4
-Methylphenyl group, 2,6-dimethoxyphenyl group,
3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 3,
4,5-trimethoxyphenyl group, 2,4-dichloro-
Examples thereof include 1-naphthyl group and 1,6-dichloro-2-naphthyl group, but are not limited thereto.

The compound represented by the general formula (1) according to the present invention has a carbamate group in the salicylic acid skeleton, and the substitution position of the carbamate group is 3-position, 4-position, 5-position in the salicylic acid skeleton. 6th position,
Substitution at the 3-position, 4-position or 5-position is more preferable, and substitution at the 4-position or 5-position is particularly preferable. That is, a salicylic acid derivative represented by the following general formula (1-a) or general formula (1-b) (formula 5) is particularly preferable.

[0024]

Embedded image (In the above formula, X ₁ , X ₂ , Y ₁ , Y ₂ , R ₁ and R ₂ are the same as above)

Specific examples of the salicylic acid derivative represented by the general formula (1) according to the present invention include the salicylic acid derivatives shown below. Of course, the present invention is not limited thereto. is not. Exemplified Compound Number 1.3- (Isopropyloxycarbonylamino) salicylic acid 2.3- (Isopentyloxycarbonylamino) salicylic acid 3.3- (n-hexyloxycarbonylamino) salicylic acid 4.3- (n-octyloxycarbonylamino) ) Salicylic acid 5.3- (n-decyloxycarbonylamino) salicylic acid 6.3-[(4'-methylcyclohexyl) oxycarbonylamino] salicylic acid 7.3-[(2'-cyclohexylethyl) oxycarbonylamino] Salicylic acid 8.3- (allyloxycarbonylamino) salicylic acid 9.3-[(2'-hexenyl) oxycarbonylamino] salicylic acid 10.3-[(2'-ethoxyethyl) oxycarbonylamino] salicylic acid 11.3 -[(3'-n-hexyloxypro ) Oxycarbonylamino] salicylic acid 12.3-[(2'-benzyloxyethyl) oxycarbonylamino] salicylic acid 13.3- (phenoxymethyloxycarbonylamino) salicylic acid 14.3-[(2'-phenoxyethyl) ) Oxycarbonylamino] salicylic acid 15.3- [2 ′-(4-chlorophenyl) oxyethyloxycarbonylamino] salicylic acid

16.3- [2 ′-(4-Methoxyphenyl) oxyethyloxycarbonylamino] salicylic acid 17.3-[(2′-phenoxyethoxyethyl) oxycarbonylamino] salicylic acid 18.3- (cinnamyloxy) Carbonylamino) salicylic acid 19.3-[(2'-n-butylthioethyl) oxycarbonylamino] salicylic acid 20.3-[(2'-methoxyethylthioethyl) oxycarbonylamino] salicylic acid 21.3- [ (2'-Allylthioethyl) oxycarbonylamino] salicylic acid 22.3-[(2'-benzylthioethyl) oxycarbonylamino] salicylic acid 23.3-[(2'-phenylthioethyl) oxycarbonylamino ] Salicylic acid 24.3-[(7'-chloroheptyl) oxyca Rubonylamino] salicylic acid 25.3- (benzyloxycarbonylamino) salicylic acid 26.3-[(4′-methylbenzyl) oxycarbonylamino] salicylic acid 27.3-[(4′-chlorobenzyl) oxycarbonylamino] salicylic acid 28 3-[(3'-phenoxybenzyl) oxycarbonylamino] salicylic acid 29.3- (phenyloxycarbonylamino) salicylic acid 30.3-[(2'-naphthyl) oxycarbonylamino] salicylic acid

31.3-[(3′-Freel) oxycarbonylamino] salicylic acid 32.3-[(3′-phenylphenyl) oxycarbonylamino] salicylic acid 33.3-[(4′-methylphenyl) oxy Carbonylamino] salicylic acid 34.3-[(4'-n-butylphenyl) oxycarbonylamino] salicylic acid 35.3-[(4'-tert-butylphenyl) oxycarbonylamino] salicylic acid 36.3- [(4'-Cyclohexylphenyl) oxycarbonylamino] salicylic acid 37.3-[(3'-methoxyphenyl) oxycarbonylamino] salicylic acid 38.3-[(4'-n-butoxyphenyl) oxycarbonylamino ] Salicylic acid 39.3-[(4'-n-octyloxyphenyl) oxycarbonyl Amino] salicylic acid 40.3-[(4'-phenoxyphenyl) oxycarbonylamino] salicylic acid 41.3-[(2'-acetylphenyl) oxycarbonylamino] salicylic acid 42.3-[(4'-allyl Carbonylphenyl) oxycarbonylamino] salicylic acid 43.3-[(4′-phenylcarbonylphenyl) oxycarbonylamino] salicylic acid 44.3-[(4′-n-butoxycarbonylphenyl) oxycarbonylamino] salicylic acid 45.3 -[(4'-Benzyloxyphenyl) oxycarbonylamino] salicylic acid

46.3-[(4′-Acetyloxyphenyl) oxycarbonylamino] salicylic acid 47.3-[(4′-ethylthiophenyl) oxycarbonylamino] salicylic acid 48.3-[(4 '-Fluorophenyl) oxycarbonylamino] salicylic acid 49.3-[(4'-chlorophenyl) oxycarbonylamino] salicylic acid 50.3-[(4'-nitrophenyl) oxycarbonylamino] salicylic acid 51.3-[( 4'-formylphenyl) oxycarbonylamino] salicylic acid 52.3-[(4'-hydroxyphenyl) oxycarbonylamino] salicylic acid 53.3-[(4'-cyanophenyl) oxycarbonylamino] salicylic acid 54. 3-[(2 ', 4'-dimethylphenyl) oxycarbonylami ] Salicylic acid 55.3-[(3 ′, 5′-dichlorophenyl) oxycarbonylamino] salicylic acid 56.5-methyl-3- (n-hexyloxycarbonylamino) salicylic acid 57.5-cyclohexyl-3- (Phenyloxycarbonylamino) salicylic acid 58.5-cumyl-3- (n-hexyloxycarbonylamino) salicylic acid 59.3- (n-octylthiolcarbonylamino) salicylic acid 60.3-[(4'-chlorobenzyl ) Thiolcarbonylamino] salicylic acid

61.3-[(3′-methylphenyl) thiolcarbonylamino] salicylic acid 62.3- (n-butylthiolthiocarbonylamino) salicylic acid 63.3- (phenylthiolthiocarbonylamino) salicylic acid 64.3 -[(4'-Ethoxyphenyl) thiolthiocarbonylamino] salicylic acid 65.3- (N-phenyl-N-phenyloxycarbonylamino) salicylic acid 66.4- (methyloxycarbonylamino) salicylic acid 67.4- (Ethyloxycarbonylamino) salicylic acid 68.4- (n-Propyloxycarbonylamino) salicylic acid 69.4- (Isopropyloxycarbonylamino) salicylic acid 70.4- (n-Butyloxycarbonylamino) salicylic acid 71.4- (Isobutylo) Cycarbonylamino) salicylic acid 72.4- (sec-butyloxycarbonylamino) salicylic acid 73.4- (n-pentyloxycarbonylamino) salicylic acid 74.4- (isopentyloxycarbonylamino) salicylic acid 75.4- (n- Hexyloxycarbonylamino) salicylic acid

76.4- (n-heptyloxycarbonylamino) salicylic acid 77.4- (n-octyloxycarbonylamino) salicylic acid 78.4-[(2′-ethylhexyl) oxycarbonylamino] salicylic acid 79.4- ( n-nonyloxycarbonylamino) salicylic acid 80.4- (n-decyloxycarbonylamino) salicylic acid 81.4- (n-undecyloxycarbonylamino) salicylic acid 82.4- (n-dodecyloxycarbonylamino) salicylic acid 83. 4- (n-tridecyloxycarbonylamino) salicylic acid 84.4- (n-tetradecyloxycarbonylamino) salicylic acid 85.4- (n-pentadecyloxycarbonylamino) salicylic acid 86.4- (n-hexadecyloxy) Carbonyl No) salicylic acid 87.4- (n-heptadecyloxycarbonylamino) salicylic acid 88.4- (n-octadecyloxycarbonylamino) salicylic acid 89.4- (cyclopentyloxycarbonylamino) salicylic acid 90.4- (cyclohexyloxycarbonylamino) ) Salicylic acid

91.4-[(4′-tert-Butylcyclohexyl) oxycarbonylamino] salicylic acid 92.4- (Cycloheptyloxycarbonylamino) salicylic acid 93.4- (Cyclooctyloxycarbonylamino) salicylic acid 94.4 (Cyclohexylmethyloxycarbonylamino) salicylic acid 95.4-[(2'-tetrahydrofurfuryl) oxycarbonylamino] salicylic acid 96.4-[(2'-methoxyethyl) oxycarbonylamino] salicylic acid 97.4- [ (2'-n-Hexyloxyethyl) oxycarbonylamino] salicylic acid 98.4-[(2'-n-octyloxyethyl) oxycarbonylamino] salicylic acid 99.4-[(3'-ethoxypropyl) oxycarbonylamino ] Salicyl 100.4-[(3'-n-butoxypropyl) oxycarbonylamino] salicylic acid 101.4-[(3'-n-octyloxypropyl) oxycarbonylamino] salicylic acid 102.4-[(2'- n-Butoxyethoxyethyl) oxycarbonylamino] salicylic acid 103.4-[(2′-benzyloxyethyl) oxycarbonylamino] salicylic acid 104.4-[(phenoxymethyl) oxycarbonylamino] salicylic acid 105.4- [ (2'-phenoxyethyl) oxycarbonylamino] salicylic acid

