JPH0664321A - Thermal recording material - Google Patents

Abstract

(57) [Summary] [Structure] A heat-sensitive recording material containing an electron-donating color-forming compound and an electron-accepting compound, which contains a benzoic acid derivative of the general formula (1) and / or a polyvalent metal salt of the derivative. Thermosensitive recording material. (In the formula, X ₁ and X ₂ represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group, an aralkyl group or an aryl group, Y ₁ and Y ₂ represent an oxygen atom or a sulfur atom, and R ₁ represents A hydrogen atom, an alkyl group, an aralkyl group or an aryl group is represented, and R ₂ is an alkyl group, an alkenyl group, an aralkyl group or an aryl group.) [Effect] A heat-sensitive recording material excellent in storage stability of uncolored portion and color image I will provide a.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermal recording material,
In particular, it relates to a thermosensitive recording material having improved storage stability of a color image.

[0002]

2. Description of the Related Art Thermal recording materials are widely used in the fields of facsimiles, recorders, printers and the like because they are relatively inexpensive and have the advantage that the recording equipment is compact and maintenance-free. 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-43-4160 and JP-B-43-4160). 45-14039). Phenolic compounds are widely used as electron-accepting compounds. Among them, 2,2-bis (4′-hydroxyphenyl) propane [alias, bisphenol A] is low in price and easily available. Although widely used, a heat-sensitive recording material using bisphenol A as an electron-accepting compound has a problem that storage stability of a color image is poor.
Further, the heat-sensitive recording material containing bisphenol A as an electron-accepting compound has a problem that the color-developing sensitivity is low.

As a phenolic compound other than bisphenol A, for example, 4-hydroxybenzoic acid esters (JP-A-56-144193, JP-B-1-306).
40), aralkyloxyphenols (JP-B-2-31678, JP-A-60-225789), and hydroxybenzophenones (JP-A-57-19).
3388) has been proposed as a heat-sensitive recording material using an electron-accepting compound. However, when 4-hydroxybenzoic acid esters, for example, 4-hydroxybenzoic acid benzyl ester is used as an electron-accepting compound, there is a drawback that the color image density decreases with time, and 4-hydroxybenzoic acid is formed on the color image. There is a problem that white crystals of benzyl acid salt are deposited, and a powdery state, that is, a so-called whitening phenomenon is exhibited. Even when aralkyloxyphenols such as 4-benzyloxyphenol are used as the electron-accepting compound, there is a drawback that the color image density decreases with time. Even when a hydroxybenzophenone, for example, 4-hydroxybenzophenone is used as an electron-accepting compound, the storage stability of the color image (for example, resistance to moist heat and water resistance) is poor, and it has sufficient performance in practice. I can't say.

Further, as a method for improving the coloring sensitivity,
A heat-sensitive recording material containing a heat-fusible compound (sensitizer) in addition to the electron-donating color-forming compound and the electron-accepting compound is also widely used. As the heat-fusible compound, terphenyls (Japanese Patent Publication No. 63-7958), benzyl 4-benzyloxybenzoate (Japanese Patent Publication No. 63-3087).
No. 8), naphthol derivatives (Japanese Patent Publication No. 63-4259).
No. 0), aminophenol derivatives (JP-A-58-2).
11494), benzyl biphenyls (Japanese Patent Publication No. 2)
-11437), diaryloxyalkane derivatives (JP-A-60-56588, JP-A-61-16).
1988) or oxalate derivative (JP-A-1-1583). However, the heat-sensitive recording material containing these heat-fusible compounds, although the color development sensitivity is improved to some extent, the storage stability of the color image is significantly poor, usually compared to the case where no heat-fusible compound is added, At present, there is a problem that the storage stability of a color image is further deteriorated. At present, there is a strong demand for a heat-sensitive recording material that overcomes the above-mentioned problems and is excellent in storage stability of a color image.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-sensitive recording material in which the storage stability of a color image is remarkably improved.

[0006]

SUMMARY OF THE INVENTION The present inventors have completed the present invention as a result of extensive studies on a heat-sensitive recording material in order to meet the above-mentioned demand. That is, the present invention is
A heat-sensitive recording material containing an electron-donating color-forming compound and an electron-accepting compound contains at least one benzoic acid derivative represented by the general formula (1) or (2) and / or a polyvalent metal salt of the derivative. The present invention relates to a thermosensitive recording material.

[0007]

[Chemical 2] (In the formula, X ₁ and X ₂ represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group, an aralkyl group or an aryl group, Y ₁ and Y ₂ represent an oxygen atom or a sulfur atom, and 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 benzoic acid derivative represented by the general formula (1) according to the present invention, X ₁ and X ₂ represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group, an aralkyl group or an aryl group, Preferably a hydrogen atom,
Fluorine atom, chlorine atom, bromine atom, nitro group, carbon number 1
To a C20 alkyl group, a C5 to C14 cycloalkyl group, a C1 to C20 alkoxy group, a C7 to C20 aralkyl group or a phenyl group, and more preferably a hydrogen atom, a chlorine atom, or a nitro group. , An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group or a phenyl group, and a hydrogen atom is particularly preferable. In the general formula (1), Y ₁ and Y ₂ are oxygen atoms or sulfur atoms, and preferably oxygen atoms.

In the general formula (1), R ₁ is a hydrogen atom,
It represents an alkyl group, an aralkyl group or an aryl group, and preferably has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or a substituent. Is also a phenyl group, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a benzyl group or a phenyl group, and further preferably a hydrogen atom or a carbon number of 1 to 1 4 alkyl group or phenyl group, and particularly preferably a hydrogen atom. In the benzoic acid derivative represented by the general formula (1), 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. Optionally cyclic alkyl group, optionally substituted chain alkenyl group, optionally substituted cyclic alkenyl group, optionally substituted aralkyl group, optionally substituted Is a phenyl group, a naphthyl group which may have a substituent, or a heteroaromatic ring group which may have a substituent.

The alkyl group and alkenyl group of R ₂ are
For example, an alkoxy group having 1 to 20 carbon atoms, 2 to 2 carbon atoms
An alkoxyalkyloxy group having 0, an alkenyloxy group having 2 to 20 carbon atoms, an aralkyloxy group having 7 to 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, an arylalkenyl group having 8 to 20 carbon atoms, an aralkylalkenyl group having 9 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, 2 to 2 carbon atoms
0 alkoxyalkylthio group, C2-20 alkylthioalkylthio group, C2-20 alkenylthio group, C7-20 aralkylthio group, C8
~ 20 aralkyloxyalkylthio groups, 8 carbon atoms ~
20 aralkylthioalkylthio groups, having 6 to 20 carbon atoms
Arylthio group, a C 7-20 aryloxyalkylthio group, a C 7-20 arylthioalkylthio group, a heteroatom-containing cyclic alkyl group, a substituent such as a halogen atom, which may be mono- or polysubstituted. Is also good. Further, the aryl group contained in these substituents further has 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, and 7 to 7 carbon atoms.
It may be substituted with 10 aralkyl groups, C 7-10 aralkyloxy groups, hydroxyl groups, halogen atoms and 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
An alkoxyalkyloxy group having 0, an alkenyloxy group having 2 to 20 carbon atoms, an alkenyloxyalkyl group having 3 to 20 carbon atoms, an alkenyloxyalkyloxy group having 3 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, Aralkyloxyalkyl group having 8 to 20 carbon atoms, 8 carbon atoms
~ 20 aralkyloxyalkyloxy groups, 6 carbon atoms
To aryloxy group having 7 to 20 carbon atoms, aryloxyalkyl group having 7 to 20 carbon atoms, aryloxyalkyloxy group having 7 to 20 carbon atoms, alkylcarbonyl group having 2 to 20 carbon atoms, alkenylcarbonyl group having 3 to 20 carbon atoms, Aralkylcarbonyl group having 8 to 20 carbon atoms, arylcarbonyl group having 7 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, alkenyloxycarbonyl group having 3 to 20 carbon atoms, aralkyloxycarbonyl having 8 to 20 carbon atoms Group, aryloxycarbonyl group having 7 to 20 carbon atoms, alkylcarbonyloxy group having 2 to 20 carbon atoms, and 3 carbon atoms
~ 20 alkenylcarbonyloxy group, 8 to 2 carbon atoms
0 aralkylcarbonyloxy group, C 7-20 arylcarbonyloxy group, C 14-20 aralkyloxy aralkyl group, C 1-20 alkylthio group, C 7-20 aralkylthio group, carbon number 6
It may be mono- or poly-substituted with a substituent such as an arylthio group, a nitro group, a formyl group, a halogen atom, a hydroxyl group and a cyano group.