106.4- [2 ′-(4-chlorophenyl) oxyethyloxycarbonylaminoamino] salicylic acid 107.4- [2 ′-(4-methoxyphenyl) oxyethyloxycarbonylamino] salicylic acid 108.4- [ (2'-Phenoxyethoxyethyl) oxycarbonylamino] salicylic acid 109.4-[(3'-n-butylthiopropyl) oxycarbonylamino] salicylic acid 110.4-[(6'-ethylthiohexyl) oxycarbonyl Amino] salicylic acid 111.4-[(2'-benzylthioethyl) oxycarbonylamino] salicylic acid 112.4-[(2'-phenylthioethyl) oxycarbonylamino] salicylic acid 113.4- [ (2'-Chloroethyl) oxycarbonylamino] salicylic acid 114 4-[(9′-decenyl) oxycarbonylamino] salicylic acid 115.4- (benzyloxycarbonylamino) salicylic acid 116.4-[(4′-methylbenzyl) oxycarbonylamino] salicylic acid 117.4-[(4 '-Chlorobenzyl) oxycarbonylamino] salicylic acid 118.4-[(2'-phenylethyl) oxycarbonylamino] salicylic acid 119.4- (phenyloxycarbonylamino) salicylic acid 120.4-[(1'-naphthyl) oxy Carbonylamino] salicylic acid

121.4-[(2'-naphthyl) oxycarbonylamino] salicylic acid 122.4-[(2'-furyl) oxycarbonylamino] salicylic acid 123.4-[(4'-phenylphenyl) oxycarbonylamino ] Salicylic acid 124.4-[(4'-methylphenyl) oxycarbonylamino] salicylic acid 125.4-[(3'-methylphenyl) oxycarbonylamino] salicylic acid 126.4-[(2'-methylphenyl) oxy Carbonylamino] salicylic acid 127.4-[(4'-ethylphenyl) oxycarbonylamino] salicylic acid 128.4-[(4'-tert-butylphenyl) oxycarbonylamino] salicylic acid 129.4-[(4 ' -Cyclohexylphenyl) oxycarbonylamino] salicyl Acid 130.4-[(2'-cyclohexylphenyl) oxycarbonylamino] salicylic acid 131 4-[(4'-cumylphenyl) oxycarbonylamino] salicylic acid 132.4-[(4'-methoxyphenyl) oxycarbonylamino ] Salicylic acid 133.4-[(3'-methoxyphenyl) oxycarbonylamino] salicylic acid 134.4-[(2'-ethoxyphenyl) oxycarbonylamino] salicylic acid 135.4-[(4'-n- Butoxyphenyl) oxycarbonylamino] salicylic acid

136.4-[(4′-n-hexyloxyphenyl) oxycarbonylamino] salicylic acid 137.4-[(4′-benzyloxyphenyl) oxycarbonylamino] salicylic acid 138.4- [4 ′ -(4-Benzyloxycumyl) phenyloxycarbonylamino] salicylic acid 139.4-[(4'-phenoxyphenyl) oxycarbonylamino] salicylic acid 140.4- [2 '-(6-benzyloxy) naphthyloxy Carbonylamino] salicylic acid 141.4-[(4'-phenylcarbonylphenyl) oxycarbonylamino] salicylic acid 142.4-[(4'-acetylphenyl) oxycarbonylamino] salicylic acid 143.4-[(4'-ethoxy) Carbonylphenyl) oxycarbonylamino ] Salicylic acid 144.4-[(4'-cyclohexyloxycarbonylphenyl) oxycarbonylamino] salicylic acid 145.4-[(4'-n-propylcarbonyloxyphenyl) oxycarbonylamino] salicylic acid 146.4-[(4'-methylthio Phenyl) oxycarbonylamino] salicylic acid 147.4-[(4'-benzylthiophenyl) oxycarbonylamino] salicylic acid 148 4-[(4'-fluorophenyl) oxycarbonylamino] salicylic acid 149.4- [(2'-Fluorophenyl) oxycarbonylamino] salicylic acid 150.4-[(4'-chlorophenyl) oxycarbonylamino] salicylic acid

151.4-[(3′-chlorophenyl) oxycarbonylamino] salicylic acid 152.4-[(4′-bromophenyl) oxycarbonylamino] salicylic acid 153.4-[(4′-nitrophenyl) oxycarbonyl Amino] salicylic acid 154.4-[(4'-formylphenyl) oxycarbonylamino] salicylic acid 155.4-[(4'-cyanophenyl) oxycarbonylamino] salicylic acid 156.4-[(2 ', 4'- Dimethylphenyl) oxycarbonylamino] salicylic acid 157.4-[(3 ′, 5′-dimethylphenyl) oxycarbonylamino] salicylic acid 158.4-[(2 ′, 4′-dichlorophenyl) oxycarbonylamino] Salicylic acid 159.4-[(3 ', 5'-dimethoxyphenyi ) Oxycarbonylamino] salicylic acid 160.4-[(3'-nitro-4'-chlorophenyl) oxycarbonylamino] salicylic acid 161.4-[(4'-chloro-2'-methylphenyl) oxycarbonylamino) ] Salicylic acid 162.4- (n-octylthiolcarbonylamino) salicylic acid 163.4- (phenylthiolcarbonylamino) salicylic acid 164.4-[(4'-ethoxyphenylthiol) carbonylamino] salicylic acid 165.4- ( n-hexylthiolthiocarbonylamino) salicylic acid

166.4-[(4′-Methylphenylthiol) thiocarbonylamino] salicylic acid 167.4- (n-decyloxythiocarbonylamino) salicylic acid 168.4- (Nn-butyl-N-) Heptyloxycarbonylamino) salicylic acid 169.3-Ethyl-4- (phenyloxycarbonylamino) salicylic acid 170.3-chloro-4- (n-butyloxycarbonylamino) salicylic acid 171.5- (methyloxycarbonylamino) Salicylic acid 172.5- (ethyloxycarbonylamino) salicylic acid 173.5- (n-propyloxycarbonylamino) salicylic acid 174.5- (n-butyloxycarbonylamino) salicylic acid 175.5- (isobutyloxycarbonylamino) salicylic acid 176 ． 5- (n-pentyloxycarbonylamino) salicylic acid 177.5- (isopentyloxycarbonylamino) salicylic acid 178.5- (n-hexyloxycarbonylamino) salicylic acid 179.5- (n-heptyloxycarbonylamino) salicylic acid 180 5- (n-octyloxycarbonylamino) salicylic acid

181.5-[(2′-ethylhexyl) oxycarbonylamino] salicylic acid 182.5- (n-nonyloxycarbonylamino) salicylic acid 183.5- (n-decyloxycarbonylamino) salicylic acid 184.5- ( n-Undecyloxycarbonylamino) salicylic acid 185.5- (n-dodecyloxycarbonylamino) salicylic acid 186.5- (n-tetradecyloxycarbonylamino) salicylic acid 187.5- (n-hexadecyloxycarbonylamino) salicylic acid 188.5- (Cyclohexyloxycarbonylamino) salicylic acid 189.5-[(4'-methylcyclohexyl) oxycarbonylamino] salicylic acid 190.5-[(4'-tert-butylcyclohexyl) oxycarbonylami ] Salicylic acid 191.5-[(2'-cyclohexylethyl) oxycarbonylamino] salicylic acid 192.5- (Cyclooctyloxycarbonylamino) salicylic acid 193.5-[(2'-tetrahydrofurfuryl) oxycarbonylamino] Salicylic acid 194.5-[(2'-methoxyethyl) oxycarbonylamino] salicylic acid 195.5-[(2'-n-hexyloxyethyl) oxycarbonylamino] salicylic acid

196.5-[(3′-Ethoxypropyl) oxycarbonylamino] salicylic acid 197.5-[(3′-isopropoxypropyl) oxycarbonylamino] salicylic acid 198.5-[(2′- Methoxyethoxyethyl) oxycarbonylamino] salicylic acid 199.5- (phenoxymethyloxycarbonylamino) salicylic acid 200.5- (2′-phenoxyethyloxycarbonylamino) salicylic acid 201.5- [2 ′-(4-chlorophenyl) ) Oxyethyloxycarbonylamino] salicylic acid 202.5- [2 ′-(4-methoxyphenyl) oxyethyloxycarbonylamino] salicylic acid 203.5-[(2′-phenoxyethoxyethyl) oxycarbonylamino] salicylic acid 204. 5-[( '-N-Hexylthioethyl) oxycarbonylamino] salicylic acid 205.5-[(2'-phenylthioethyl) oxycarbonylamino] salicylic acid 206.5- (2'-chloroethyloxycarbonylamino) salicylic acid 207.5- (5'-Hexenyloxycarbonylamino) salicylic acid 208.5- (Benzyloxycarbonylamino) salicylic acid 209.5-[(4'-methylbenzyl) oxycarbonylamino] salicylic acid 210.5-[(4 ' -Chlorobenzyl) oxycarbonylamino] salicylic acid