Further, the aryl group contained in these substituents is further an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms.
And an alkylthio group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aralkyloxy group having 7 to 10 carbon atoms, a hydroxyl group, a halogen atom and the like. Preferably, R ₂ may have an alkyl group having a total carbon number of 1 to 24, which may have a substituent, an alkenyl group having a total carbon number of 2 to 24, which may have a substituent, or a substituent. An aralkyl group having 7 to 24 carbon atoms or an aryl group having 6 to 24 carbon atoms 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 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-octyloxy group Opropyl 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-chloro Octyl 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,

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-hexyl Phenyl 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, 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, 1- (4-ethylnaphthyl) group, 2- (6-
Butylnaphthyl) group, 1- (2-methoxynaphthyl)
Group, 1- (4-methoxynaphthyl) group, 1- (4-n-
Butoxynaphthyl) group, 1- (5-ethoxynaphthyl)
Group, 2- (6-ethoxynaphthyl) group, 2- (6-n-
Hexyloxynaphthyl) group, 2- (7-methoxynaphthyl) group, 2- (7-n-butoxynaphthyl) 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, 1- (4-allyloxynaphthyl) 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, 1- (4 -Benzyloxy) naphthyl group, 2- (6-benzyloxynaphthyl)
Group, 2- (7-benzyloxynaphthyl) 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, 1- (4-phenoxynaphthyl)
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,
1- (4-acetylnaphthyl) 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, 1- (4-phenylcarbonylnaphthyl) group,

4-methoxycarbonylphenyl group, 2-
Methoxycarbonylphenyl 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, 1- (4- Ethoxycarbonylnaphthyl) group,
2- (6-methoxycarbonylnaphthyl) group, 2- (6
-N-butoxycarbonylnaphthyl) group, 4-allyloxycarbonylphenyl group, 4-benzyloxycarbonylphenyl group, 4- (4'-chlorobenzyl) oxycarbonylphenyl group, 4-phenethyloxycarbonylphenyl group, 2- ( 6-benzyloxycarbonylnaphthyl) group, 4-phenyloxycarbonylphenyl group, 4- (4'-ethylphenyl) oxycarbonylphenyl group, 4- (4'-chlorophenyl) oxycarbonylphenyl group, 4- (4'- Ethoxyphenyl) oxycarbonylphenyl group, 2- (6-phenyloxycarbonylnaphthyl) 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, 1- (4-acetyloxynaphthyl) group, 1- (5-acetyloxynaphthyl)
Group, 2- (6-ethylcarbonyloxynaphthyl) group,
4-allylcarbonyloxyphenyl group, 4-benzylcarbonyloxyphenyl group, 4-phenethylcarbonyloxyphenyl group, 2- (6-benzylcarbonyloxynaphthyl) group, 4-phenylcarbonyloxyphenyl group, 4- (4'- Methylphenyl) carbonyloxyphenyl group, 4- (2'-methylphenyl) carbonyloxyphenyl group, 4- (4'-chlorophenyl) carbonyloxyphenyl group, 4- (2'-chlorophenyl) carbonyloxyphenyl group, 1- (4-phenylcarbonyloxynaphthyl) group, 2- (6-phenylcarbonyloxynaphthyl) 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-phenylthiophenyl group, 4- (4'-methylphenylthio) phenyl group, 4- (4'-methoxyphenylthio) phenyl group, 4 -(4'-chlorophenylthio) phenyl group, 1- (4-methylthionaphthyl) group,
2- (6-ethylthionaphthyl) group, 2- (6-phenylthionaphthyl) group,

4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group,
4-bromophenyl group, 1- (4-chloronaphthyl)
Group, 2- (4-chloronaphthyl) group, 2- (6-bromonaphthyl) group, 4-nitrophenyl group, 3-nitrophenyl group, 4-formylphenyl group, 3-formylphenyl group, 2-formylphenyl group Group, 1- (4-formylnaphthyl) group, 2- (1-formylnaphthyl) group, 4-hydroxyphenyl group, 3-hydroxyphenyl group, 2-
Hydroxyphenyl group, 1- (4-hydroxynaphthyl) group, 2- (6-hydroxynaphthyl) group, 4-cyanophenyl group, 2-cyanophenyl group, 2- (6-cyanonaphthyl) 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, 2,3,5-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
Examples thereof include a -di-n-butoxyphenyl group, a 3,4,5-trimethoxyphenyl group and a 1- (2,4-dichloronaphthyl) group.

The compound represented by the general formula (1) according to the present invention has a carbamate group in the benzoic acid skeleton. The carbamate group is substituted at the 2-position with respect to the carboxylic acid group. The position of the 3rd or 4th position, specifically, the following general formula (1-a), (1-b) or (1-
c) A benzoic acid derivative represented by (Chemical Formula 3).

[0027]

[Chemical 3] (In the formula, X ₁ , X ₂ , Y ₁ , Y ₂ , R ₁ and R ₂ are the same as above)

Specific examples of the benzoic acid derivative represented by the general formula (1) and the polyvalent metal salt of the derivative according to the present invention include the following benzoic acid derivatives and the polyvalent metal salt of the derivative. Of course, the present invention is not limited to these. -Exemplified compound number Compound 1.2- (Methyloxycarbonylamino) benzoic acid 2.2- (Ethyloxycarbonylamino) benzoic acid 3.2- (Ethyloxycarbonylamino) -3-methylbenzoic acid 4.2- ( Ethyloxycarbonylamino) -5-methylbenzoic acid 5.2- (Ethyloxycarbonylamino) -4-nitrobenzoic acid 6.2- (n-Propyloxycarbonylamino) benzoic acid 7.2- (n-Propyloxy) Carbonylamino) -6-ethylbenzoic acid 8.2- (Isopropyloxycarbonylamino) benzoic acid 9.2- (Isopropyloxycarbonylamino) -5-chlorobenzoic acid 10.2- (n-Butyloxycarbonylamino) benzoic acid acid

11.2- (Isobutyloxycarbonylamino) benzoic acid 12.2- (tert-Butyloxycarbonylamino) benzoic acid 13.2- (tert-Butyloxycarbonylamino) -4-chlorobenzoic acid 14.2 -(2-Ethylbutyloxycarbonylamino) benzoic acid 15.2- (2-Ethylhexyloxycarbonylamino) benzoic acid 16.2- (n-octyloxycarbonylamino) benzoic acid 17.2- (n-decyloxycarbonyl) Amino) benzoic acid 18.2- (cyclohexyloxycarbonylamino) benzoic acid 19.2-[(2′-cyclohexylethyl) oxycarbonylamino] benzoic acid 20.2- (allyloxycarbonylamino) benzoic acid 21.2 -[(2'-hexenyl) oxycarbonylamino] Benzoic acid 22.2-[(2'-ethoxyethyl) oxycarbonylamino] benzoic acid 23.2-[(3'-n-hexyloxypropyl) oxycarbonylamino] benzoic acid 24.2-[(2 ' -Benzyloxyethyl) oxycarbonylamino] benzoic acid 25.2- (phenoxymethyloxycarbonylamino) benzoic acid