211.5-[(2′-Phenylethyl) oxycarbonylamino] salicylic acid 212.5- (phenyloxycarbonylamino) salicylic acid 213.5-[(2′-naphthyl) oxycarbonylamino] salicylic acid 214.5 -[(4'-Phenylphenyl) oxycarbonylamino] salicylic acid 215.5-[(3'-methylphenyl) oxycarbonylamino] salicylic acid 216.5-[(4'-ethylphenyl) oxycarbonylamino] salicylic acid 217 .5-[(4'-Cyclohexylphenyl) oxycarbonylamino] salicylic acid 218.5-[(4'-cumylphenyl) oxycarbonylamino] salicylic acid 219.5-[(4'-methoxyphenyl) oxycarbonylamino] Salicylic acid 220. 5-[(3'-ethoxyphenyl) oxycarbonylamino] salicylic acid 221.5-[(4'-n-butoxyphenyl) oxycarbonylamino] salicylic acid 222.5-[(4'-phenoxyphenyl) oxy Carbonylamino] salicylic acid 223.5-[(4'-acetylphenyl) oxycarbonylamino] salicylic acid 224.5-[(4'-methoxycarbonylphenyl) oxycarbonylamino] salicylic acid 225.5-[(4 ' -Ethylcarbonyloxyphenyl) oxycarbonylamino] salicylic acid

226.5-[(4′-Ethylthiophenyl) oxycarbonylamino] salicylic acid 227.5-[(4′-Phenylthiophenyl) oxycarbonylamino] salicylic acid 228.5-[(4 '-Fluorophenyl) oxycarbonylamino] salicylic acid 229.5-[(3'-fluorophenyl) oxycarbonylamino] salicylic acid 230.5-[(4'-chlorophenyl) oxycarbonylamino] salicylic acid 231.5- [ (3'-Chlorophenyl) oxycarbonylamino] salicylic acid 232.5-[(2'-chlorophenyl) oxycarbonylamino] salicylic acid 233.5-[(2'-formylphenyl) oxycarbonylamino] salicylic acid 234.5- [ (2'-Cyanophenyl) oxycarboni Amino] salicylic acid 235.5-[(2 ', 4'-dimethylphenyl) oxycarbonylamino] salicylic acid 236.5-[(3', 5'-dimethylphenyl) oxycarbonylamino] salicylic acid 237.5 -[(3'-Nitro-4'-chlorophenyl) oxycarbonylamino] salicylic acid 238.5- (n-butylthiolcarbonylamino) salicylic acid 239.5- (phenylthiolcarbonylamino) salicylic acid 240.5-[(2 '-Naphthylthiol) carbonylamino] salicylic acid

241.5-[(4′-Methylphenylthiol) carbonylamino] salicylic acid 242.5- (n-heptylthiolthiocarbonylamino) salicylic acid 243.5- (n-dodecylthiolthiocarbonylamino) salicylic acid 244 .5- (n-Pentyloxythiocarbonylamino) salicylic acid 245.5-[(4'-chlorophenyl) oxythiocarbonylamino] salicylic acid 246.5- (N-methyl-N-phenyloxycarbonylamino) salicylic acid 247 3-Methyl-5- (methyloxycarbonylamino) salicylic acid 248.3-Ethoxy-5- (n-butyloxycarbonylamino) salicylic acid 249.3-α-methylbenzyl-5- (ethyloxycarbonylamino) salicylic acid Acid 250.3- Phenyl-5- (n-hexyloxycarbonylamino) salicylic acid 251.6- (n-propyloxycarbonylamino) salicylic acid 252.6- (isopentyloxycarbonylamino) salicylic acid 253.6- (n-heptyloxycarbonylamino) ) Salicylic acid 254.6-[(1'-methylheptyl) oxycarbonylamino] salicylic acid 255.6- (n-dodecyloxycarbonylamino) salicylic acid

256.6-[(2 ′, 5′-Dimethylcyclohexyl) oxycarbonylamino] salicylic acid 257.6-[(2′-cyclohexylmethyl) oxycarbonylamino] salicylic acid 258.6-[(3 '-Butenyl) oxycarbonylamino] salicylic acid 259.6-[(10'-undecenyl) oxycarbonylamino] salicylic acid 260.6-[(2'-isopropoxyethyl) oxycarbonylamino] salicylic acid 261.6- [ (3′-Cyclohexyloxypropyl) oxycarbonylamino] salicylic acid 262.6-[(2′-phenethyloxyethyl) oxycarbonylamino] salicylic acid 263.6-[(2′-phenoxyethyl) oxycarbonylamino] Salicylic acid 264.6- [2 '-(4 Chlorophenoxy) ethyloxycarbonylamino] salicylic acid 265.6-[(3′-n-butylthiopropyl) oxycarbonylamino] salicylic acid 266.6- [3 ′-(4-methylbenzylthio) propyloxycarbonyla Mino] salicylic acid 267.6-[(2'-phenylthioethyl) oxycarbonylamino] salicylic acid 268.6-[(2'-tetrahydrofurfuryl) oxycarbonylamino] salicylic acid 269.6-[(2 '-Chloroethyl) oxycarbonylamino] salicylic acid 270.6- (benzyloxycarbonylamino) salicylic acid

271.6-[(4′-chlorobenzyl) oxycarbonylamino] salicylic acid 272.6- (phenyloxycarbonylamino) salicylic acid 273.6-[(1′-naphthyl) oxycarbonylamino] salicylic acid 274.6 -[(4'-phenylphenyl) oxycarbonylamino] salicylic acid 275.6-[(2'-ethylphenyl) oxycarbonylamino] salicylic acid 276.6-[(4'-tert-butylphenyl) oxycarbonylamino] Salicylic acid 277.6-[(3'-methoxyphenyl) oxycarbonylamino] salicylic acid 278.6-[(4'-n-hexyloxyphenyl) oxycarbonylamino] salicylic acid 279.6-[(3'- Phenoxyphenyl) oxycarbonylamino] sari Acid 280.6-[(4'-ethylcarbonylphenyl) oxycarbonylamino] salicylic acid 281.6-[(4'-benzylcarbonylphenyl) oxycarbonylamino] salicylic acid 282.6-[(4'-methoxycarbonylphenyl) ) Oxycarbonylamino] salicylic acid 283.6-[(4′-methylthiophenyl) oxycarbonylamino] salicylic acid 284.6-[(3′-fluorophenyl) oxycarbonylamino] salicylic acid 285.6-[(2 '-Chlorophenyl) oxycarbonylamino] salicylic acid

286.6-[(3′-Nitrophenyl) oxycarbonylamino] salicylic acid 287.6-[(2′-formylphenyl) oxycarbonylamino] salicylic acid 288.6-[(3′-hydroxyphenyl) Oxycarbonylamino] salicylic acid 289.6-[(4'-cyanophenyl) oxycarbonylamino] salicylic acid 290.6-[(3 ', 4'-dimethylphenyl) oxycarbonylamino] salicylic acid 291.6- [(2 ′, 4′-Dichlorophenyl) oxycarbonylamino] salicylic acid 292.3-ethyl-6- (n-hexyloxycarbonylamino) salicylic acid 293.3-tert-butyl-6- (phenyloxycarbonylamino) Salicylic acid 294.6- (N-ethyl-N-phenyloxyca Bonylamino) salicylic acid 295.6- (n-octylthiolcarbonylcarbonyl) salicylic acid 296.6-[(4'-methylbenzyl) thiolcarbonylamino] salicylic acid 297.6-[(4'-methylphenyl) thiolcarbonylamino] Salicylic acid 298.6- (n-octylthiolthiocarbonylamino) salicylic acid 299.6- (Phenylthiolthiocarbonylamino) salicylic acid 300.6-[(4'-methoxyphenyl) thiolthiocarbonylamino] salicylic acid

In the heat-sensitive recording material of the present invention, the salicylic acid derivative represented by the general formula (1) and the metal salt of the derivative as the electron-accepting compound may be used alone or in combination. May be.

The salicylic acid derivative represented by the general formula (1) according to the present invention can be prepared by a known method, for example, Bull. De. Soci.
e. Chim. France, 1189 (1955), J. Pharm. Sci., 52 ,
927 (1963) or the method described in JP-A-6-72984 can be suitably used for production. That is, the aminosalicylic acid derivative represented by the general formula (3) (Chemical Formula 6) is added to the aminosalicylic acid derivative in the presence of a base (eg, sodium hydroxide or sodium hydrogen carbonate) in an aqueous solution or an alcohol solvent (eg, methanol, ethanol, propanol). ,
(Butanol, pentanol, heptanol, octanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, etc.) can be produced by reacting the compound represented by the general formula (4) (formula 6).