26.2-[(2′-phenoxyethyl) oxycarbonylamino] benzoic acid 27.2- [2 ′-(4-chlorophenyl) oxyethyloxycarbonylamino] benzoic acid 28.2- [2 ′ -(4-Methoxyphenyl) oxyethyloxycarbonylamino] benzoic acid 29.2-[(2'-phenoxyethoxyethyl) oxycarbonylamino] benzoic acid 30.2- (cinnamyloxycarbonylamino) benzoic acid 31.2 -[(2'-n-Butylthioethyl) oxycarbonylamino] benzoic acid 32.2-[(2'-methoxyethylthioethyl) oxycarbonylamino] benzoic acid 33.2-[(2'-allylthio) Ethyl) oxycarbonylamino] benzoic acid 34.2-[(2'-benzylthioethyl) oxycal Nylamino] benzoic acid 35.2-[(2'-phenylthioethyl) oxycarbonylamino] benzoic acid 36.2-[(7'-chloroheptyl) oxycarbonylamino] benzoic acid 37.2- (benzyloxycarbonylamino) ) Benzoic acid 38.2- (benzyloxycarbonylamino) -4-chlorobenzoic acid 39.2-[(4'-methylbenzyl) oxycarbonylamino] benzoic acid 40.2-[(4'-chlorobenzyl) oxy Carbonylamino] benzoic acid

41.2-[(3'-phenoxybenzyl) oxycarbonylamino] benzoic acid 42.2- (phenyloxycarbonylamino) benzoic acid 43.2- (phenyloxycarbonylamino) -4-methylbenzoic acid 44 2- (phenyloxycarbonylamino) -4-phenylbenzoic acid 45.2- (phenyloxycarbonylamino) -5-nitrobenzoic acid 46.2- (phenyloxycarbonylamino) -4-chlorobenzoic acid 47.2 -(Phenyloxycarbonylamino) -5-chlorobenzoic acid 48.2-[(2'-naphthyl) oxycarbonylamino] benzoic acid 49.2-[(3'-freel) oxycarbonylamino] benzoic acid 50.2 -[(3'-phenylphenyl) oxycarbonylamino] benzoic acid 51. -[(4'-Methylphenyl) oxycarbonylamino] benzoic acid 52.2-[(4'-n-butylphenyl) oxycarbonylamino] benzoic acid 53.2-[(4'-tert-butylphenyl) oxy Carbonylamino] benzoic acid 54.2-[(4'-cyclohexylphenyl) oxycarbonylamino] benzoic acid 55.2-[(3'-methoxyphenyl) oxycarbonylamino] benzoic acid 56.2-[( 4'-n-butoxyphenyl) oxycarbonylamino] benzoic acid 57.2-[(4'-n-octyloxyphenyl) oxycarbonylamino] benzoic acid 58.2-[(4'-phenoxyphenyl) oxycarbonyl Amino] benzoic acid 59.2-[(2'-acetylphenyl) oxycarbonylamino] benzoic acid 60.2 [(4'-allyl carbonyl phenyl) oxycarbonyl amino] benzoic acid

61.2-[(4'-phenylcarbonylphenyl) oxycarbonylamino] benzoic acid 62.2-[(4'-n-butoxycarbonylphenyl) oxycarbonylamino] benzoic acid 63.2-[( 4'-benzyloxyphenyl) oxycarbonylamino] benzoic acid 64.2-[(4'-acetyloxyphenyl) oxycarbonylamino] benzoic acid 65.2-[(4'-ethylthiophenyl) oxy Carbonylamino] benzoic acid 66.2-[(4'-fluorophenyl) oxycarbonylamino] benzoic acid 67.2-[(4'-chlorophenyl) oxycarbonylamino] benzoic acid 68.2-[(3'-chlorophenyl) ) Oxycarbonylamino] benzoic acid 69.2-[(4′-nitrophenyl) oxycarboni Amino] benzoic acid 70.2-[(4'-formylphenyl) oxycarbonylamino] benzoic acid 71.2-[(4'-hydroxyphenyl) oxycarbonylamino] benzoic acid 72.2-[(4'-cyano Phenyl) oxycarbonylamino] benzoic acid 73.2-[(2 ', 4'-dimethylphenyl) oxycarbonylamino] benzoic acid 74.2-[(3', 5'-dichlorophenyl) oxycarbonylamino] benzoic acid Benzoic acid 75.2- (n-octylthiolcarbonylamino) benzoic acid

76.2-[(4'-chlorobenzyl) thiolcarbonylamino] benzoic acid 77.2-[(3'-methylphenyl) thiolcarbonylamino] benzoic acid 78.2- (n-butylthiolthiocarbonyl) Amino) benzoic acid 79.2- (phenylthiolthiocarbonylamino) benzoic acid 80.2-[(4'-ethoxyphenyl) thiolthiocarbonylamino] benzoic acid 81.2- (N-phenyl-N-phenyl) Oxycarbonylamino) benzoic acid 82.3- (Ethyloxycarbonylamino) benzoic acid 83.3- (n-Propyloxycarbonylamino) benzoic acid 84.3- (Isopropyloxycarbonylamino) benzoic acid 85.3- (n -Butyloxycarbonylamino) benzoic acid 86.3- (isobutyloxy) Carbonylamino) benzoic acid 87.3- (tert-butyloxycarbonylamino) benzoic acid 88.3- (n-pentyloxycarbonylamino) benzoic acid 89.3- (Isopentyloxycarbonylamino) benzoic acid 90.3- (N-hexyloxycarbonylamino) benzoic acid 91.3- (n-heptyloxycarbonylamino) benzoic acid 92.3- (n-octyloxycarbonylamino) benzoic acid 93.3-[(2′-ethylhexyl) oxy Carbonylamino] benzoic acid 94.3- (n-nonyloxycarbonylamino) benzoic acid 95.3- (n-decyloxycarbonylamino) benzoic acid

96.3- (n-Undecyloxycarbonylamino) benzoic acid 97.3- (n-dodecyloxycarbonylamino) benzoic acid 98.3- (n-Tridecyloxycarbonylamino) benzoic acid 99.3 -(N-Tetradecyloxycarbonylamino) benzoic acid 100.3- (n-pentadecyloxycarbonylamino) benzoic acid 101.3- (n-hexadecyloxycarbonylamino) benzoic acid 102.3- (n-hepta) Decyloxycarbonylamino) benzoic acid 103.3- (n-octadecyloxycarbonylamino) benzoic acid 104.3- (cyclopentyloxycarbonylamino) benzoic acid 105.3- (cyclohexyloxycarbonylamino) benzoic acid 106.3- [ (4'-tert-butylcyclohexyl Oxycarbonylamino] benzoic acid 107.3- (Cycloheptyloxycarbonylamino) benzoic acid 108.3- (Cyclooctyloxycarbonylamino) benzoic acid 109.3- (Cyclohexylmethyloxycarbonylamino) benzoic acid 110.3- [ (2'-Tetrahydrofurfuryl) oxycarbonylamino] benzoic acid

111.3-[(2′-Methoxyethyl) oxycarbonylamino] benzoic acid 112.3-[(2′-n-hexyloxyethyl) oxycarbonylamino] benzoic acid 113.3-[(2 ′ -N-octyloxyethyl) oxycarbonylamino] benzoic acid 114.3-[(3'-ethoxypropyl) oxycarbonylamino] benzoic acid 115.3-[(3'-n-butoxypropyl) oxycarbonylamino] benzoic acid Aromatic acid 116.3-[(3'-n-octyloxypropyl) oxycarbonylamino] benzoic acid 117.3-[(2'-n-butoxyethoxyethyl) oxycarbonylamino] benzoic acid 118.3-[( 2'-Benzyloxyethyl) oxycarbonylamino] benzoic acid 119.3-[(phenoxy Tyl) oxycarbonylamino] benzoic acid 120.3-[(2′-phenoxyethyl) oxycarbonylamino] benzoic acid 121.3- [2 ′-(4-chlorophenyl) oxyethyloxycarbonylamino] benzoic acid 122. 3- [2 '-(4-Methoxyphenyl) oxyethyloxycarbonylamino] benzoic acid 123.3-[(2'-phenoxyethoxyethyl) oxycarbonylamino] benzoic acid 124.3-[(3'-n- Butylthiopropyl) oxycarbonylamino] benzoic acid 125.3-[(6′-ethylthiohexyl) oxycarbonylamino] benzoic acid 126.3-[(2′-benzylthioethyl) oxycarbonylamino] benzoic acid 127.3-[(2'-phenylthioethyl) oxycarbonylamino] Benzoic acid 128.3-[(2'-chloroethyl) oxycarbonylamino] benzoic acid 129.3-[(9'-decenyl) oxycarbonylamino] benzoic acid 130.3- (benzyloxycarbonylamino) benzoic acid