[0047]

[Chemical 6] (In the above formula, X ₁ , X ₂ , Y ₁ , Y ₂ , R ₁ and R ₂ are the same as above, and Z represents a halogen atom.)

In the metal salt of the salicylic acid derivative represented by the general formula (1) according to the present invention, the metal salt includes monovalent metal salts such as sodium, potassium and lithium, and is more preferable. Is a polyvalent metal salt, more preferably a divalent, trivalent or tetravalent metal salt, and particularly preferably a divalent metal salt. Specific examples of the polyvalent metal salt include, for example, zinc, magnesium, calcium, barium, nickel, tin, copper, molybdenum, tungsten, zirconium, manganese, cobalt, titanium, aluminum and iron salts, and are preferable. Is a salt of zinc, magnesium, calcium, barium, nickel, manganese, cobalt or aluminum, more preferably a salt of zinc, magnesium, nickel or manganese, and particularly preferably a zinc salt.

The metal salt of the salicylic acid derivative represented by the general formula (1) according to the present invention, for example, an alkali metal salt such as monovalent sodium, potassium or lithium salt is usually represented by the general formula (1). To 1 equivalent of salicylic acid derivative
0.8 to 1.2 equivalents, preferably 1.0 to 1.1 equivalents of an alkali metal hydroxide compound, an alkali metal carbonate compound, an alkali metal hydrogen carbonate compound (for example, sodium hydroxide, potassium hydroxide, hydroxide Lithium, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, etc.) can be allowed to act in an aqueous solution.

In the salicylic acid derivative metal salt represented by the general formula (1), the polyvalent metal salt is usually an alkali metal salt 1 of the salicylic acid derivative represented by the general formula (1) in the presence of water. It can be produced by reacting 0.8 to 1.5 equivalents, preferably 1.0 to 1.2 equivalents of a water-soluble polyvalent metal compound with respect to the equivalent amount. The equivalent weight in this case means that the polyvalent metal compound is, for example, a divalent metal compound (for example, zinc sulfate) with respect to 1 mol of the alkali metal salt of the salicylic acid derivative represented by the general formula (1). Is equivalent to 1 equivalent of 0.5 mol of the divalent metal compound. At this time, heating may be performed or an organic solvent may coexist as desired.

As the aqueous solution of the alkali metal salt of salicylic acid derivative represented by the general formula (1), a plurality of different aqueous solutions of alkali metal salt of the salicylic acid derivative represented by the general formula (1) may be used. , For example, a mixed aqueous solution of 4- (n-butyloxycarbonylamino) salicylic acid and 4- (n-octyloxycarbonylamino) salicylic acid alkali metal salt solutions or 4- (phenyloxycarbonylamino) salicylic acid and 5- ( A polyvalent metal salt prepared by using a mixed aqueous solution of respective alkali metal salt aqueous solutions of cyclohexyloxycarbonylamino) salicylic acid can also be used as the electron-accepting compound for the heat-sensitive recording material of the present invention. Specific examples of the polyvalent metal compound include, for example, sulfates such as zinc sulfate, magnesium sulfate, and aluminum sulfate, zinc chloride, magnesium chloride,
Examples thereof include chlorides such as calcium chloride, barium chloride, nickel chloride, cobalt chloride and aluminum chloride, acetates such as zinc acetate and manganese acetate, nitrates such as zinc nitrate and the like. The polyvalent metal compounds may be used alone or in combination.

The salicylic acid derivative represented by the general formula (1) or the metal salt of the derivative produced as described above depends on the production conditions, the type of salicylic acid derivative represented by the general formula (1) or the type of metal. May sometimes form a solvate such as a hydrate, and the solvate is also suitable as an electron-accepting compound for the heat-sensitive recording material of the present invention. Of course, by a known method (for example, by drying),
From the solvate, a salicylic acid derivative or a metal salt of the derivative can be produced by removing a solvent such as water. Of course, the unsolvated salicylic acid derivative or the metal salt of the derivative can also be used in the thermosensitive recording of the present invention. It can be used as an electron-accepting compound for materials.

In the heat-sensitive recording material of the present invention, the salicylic acid derivative represented by the general formula (1) or the metal salt of the derivative as the electron-accepting compound may be used alone or in combination. Good. Furthermore, one or more salicylic acid derivatives represented by the general formula (1),
You may use together the metal salt of 1 or more types of salicylic acid derivative represented by General formula (1). In the heat-sensitive recording material of the present invention, the amount of the salicylic acid derivative represented by the general formula (1) or the metal salt of the derivative is not particularly limited, but is usually 100 parts by weight of the electron-donating color forming compound. 50 to 700 parts by weight, preferably 1
It is desirable to use about 100 to 500 parts by weight.

In the compound represented by the general formula (2) according to the present invention, X _{3 to} X ₆ represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an arylthio group or a halogen atom, and more preferably , A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
It represents an aryloxy group having 6 to 14 carbon atoms, an arylthio group having 6 to 14 carbon atoms, a fluorine atom, a chlorine atom and a bromine atom. Incidentally, the substitution position of the substituents X ₃ to X _6, to the -Y-, ortho, meta or para position. In the compound represented by the general formula (2), R ₃ and R ₄ represent an alkyl group or an aralkyl group, and more preferably,
It represents an alkyl group having 1 to 10 carbon atoms and an aralkyl group having 7 to 14 carbon atoms. In the compound represented by the general formula (2), Y represents a single bond, an oxygen atom or a sulfur atom, and n represents 0 or 1. Further, in the compound represented by the general formula (2), the substituents R ₃ CO— and R ₄ CO— have a substitution position with respect to —Y— in an ortho position, a meta position or a para position, and preferably , Para position. In consideration of various characteristics of the heat-sensitive recording material, among the compounds represented by the general formula (2), a compound having a melting point of about 70 to 150 ° C., more preferably about 80 to 130 ° C. is used. Preferably.

Specific examples of the compound represented by the general formula (2) include 4-methylcarbonylbiphenyl and 4
-Ethylcarbonylbiphenyl, 4-n-propylcarbonylbiphenyl, 4-n-butylcarbonylbiphenyl, 4-isobutylcarbonylbiphenyl, 4-n-hexylcarbonylbiphenyl, 4-n-octylcarbonylbiphenyl, 4-methyl-4'- Methylcarbonylbiphenyl, 4-methoxy-4'-methylcarbonylbiphenyl, 4-fluoro-4'-ethylcarbonylbiphenyl, 4-benzylcarbonylbiphenyl, 4-
(4'-methylbenzyl) carbonylbiphenyl, 4-
(4'-methylbenzyl) carbonylbiphenyl, 4-
(2'-chlorobenzyl) carbonylbiphenyl, 4-
Phenethylcarbonylbiphenyl,

4-methylcarbonyl-4'-fluorodiphenyl ether, 4-methylcarbonyl-4'-chlorodiphenyl ether, 4-methylcarbonyl-4'-
Bromodiphenyl ether, 4-methylcarbonyl-
4'-phenyloxydiphenyl ether, 4-methylcarbonyl-4'-phenylthiodiphenyl ether,
4-benzylcarbonyldiphenyl ether, 4-
(4'-methylbenzyl) carbonyl diphenyl ether, 4- (4'-chlorobenzyl) carbonyl diphenyl ether, 4-benzylcarbonyl-4'-chlorodiphenyl ether, 4-methylcarbonyl-4'-bromodiphenyl sulfide, 4-methylcarbonyl- 4 '
-Phenyloxydiphenyl sulfide, 4-methylcarbonyl-4'-phenylthiodiphenyl sulfide,
4-benzylcarbonyldiphenyl sulfide, 4-
(4'-methylbenzyl) carbonyldiphenyl sulfide, 4- (2'-methylbenzyl) carbonyldiphenyl sulfide, 4- (4'-chlorobenzyl) carbonyldiphenyl sulfide, 4-benzylcarbonyl-
4'-methyldiphenyl sulfide,

4,4'-Dimethylcarbonyldiphenyl ether, 4,4'-diethylcarbonyldiphenyl ether, 4,4'-di-n-propylcarbonyldiphenyl ether, 4,4'-di-n-butylcarbonyldiphenyl ether, 4,4 '-Di-isobutylcarbonyldiphenyl ether, 4,4'-di-n-pentylcarbonyldiphenyl ether, 4,4'-di-n-hexylcarbonyldiphenyl ether, 4,4'-di-n
-Octylcarbonyl diphenyl ether, 4,4'-
Di-n-nonylcarbonyldiphenyl ether, 4,
4'-di-n-decylcarbonyldiphenyl ether,
4,4'-dicyclopentylcarbonyldiphenyl ether, 4,4'-dicyclohexylcarbonyldiphenyl ether, 4- (methylcarbonyl) -4 '-(ethylcarbonyl) diphenyl ether, 4- (methylcarbonyl) -4'-(n-butylcarbonyl) ) Diphenyl ether, 4- (ethylcarbonyl) -4 '-(n-pentylcarbonyl) diphenyl ether, 4,4'-dibenzylcarbonyldiphenyl ether, 4,4'-di (4 "-methylbenzyl) carbonyldiphenyl ether,

4,4'-Dimethylcarbonyldiphenyl sulfide, 4,4'-diethylcarbonyldiphenyl sulfide, 4,4'-di-n-propylcarbonyldiphenyl sulfide, 4,4'-di-n-butylcarbonyldiphenyl sulfide , 4,4'-di-isobutylcarbonyldiphenyl sulfide, 4,4'-di-n-
Pentyl carbonyl diphenyl sulfide, 4,4'-
Di-n-hexylcarbonyldiphenyl sulfide,
4,4'-di-n-octylcarbonyldiphenyl sulfide, 4,4'-di-n-nonylcarbonyldiphenyl sulfide, 4,4'-di-n-decylcarbonyldiphenyl sulfide, 4,4'-dicyclopentylcarbonyl Diphenyl sulfide, 4,4'-dicyclohexylcarbonyl diphenyl sulfide, 4- (methylcarbonyl) -4 '-(ethylcarbonyl) diphenyl sulfide, 4- (methylcarbonyl) -4'-(n-butylcarbonyl) diphenyl sulfide, 4 Examples thereof include-(ethylcarbonyl) -4 '-(n-pentylcarbonyl) diphenylsulfide, 4,4'-dibenzylcarbonyldiphenylsulfide, 4,4'-di (4 "-methylbenzyl) carbonyldiphenylsulfide. Yes, but limited to these In the heat-sensitive recording material of the present invention, these compounds represented by the general formula (2) may be used alone or in combination.

The compound represented by the general formula (2) according to the present invention can be prepared by a known method, for example, J. Org. Chem., 23 , 1
539 (1958), J. Chem. Soc., 873 (195
4), Bull. Soc. Chim. De France, 1000 (197)
1), Bull. Soc. Chim. De France, 3234 (197).
It can be produced by the method described in 2). That is, for example, when -Y- is an oxygen atom, it is produced by a method of allowing a diphenyl ether derivative and an alkylcarbonyl halide derivative or an aralkyl halide derivative to act in the presence of a Friedel-Crafts catalyst such as aluminum chloride. be able to. In the heat-sensitive recording material of the present invention, the amount of the compound represented by the general formula (2) used is not particularly limited, but is usually
50 to 7 per 100 parts by weight of the electron-donating color forming compound
It is desirable to use about 100 parts by weight, preferably about 100 to 500 parts by weight.

The colorless or light-colored electron-donating color-forming compound used in the heat-sensitive recording material of the present invention is not particularly limited, but triarylmethane compounds, vinylphthalide compounds, diarylmethane compounds, rhodamine-type compounds. Lactam compounds, thiazine compounds, fluorane compounds, pyridine compounds, spiro compounds, various known electron-donating color-forming compounds such as fluorene compounds, and more preferably fluoran compounds, among which the general formula The fluoran compound represented by (A) (Chemical Formula 7) is preferable.

[0061]

[Chemical 7] (In the formula, A and B are an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkoxyalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a tetrahydrofurfuryl group. Further, A and B may form a heterocycle with adjacent nitrogen atoms, and Z ₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom. Z ₂ and Z ₃ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom or a trifluoromethyl group.) Specific examples of the electron-donating color forming compound include triarylmethane compounds. For example, 3,3-bis (4
-Dimethylaminophenyl) -6-dimethylaminophthalide ["Crystal violet lactone"], 3,3
-Bis (4-dimethylaminophenyl) phthalide, 3-
(4-Dimethylaminophenyl) -3- (4-diethylamino-2-methylphenyl) -6-dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3-
(1,2-dimethylindol-3-yl) phthalide,
3- (4-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3 , 3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3,3 -Bis (2
-Phenylindol-3-yl) -6-dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3
Examples include-(1-methylpyrrol-3-yl) -6-dimethylaminophthalide.

Examples of the vinyl phthalide compound include 3,3-bis [1,1-bis (4-dimethylaminophenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide, 3 , 3-bis [1,1-bis (4
-Pyrrolidinophenyl) ethylene-2-yl] -4,
5,6,7-Tetrabromophthalide, 3,3-bis [1
-(4-Dimethylaminophenyl) -1- (4-methoxyphenyl) ethylene-2-yl] -4,5,6,7-
Tetrachlorophthalide, 3,3-bis [1- (4-pyrrolidinophenyl) -1- (4-methoxyphenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide, etc. is there.

Examples of the diarylmethane compound include 4,4-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine,
N-2,4,5-trichlorophenyl leuco auramine and the like. As the rhodamine-lactam compound,
For example, rhodamine-B-anilinolactam, rhodamine- (4-nitroanilino) lactam, rhodamine-B
-(4-chloroanilino) lactam and the like. Examples of the thiazine compound include 3,7-bis (diethylamino) -10-benzoylphenoxazine, benzoylleuco methylene blue, and 4-nitrobenzoylmethylene blue.

Examples of fluoran compounds include:
3,6-dimethoxyfluorane, 3-dimethylamino-
7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3-N-cyclohexyl-Nn-butylamino-7-methylfluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-
Octylaminofluorane, 3-diethylamino-7-
Di-n-hexylaminofluorane, 3-diethylamino-7-anilinofluorane, 3-diethylamino-7
-(2'-fluorophenylamino) fluorane, 3-
Diethylamino-7- (2'-chlorophenylamino)
Fluorane, 3-diethylamino-7- (3'-chlorophenylamino) fluorane, 3-diethylamino-7
-(2 ', 3'-dichlorophenylamino) fluorane, 3-diethylamino-7- (3'-trifluoromethylphenylamino) fluorane, 3-di-n-butylamino-7- (2'-fluorophenylamino) Fluorane, 3-di-n-butylamino-7- (2'-chlorophenylamino) fluorane,

3-N-isopentyl-N-ethylamino-7- (2'-chlorophenylamino) fluorane, 3
-N-n-hexyl-N-ethylamino-7- (2'-
Chlorophenylamino) fluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-di-n
-Butylamino-6-chloro-7-anilinofluorane, 3-diethylamino-6-methoxy-7-anilinofluorane, 3-di-n-butylamino-6-ethoxy-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-morpholino-6-
Methyl-7-anilinofluorane, 3-dimethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-di-n-butylamino-6 -Methyl-7-anilinofluorane, 3-di-n-pentylamino-6-methyl-7-
Anilinofluorane, 3-N-ethyl-N-methylamino-6-methyl-7-anilinofluorane, 3-Nn
-Propyl-N-methylamino-6-methyl-7-anilinofluorane, 3-N-n-propyl-N-ethylamino-6-methyl-7-anilinofluorane, 3-N-
n-butyl-N-methylamino-6-methyl-7-anilinofluorane, 3-N-n-butyl-N-ethylamino-6-methyl-7-anilinofluorane, 3-N-isobutyl- N-methylamino-6-methyl-7-anilinofluorane, 3-N-isobutyl-N-ethylamino-6-methyl-7-anilinofluorane, 3-N-isopentyl-N-ethylamino-6 -Methyl-7-anilinofluorane, 3-N-n-hexyl-N-methylamino-6-methyl-7-anilinofluorane,

3-N-cyclohexyl-N-ethylamino-6-methyl-7-anilinofluorane, 3-N-cyclohexyl-N-n-propylamino-6-methyl-
7-anilinofluorane, 3-N-cyclohexyl-N
-N-butylamino-6-methyl-7-anilinofluorane, 3-N-cyclohexyl-Nn-hexylamino-6-methyl-7-anilinofluorane, 3-N-cyclohexyl-Nn -Octylamino-6-methyl-
7-anilinofluorane, 3-N-2'-methoxyethyl-N-methylamino-6-methyl-7-anilinofluorane, 3-N-2'-methoxyethyl-N-ethylamino-6- Methyl-7-anilinofluorane, 3-N-
2'-methoxyethyl-N-isobutylamino-6-methyl-7-anilinofluorane, 3-N-2'-ethoxyethyl-N-methylamino-6-methyl-7-anilinofluorane, 3- N-2'-ethoxyethyl-N-ethylamino-6-methyl-7-anilinofluorane, 3
-N-3'-methoxypropyl-N-methylamino-6
-Methyl-7-anilinofluorane, 3-N-3'-methoxypropyl-N-ethylamino-6-methyl-7-
Anilinofluorane, 3-N-3'-ethoxypropyl-N-methylamino-6-methyl-7-anilinofluorane, 3-N-3'-ethoxypropyl-N-ethylamino-6-methyl- 7-anilino fluoran,

3-N-2'-tetrahydrofurfuryl-
N-ethylamino-6-methyl-7-anilinofluorane, 3-N- (4'-methylphenyl) -N-ethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6- Ethyl-7-anilinofluorane, 3
-Diethylamino-6-methyl-7- (3'-methylphenylamino) fluorane, 3-diethylamino-6-
Methyl-7- (2 ', 6'-dimethylphenylamino)
Fluorane, 3-di-n-butylamino-6-methyl-
7- (2 ', 6'-dimethylphenylamino) fluorane, 3-di-n-butylamino-7- (2', 6'-dimethylphenylamino) fluorane, 2,2-bis [4 '-(3 -N-cyclohexyl-N-methylamino-6-methylfluorane) -7-ylaminophenyl]
Propane, 3- [4 '-(4-phenylaminophenyl) aminophenyl] amino-6-methyl-7-chlorofluorane, and the like.