131.3- (Benzyloxycarbonylamino) -2,6-dimethoxybenzoic acid 132.3-[(4′-methylbenzyl) oxycarbonylamino] benzoic acid 133.3-[(4′-chlorobenzyl) ) Oxycarbonylamino] benzoic acid 134.3-[(2′-phenylethyl) oxycarbonylamino] benzoic acid 135.3- (phenyloxycarbonylamino) benzoic acid 136.3-[(1′-naphthyl) oxycarbonyl Amino] benzoic acid 137.3-[(2'-naphthyl) oxycarbonylamino] benzoic acid 138.3-[(2'-furyl) oxycarbonylamino] benzoic acid 139.3-[(4'-phenylphenyl) Oxycarbonylamino] benzoic acid 140.3-[(4'-methylphenyl) oxyca Bonylamino] benzoic acid 141.3-[(3'-methylphenyl) oxycarbonylamino] benzoic acid 142.3-[(2'-methylphenyl) oxycarbonylamino] benzoic acid 143.3-[(4'-ethyl) Phenyl) oxycarbonylamino] benzoic acid 144.3-[(4'-tert-butylphenyl) oxycarbonylamino] benzoic acid 145.3-[(4'-cyclohexylphenyl) oxycarbonylamino] benzoic acid

146.3-[(2′-Cyclohexylphenyl) oxycarbonylamino] benzoic acid 147 3-[(4′-cumylphenyl) oxycarbonylamino] benzoic acid 148.3-[(4′-methoxyphenyl) ) Oxycarbonylamino] benzoic acid 149.3-[(3'-methoxyphenyl) oxycarbonylamino] benzoic acid 150.3-[(2'-ethoxyphenyl) oxycarbonylamino] benzoic acid 151.3-[(4 '-N-Butoxyphenyl) oxycarbonylamino] benzoic acid 152.3-[(4'-n-hexyloxyphenyl) oxycarbonylamino] benzoic acid 153.3-[(4'-benzyloxyphenyl) oxycarbonyl Amino] benzoic acid 154.3- [4 '-(4-benzyloxycumyl] Phenyloxycarbonyl amino] benzoic acid 155.3-[(4'-phenoxyphenyl) oxycarbonylamino] benzoic acid 156.3- [2 '-(6-benzyloxy) naphthyloxycarbonylamino] benzoic acid 157.3- [(4'-Phenylcarbonylphenyl) oxycarbonylamino] benzoic acid 158.3-[(4'-Acetylphenyl) oxycarbonylamino] benzoic acid 159.3-[(4'-ethoxycarbonylphenyl) oxycarbonylamino] Benzoic acid 160.3-[(4'-cyclohexyloxycarbonylphenyl) oxycarbonylamino] benzoic acid

161.3-[(4′-n-Propylcarbonyloxyphenyl) oxycarbonylamino] benzoic acid 162.3-[(4′-methylthiophenyl) oxycarbonylamino] benzoic acid 163.3-[(4 ′ -Benzylthiophenyl) oxycarbonylamino] benzoic acid 164 3-[(4'-fluorophenyl) oxycarbonylamino] benzoic acid 165.3-[(2'-fluorophenyl) oxycarbonylamino] benzoic acid 166.3 -[(4'-Chlorophenyl) oxycarbonylamino] benzoic acid 167.3-[(3'-chlorophenyl) oxycarbonylamino] benzoic acid 168.3-[(4'-Bromophenyl) oxycarbonylamino] benzoic acid 169 . 3-[(4'-nitrophenyl) oxycarboni Ruamino] benzoic acid 170.3-[(4'-formylphenyl) oxycarbonylamino] benzoic acid 171.3-[(4'-Cyanophenyl) oxycarbonylamino] benzoic acid 172.3-[(2 ', 4 '-Dimethylphenyl) oxycarbonylamino] benzoic acid 173.3-[(3', 5'-dimethylphenyl) oxycarbonylamino] benzoic acid 174.3-[(2 ', 4'-dichlorophenyl) Oxycarbonylamino] benzoic acid 175.3-[(3 ′, 5′-dimethoxyphenyl) oxycarbonylamino] benzoic acid