Examples of the pyridine compound include 3-
(2-Ethoxy-4-diethylaminophenyl) -3-
(1-octyl-2-methylindol-3-yl)-
4 or 7-azaphthalide, 3- (2-ethoxy-4-
Diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4 or 7-azaphthalide, 3- (2-hexyloxy-4-diethylaminophenyl) -3- (1-ethyl-2- Methylindole-
3-yl) -4 or 7-azaphthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4 or 7-azaphthalide, 3- ( 2-butoxy-4-diethylaminophenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4 or 7-azaphthalide.

Examples of the spiro compound include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-
Dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxybenzo) spiropyran, 3
-Propyl-spiro-dibenzopyran and the like. Examples of the fluorene compound include 3,6-bis (dimethylamino) fluorene-9-spiro-3 ′-(6′-
Examples include dimethylamino) phthalide and 3,6-bis (diethylamino) fluorene-9-spiro-3 ′-(6′-dimethylamino) phthalide. Of course, it is not limited to these electron donating color forming compounds, and these electron donating color forming compounds may be used alone or in combination.

The heat-sensitive recording material of the present invention is characterized by containing at least one salicylic acid derivative represented by the general formula (1) or a metal salt of the derivative as an electron-accepting compound. Other electron-accepting compounds may be used in combination within the range that does not impair the desired effects of the present invention. In this case, the proportion of the salicylic acid derivative represented by the general formula (1) or the metal salt of the derivative in the total electron-accepting compound is usually 10% by weight or more, preferably,
It is desirable to adjust to 20% by weight or more, more preferably 30% by weight or more. The electron-accepting compound other than the salicylic acid derivative represented by the general formula (1) or the metal salt of the derivative is not particularly limited, but is a phenol derivative or a metal salt thereof, an organic acid derivative or a metal salt or complex thereof. Examples thereof include various known electron-accepting compounds such as organic electron-accepting compounds such as urea derivatives and inorganic electron-accepting compounds.

Specific examples of the electron-accepting compound other than the salicylic acid derivative represented by the general formula (1) or the metal salt of the derivative include 4-tert-butylphenol and 4
-Tert-octylphenol, 4-phenylphenol, 1-naphthol, 2-naphthol, hydroquinone, resorcinol, 4-tert-octylcatechol,
2,2'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 2,2-bis (4'-hydroxyphenyl) propane ["bisphenol A"],
1,1-bis (4′-hydroxyphenyl) cyclohexane, 2,2-bis (4′-hydroxy-3′-methylphenyl) propane, 1,3-bis (4′-hydroxycumyl) benzene, 1, 4-bis (4'-hydroxycumyl) benzene, 1,3,5-tris (4'-hydroxycumyl) benzene, 2,2-bis (4'-hydroxyphenyl) acetic acid ethyl ester, 4,4- (4'-Hydroxyphenyl) pentanoic acid-n-butyl ester, 4
-Hydroxybenzoic acid benzyl ester, 4-hydroxybenzoic acid phenethyl ester, 2,4-dihydroxybenzoic acid phenoxyethyl ester, 4-hydroxyphthalic acid dimethyl ester, gallic acid-n-propyl ester, gallic acid-n-octyl ester, Gallic acid-n
-Dodecyl ester, gallic acid-n-octadecyl ester,

Hydroquinone monobenzyl ether, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (2-methyl-4-hydroxyphenyl) sulfide, bis (3-phenyl-4-hydroxyphenyl) sulfide, bis (3 -Cyclohexyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxy) Phenyl) sulfone, 4-hydroxy-4'-methyldiphenyl sulfone, 4-hydroxy-4'-te
rt-Butyldiphenylsulfone, 4-hydroxy-
4'-chlorodiphenyl sulfone, 4-hydroxy-
4'-methoxydiphenyl sulfone, 4-hydroxy-4'-n-propoxydiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy-4'-n-butoxydiphenyl sulfone, 4-hydroxy-4 '-Benzyloxydiphenyl sulfone, 3,4-dihydroxy-4'-methyldiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone,

2-methoxy-4'-hydroxydiphenyl sulfone, 2-ethoxy-2'-hydroxydiphenyl sulfone, 4-hydroxy-3-methyl-4'-
n-propoxydiphenyl sulfone, bis (2-hydroxy-5-tert-butylphenyl) sulfone, bis (2-hydroxy-5-chlorophenyl) sulfone,
Bis [4- (3'-hydroxyphenyloxy) phenyl] sulfone, 4-hydroxybenzophenone, 2,
4-dihydroxybenzophenone, 2,4'-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 1,7-di (4'-hydroxyphenylthio)
Phenol derivatives such as -3,5-dioxaheptane and 1,5-di (4'-hydroxyphenylthio) -3-oxapentane, or metal salts of these phenol derivatives (for example, nickel, zinc, aluminum, calcium) Metal salts such as),

For example, 5- [4 '-(2- [4-methoxyphenoxy] ethoxy) cumyl] salicylic acid, 4-
[3 ′-(4-methylphenylsulfonyl) propoxy] salicylic acid, 4- [2 ′-(4-methoxyphenoxy) ethoxy] salicylic acid, 1-naphthoic acid, 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, 1-acetyloxy-2-naphthoic acid, 2-acetyloxy-1-naphthoic acid, 2-acetyloxy-3-
Naphthoic acid, phthalic acid monobenzyl ester, phthalic acid monophenyl ester, isophthalic acid, terephthalic acid,
4-methylbenzoic acid, 2-benzoylbenzoic acid, 2-
(4′-chlorobenzoyl) benzoic acid, 4-nitrobenzoic acid, 4-chlorobenzoic acid, 4-trifluoromethylbenzoic acid, 4-formylbenzoic acid, 4-cyanobenzoic acid,
Organic acid derivatives such as stearic acid, or metal salts of these organic acid derivatives (for example, metal salts such as nickel, zinc, aluminum, and calcium), for example, complexes such as zinc thiocyanate antipyrine complex and molybdic acid acetylacetone complex.

For example, N, N'-diphenylthiourea,
N, N'-di (3-trifluoromethylphenyl) thiourea, N, N'-di (3-chlorophenyl) thiourea,
1,4-di (3'-chlorophenyl) -3-thiosemicarbazide, N-phenyl-N '-(4-methylphenylsulfonyl) urea, 4,4'-bis (4 "-methylphenylsulfonylcarbonylamino) diphenylmethane Organic electron-accepting compounds such as urea derivatives such as, for example, acid clay, attapulgite, activated clay, inorganic electron-accepting compounds such as aluminum chloride, zinc chloride, zinc bromide, but are limited to these compounds A plurality of these electron-accepting compounds may be used in combination.

The heat-sensitive recording material of the present invention uses the compound represented by the general formula (2) as the heat-fusible compound (sensitizer), but does not impair the desired effects of the present invention. In the range, other known heat-fusible compounds (melting point about 70-15
It is also possible to jointly use 0 ° C., more preferably a compound having a melting point of about 80 to 130 ° C.). In this case, the proportion of the compound represented by the general formula (2) in the total heat-fusible compound is usually 30% by weight or more, preferably 50% by weight.
As described above, it is desirable to adjust the content to 60% by weight or more.

Specific examples of the heat-fusible compound other than the compound represented by the general formula (2) include, for example, caproic acid amide, capric acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, and erucic acid. Amide, linoleic acid amide, linolenic acid amide, N-ethylcapric acid amide, N-butyllauric acid amide, N-methylstearic acid amide, N-methyloleic acid amide, N
-Stearylcyclohexylamide, N-octadecylacetamide, N-oleylacetamide, stearylurea, stearic acid anilide, linoleic acid anilide, N
-Nitrogen-containing compounds such as ethylcarbazole, 4-methoxydiphenylamine, N-hydroxymethylstearic acid amide, ethylenebisstearic acid amide, for example, 4-benzyloxybenzoic acid benzyl ester, 2
-Naphthoic acid phenyl ester, 1-hydroxy-2-
Naphthoic acid phenyl ester, oxalic acid dibenzyl ester, oxalic acid di (4-methylbenzyl) ester, oxalic acid di (4-chlorobenzyl) ester, adipic acid diphenyl ester, glutaric acid diphenacyl ester, di (4-methyl) Ester compounds such as phenyl) carbonate and dibenzyl terephthalate,

Hydrocarbon compounds such as 4-benzylbiphenyl, m-terphenyl, fluorene, fluoranthene, 2,6-diisopropylnaphthalene and 3-benzylacenaphthene, for example, 2-benzyloxynaphthalene, 2- (4 ' -Methylbenzyloxy) naphthalene, 1,4-diethoxynaphthalene, 1,2-diphenoxyethane, 1,2-bis (3'-methylphenoxy)
Ethane, 1-phenoxy-2- (4'-methylphenoxy) ethane, 1-phenoxy-2- (4'-ethylphenoxy) ethane, 1- (4'-methoxyphenoxy)-
2-phenoxyethane, 1- (4'-methoxyphenoxy) -2- (3'-methylphenoxy) ethane, 1-
(4′-methoxyphenoxy) -2- (2′-methylphenoxy) ethane, 1,2-bis (4′-methoxyphenylthio) ethane, 1,5-bis (4′-methoxyphenoxy) -3-oxa Pentane, 1,4-bis (2'-
Vinyloxyethoxy) benzene, 4- (4'-methylphenoxy) biphenyl, 1,4-bis (2'-chlorobenzyloxy) benzene, 4,4'-di-n-butoxydiphenylsulfone, 1,2-di Phenoxybenzene, 1,4-bis (2'-chlorophenoxy) benzene, 1,4-bis (4'-methylphenoxy) benzene, 1,4-bis (3'-methylphenoxymethyl) benzene, 4-chlorobenzyl Oxy- (4′-ethoxybenzene), 4,4′-bis (phenoxy) diphenyl ether, 4,4′-bis (phenoxy) diphenylthioether, 1,4-bis (4′-benzylphenoxy) benzene, 1,4 An ether compound such as -bis [(4'-methylphenyloxy) methoxymethyl] benzene,

For example, 1,4-diglycidyloxybenzene, 4-benzyloxy-4 '-(2-methylglycidyloxy) diphenylsulfone, 4- (4-methylbenzyloxy) -4'-glycidyloxydiphenylsulfone, Epoxy compounds such as N-glycidylphthalimide, for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-tert
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)-
5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole and the like. Examples thereof include, but are not limited to, triazole compounds. These heat-fusible compounds may be used alone or in combination.

In some cases, it may be preferable to further include a metal compound in the heat-sensitive recording material of the present invention because the characteristics of the heat-sensitive recording material can be further improved. The metal compound is not particularly limited, but is preferably a polyvalent metal compound, more preferably a divalent, trivalent or tetravalent metal compound. Examples of the metal compound include zinc, magnesium, barium, calcium, aluminum, tin, titanium, nickel, cobalt, manganese, iron, and other metal oxides, hydroxides, sulfides, halides, carbonates, and the like. Phosphates, silicates, sulfates, nitrates, acetylacetonate complexes, organic carboxylates and the like can be mentioned, and zinc compounds are particularly preferable.

Specific examples of the metal compound include zinc oxide, zinc hydroxide, zinc aluminate, zinc sulfide, zinc carbonate, zinc phosphate, zinc silicate, zinc sulfate, zinc chloride, and the like.
Zinc nitrate, magnesium sulfate, magnesium aluminate, magnesium hydroxide, magnesium oxide, magnesium carbonate, barium carbonate, calcium sulfate, calcium chloride, calcium carbonate, aluminum oxide, aluminum hydroxide, aluminum silicate, aluminum phosphate,
Inorganic metal compounds such as tin oxide and titanium oxide, zinc,
Silica surface-treated with substances containing metal ions such as magnesium, barium, calcium and aluminum, zinc acetylacetonate, calcium acetylacetonate, nickel acetylacetonate, zinc stearate, magnesium stearate, calcium stearate, stearic acid Examples thereof include organometallic compounds such as aluminum, and hydrates thereof may be used. These metal compounds may be used alone or in combination. Particularly preferable metal compounds are inorganic metal compounds, and zinc oxide and zinc carbonate are particularly preferable. The amount of the metal compound is not particularly limited, but usually,
It is desirable to use 1 to 500 parts by weight, preferably 3 to 300 parts by weight, based on 100 parts by weight of the salicylic acid derivative represented by the general formula (1) or the metal salt of the derivative.

The heat-sensitive recording material of the present invention can be manufactured by a known method without using a special method. Generally, in the presence of water, an electron-donating color-forming compound, a salicylic acid derivative represented by the general formula (1) or a metal salt of the derivative, a compound represented by the general formula (2), and if desired, , A metal compound or the like, together or separately, with a ball mill, a sand mill (vertical type, horizontal type), an attritor, a colloidal mill or the like, and a pulverizer to obtain a particle size of usually 3 μm or less, preferably 2 μm or less. It is possible to prepare a coating liquid for the recording layer by pulverizing and dispersing to a mixture and mixing.

In such a coating liquid, a binder is usually added in an amount of about 5 to 50% by weight based on the total solid content. As the binder, a water-soluble binder is generally used, for example,
Polyvinyl alcohol, carboxy modified polyvinyl alcohol, sulfonation modified polyvinyl alcohol, polyvinyl alcohol derivatives such as alkyl modified polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and other cellulose derivatives, epichlorohydrin modified polyamide, ethylene-maleic anhydride Polymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylamide, methylol-modified polyacrylamide, starch, starch derivative (oxidized starch, etherified starch, etc.), casein, gelatin , Gum arabic, and the like, but are not limited thereto.

Further, if necessary, a pigment,
A water-insoluble binder, metal soap, wax, surfactant, ultraviolet absorber, ultraviolet stabilizer, crosslinking agent, hindered phenol, phosphorus compound, defoaming agent, etc. are added. As the pigment, for example, calcium carbonate, barium carbonate,
Inorganic pigments such as magnesium carbonate, zinc carbonate, zinc oxide, aluminum oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, talc, wax, kaolin, clay, diatomaceous earth, silica, styrene microballs, nylon particles , Urea-formalin fillers, polyethylene particles, cellulose fillers, starch particles and other organic pigments are used.

As the water-insoluble binder, synthetic rubber latex or synthetic resin emulsion is generally used.
Examples thereof include styrene-butadiene rubber latex, acrylonitrile-butadiene latex, methyl acrylate-butadiene rubber latex, vinyl acetate emulsion and the like. Examples of the metal soap include metal salts of higher fatty acids such as zinc stearate, calcium stearate, aluminum stearate and zinc oleate. As a wax,
Examples thereof include paraffin wax, microcrystalline wax, carboxy-modified paraffin wax, carnauba wax, polyethylene wax, polystyrene wax, candelia wax, montan wax, and higher fatty acid ester.

As the surfactant (dispersant), for example,
Sulfosuccinic acid-based alkali metal salts [for example, di (n-
Hexyl) sulfosuccinic acid, di (2-ethylhexyl)
Sodium salt of sulfosuccinic acid and the like], sodium salt of dodecylbenzenesulfonic acid, sodium salt of lauryl alcohol sulfate, fatty acid metal salt, fluorine-containing surfactant and the like. Examples of the ultraviolet absorbers and ultraviolet stabilizers include cinnamic acid derivatives, benzophenone derivatives, triazole derivatives, salicylic acid derivatives, hindered amine derivatives and the like. Examples of the cross-linking agent include aldehyde derivatives such as glyoxal,
Examples thereof include epoxy compounds, polyamide resins, diglycidyl compounds, aziridine compounds, magnesium chloride and ferric chloride.

The hindered phenol is preferably a phenol derivative in which at least one of the ortho positions of the phenolic hydroxyl group is substituted with a branched alkyl group.
2,6-diisopropyl-4-methylphenol, 2,
6-di-tert-butyl-4-methylphenol, 2-te
rt-Butyl-4-methoxyphenol, 2,5-di-te
rt-octyl-4-methoxyphenol, 2,5-di-
tert-butylhydroquinone, 2,5-di-tert-octylhydroquinone, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2 -Methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-
Tris (2-ethyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (3,5-di-tert-butyl-4-hydroxyphenyl) butane,
1,1,3-tris (2-methyl-4-hydroxy-5)
-Tert-butylphenyl) propane, 1,1-bis (2
-Methyl-5-tert-butyl-4-hydroxyphenyl) butane, tetrakis [methylene-3- (3 ', 5'
-Di-tert-butyl-4'-hydroxyphenyl) propionate] methane, bis (3-tert-butyl-5-methyl-2-hydroxyphenyl) methane, bis (3-te
rt-Butyl-5-ethyl-2-hydroxyphenyl) methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1, 3,5-Tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 1,3,5-Tris (4-tert-butyl-3)
-Hydroxy-2-methyl-6-ethylbenzyl) isocyanuric acid, bis (2-methyl-4-hydroxy-5-
tert-butylphenyl) sulfide and the like.

As the phosphorus compound, a phosphate compound is preferable, and for example, 2,2'-methylenebis (4-
Methyl-6-tert-butylphenyl) phosphate,
2,2'-methylenebis (4-ethyl-6-tert-butylphenyl) phosphate, 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate,
Diphenyl phosphate, bis (4-tert-butylphenyl) phosphate, bis (2,4-ditert-butylphenyl) phosphate, bis (4-chlorophenyl)
Mention may be made of phosphates, bis (2-phenylphenyl) phosphates, bis (4-phenylphenyl) phosphates and the like, or salts of these metals (eg potassium, sodium, zinc, calcium, magnesium, aluminum).

In the heat-sensitive recording material of the present invention, the method of forming the recording layer is not particularly limited, and the recording layer can be formed according to a conventionally known technique. For example, the coating liquid for the heat-sensitive recording layer is coated on a support with an appropriate coating device such as an air knife coater, a blade coater, a bar coater, a short dwell coater, a gravure coater, a curtain coater, and a wire bar, and dried. Can form a recording layer. The coating amount of the coating liquid is not particularly limited, but it is generally about 1.5 to 12 g / m ^{2 in} dry weight, preferably 2.5.
It is prepared at about 10 g / m ² . The support is not particularly limited, but for example, paper, plastic sheet, synthetic paper, or a composite sheet or non-woven sheet combining these, a molded product, or a metal deposition product is used.

If necessary, a protective layer (overcoat layer) may be provided on the front surface and / or the back surface of the heat-sensitive recording layer, or a single-layer or multi-layer pigment (for example, between the support and the heat-sensitive recording layer) (for example, Providing an undercoat layer (undercoat layer) made of kaolin, calcium carbonate) or synthetic resin (for example, plastic spherical particles, plastic spherical hollow particles), between the heat-sensitive recording layer and the undercoat layer,
Alternatively, it is of course possible to provide an intermediate layer composed of a pigment, a binder, etc. between the heat-sensitive recording layer and the protective layer, and further, the back surface of the support is subjected to an adhesive treatment to form an adhesive label. Various known techniques in the manufacturing method of can be applied. Further, after forming the heat-sensitive recording layer and / or the protective layer, super calendering treatment can be performed.

[0091]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise noted,% means% by weight. Example 1 3-Di-n-butylamino-6-methyl-7-anilinofluorane was used as the electron-donating color-forming compound, and zinc 4- (n-octyloxycarbonylamino) salicylic acid was used as the electron-accepting compound. A salt (zinc salt of Exemplified Compound No. 77), as the compound represented by the general formula (2):
A thermal recording material was prepared by the following method using 4'-diethylcarbonyldiphenyl ether. [Preparation of Thermosensitive Recording Material] (Composition of Liquid A) Electron-donating color-forming compound 10 g Compound represented by general formula (2) 20 g 5% aqueous solution of methylcellulose 10 g Water 80 g ───────────── ────────────────────── Total 120g (B liquid composition) Electron-accepting compound 20g 5% Methylcellulose aqueous solution 10g Water 100g ────────── ───────────────────────── Total 130g Liquid A and liquid B are dispersed in a sand mill so that the average particle size is 1.5 μm. Then, a dispersion liquid was prepared.
Next, 120 g of solution A, 130 g of solution B, 10 g of 30% paraffin wax, 10% aqueous solution of polyvinyl alcohol 1
70 g and 25 g of calcium carbonate were mixed and stirred to prepare a coating liquid for the recording layer. The coating solution was applied to a high-quality paper so that the dry coating amount was 5.5 g / m ² , dried, and then subjected to a super calender treatment.

Examples 2 to 26 In Example 1, the electron-donating color forming compound in solution A,
A heat-sensitive recording material was prepared by the method described in Example 1 except that each compound shown in Table 1 (Table 1, Table 2, Table 3, and Table 4) was used as the electron-accepting compound in the liquid B. did.
Further, as the compound represented by the general formula (2), 4-methylcarbonylbiphenyl (Examples 2 to 4), 4-methylcarbonyl-4′-phenyloxydiphenyl ether (Examples 5 to 8), 4-benzyl Carbonyl diphenyl sulfide (Examples 9 to 13), 4,4'-diethyl carbonyl diphenyl ether (Examples 14 to 18),
4,4-di-n-butylcarbonyldiphenyl ether (Examples 19 to 22) and 4,4-di-n-propylcarbonyldiphenyl sulfide (Examples 23 to 26) were used.

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

[Table 3]

[0096]

[Table 4]

Examples 27 to 29 In Example 1, as the electron accepting compound in the liquid B,
Instead of using 20 g of zinc salt of 4-n-octyloxycarbonylaminosalicylic acid (zinc salt of Exemplified Compound No. 77), 14 g of zinc salt of Exemplified Compound No. 77 and 4,
6 g of 4'-dihydroxybenzophenone (Example 2
7), 15 g of zinc salt of Exemplified Compound No. 70 and 5 g of 1,4-bis (4′-hydroxycumyl) benzene (Example 2)
8), 12 g of a zinc salt of Exemplified Compound No. 188 and bis [4
Example 1 except that 8 g of-(3'-hydroxyphenyloxy) phenyl] sulfone (Example 29) was used.
A thermal recording material was prepared according to the method described in 1.

Examples 30 to 37 In Example 1, instead of 130 g of the B solution, the C solution 13 was used.
According to the method described in Example 1 except that 0 g was used,
A thermal recording material was prepared. (C liquid composition) Electron-accepting compound 20 g Metal compound 10 g 5% Methylcellulose aqueous solution 5 g Water 95 g ──────────────────────────────── ──── Total 130g Incidentally, as the metal compound in the liquid C, zinc oxide (Example 3
0), zinc oxide 50% and zinc carbonate 50% (Example 3
1), zinc oxide (Example 32), zinc oxide 50% and zinc carbonate 50% (Example 33), zinc oxide (Examples 34 to 3)
7) was used. The electron-donating color-forming compound in the solution A and the electron-accepting compound in the solution C used in each Example were the second
The results are shown in Tables (Table 5 and Table 6).

[0099]

[Table 5]

[0100]

[Table 6]

Comparative Example 1 In Example 1, as an electron-accepting compound, 4-n-
A heat-sensitive recording material was prepared according to the method described in Example 1 except that 2,2-bis (4′-hydroxyphenyl) propane was used instead of using the zinc salt of octyloxycarbonylaminosalicylic acid.

Comparative Example 2 In Example 1, as an electron-accepting compound, 4-n-
According to the method described in Example 1, except that the zinc salt of 4- [2 ′-(4-methoxyphenoxy) ethoxy] salicylic acid was used instead of the zinc salt of octyloxycarbonylaminosalicylic acid, the heat-sensitive recording material was used. Was produced.

Comparative Example 3 A thermosensitive recording material was prepared in the same manner as in Example 1 except that stearamide was used instead of 4,4′-diethylcarbonyldiphenyl ether.

The thermosensitive recording materials obtained in the above Examples and Comparative Examples were evaluated according to the following evaluation methods, and the results are shown in Table 3 (Tables 7 and 8). [Evaluation Method of Thermosensitive Recording Material] (Storage Stability Test of Uncolored Part) The whiteness of the uncolored part (background) immediately after the application of each thermal recording material was measured by using a color difference meter (Σ-80, manufactured by Nippon Denshoku). To measure. The storage stability test
A heat resistance test was conducted, and the whiteness of the uncolored part of each thermal recording paper after the test was examined. The heat resistance test was conducted using a thermosensitive recording material at 60
After storing at 24 ° C. for 24 hours, the whiteness of the uncolored part is measured using a color difference meter. The larger the value, the higher the whiteness and the better the storage stability of the uncolored part. (Storage stability test of colored image) Each thermal recording material was measured using a thermal recording material coloring device (TH-PMD manufactured by Okura Electric Co., Ltd.).
A storage stability test is performed after forming a color image having a color density of 0.9 measured using a Macbeth densitometer (TR-524 type). As the storage stability test, a plasticizer resistance test was conducted to examine the storage stability of the color image of each thermosensitive recording material after the test. In the plasticizer resistance test, a vinylidene chloride wrap film [made by Mitsui Toatsu Chemicals, Inc.] was wound around a polypropylene pipe (40 mmΦ) in three layers, and the coloring surface of the thermosensitive recording material was placed on the outside. Scissors, and then wrap the vinylidene chloride wrap film in three layers and leave it at 25 ° C for 4 days, and then measure the color image density using a Macbeth densitometer. I asked.

[0105] The larger the value, the better the storage stability of the color image. (Coloring sensitivity test) 0.49 mj / d of each thermal recording material
After the color was developed with the energy of ot, the obtained color image density was measured using a Macbeth densitometer. The larger the value, the better the color development sensitivity.

[0106]

[Table 7]

[0107]

[Table 8]

As is clear from Table 3, the heat-sensitive recording material of the present invention is excellent in color developing sensitivity, and is also excellent in storage stability of uncolored portion and color image.

[0109]

According to the present invention, it is possible to provide a heat-sensitive recording material which is excellent in color developing sensitivity and storage stability of uncolored portion and color image.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiyoharu Hasegawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. A heat-sensitive recording material containing an electron-donating color forming compound and an electron-accepting compound, wherein the electron-accepting compound is a salicylic acid derivative represented by the general formula (1) A heat-sensitive recording material containing at least one selected from salts and further containing a compound represented by the general formula (2) (Chemical Formula 2). Embedded image (In the formula, X ₁ and X ₂ represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group or a halogen atom, Y ₁ and Y ₂ represent an oxygen atom or a sulfur atom, R ₁ represents a hydrogen atom, An alkyl group, an aralkyl group or an aryl group, and R ₂ represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group) (In the formula, X _{3 to} X ₆ represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an arylthio group or a halogen atom, R ₃ and R ₄ represent an alkyl group or an aralkyl group, and Y is a single bond, Represents an oxygen atom or a sulfur atom, and n represents 0 or 1.)