176.3-[(3′-Nitro-4′-chlorophenyl) oxycarbonylamino] benzoic acid 177.3-[(4′-Chloro-2′-methylphenyl) oxycarbonylamino] benzoic acid 178.3- (n-octylthiolcarbonylamino) benzoic acid 179.3- (phenylthiolcarbonylamino) benzoic acid 180.3-[(4'-ethoxyphenylthiol) carbonylamino] benzoic acid 181.3- (n -Hexylthiolthiocarbonylamino) benzoic acid 182.3-[(4'-methylphenylthiol) thiocarbonylamino] benzoic acid 183.3- (n-decyloxythiocarbonylamino) benzoic acid 184.3- (N -N-Butyl-N-heptyloxycarbonylamino) benzoic acid 185.4- Methyloxycarbonylamino) benzoic acid 186.4- (Methyloxycarbonylamino) -6-methylbenzoic acid 187.4- (Methyloxycarbonylamino) -6-chlorobenzoic acid 188.4- (Ethyloxycarbonylamino) benzoic acid Acid 189.4- (Ethyloxycarbonylamino) -6-nitrobenzoic acid 190.4- (n-Propyloxycarbonylamino) benzoic acid

191.4- (n-Propyloxycarbonylamino) -5-benzylbenzoic acid 192.4- (n-Butyloxycarbonylamino) benzoic acid 193.4- (isobutyloxycarbonylamino) benzoic acid 194 4- (Sec-Butyloxycarbonylamino) benzoic acid 195.4- (n-pentyloxycarbonylamino) benzoic acid 196.4- (isopentyloxycarbonylamino) benzoic acid 197.4- (n-hexyloxycarbonylamino) benzoic acid Acid 198.4- (n-heptyloxycarbonylamino) benzoic acid 199.4- (n-octyloxycarbonylamino) benzoic acid 200.4-[(2'-ethylhexyl) oxycarbonylamino] benzoic acid 201.4- (N-nonyloxycarbonylamino) Benzoic acid 202.4- (n-decyloxycarbonylamino) benzoic acid 203.4- (n-undecyloxycarbonylamino) benzoic acid 204.4- (n-dodecyloxycarbonylamino) benzoic acid 205.4- ( n-tetradecyloxycarbonylamino) benzoic acid

206.4- (n-Hexadecyloxycarbonylamino) benzoic acid 207 4- (Cyclopentyloxycarbonylamino) benzoic acid 208.4- (Cyclohexyloxycarbonylamino) benzoic acid 209 4-[(2'-methyl Cyclohexyl) oxycarbonylamino] benzoic acid 210.4-[(4′-methylcyclohexyl) oxycarbonylamino] benzoic acid 211.4-[(4′-tert-butylcyclohexyl) oxycarbonylamino] benzoic acid 212. 4-[(2'-Cyclohexylethyl) oxycarbonylamino] benzoic acid 213.4- (Cyclooctyloxycarbonylamino) benzoic acid 214.4-[(2'-Tetrahydrofurfuryl) oxycarbonylamino] benzoic acid Acid 215.4-[(2 - methoxyethyl) oxy carbonylamino] benzoic acid

216.4-[(2′-n-hexyloxyethyl) oxycarbonylamino] benzoic acid 217.4-[(3′-ethoxypropyl) oxycarbonylamino] benzoic acid 218.4-[(3 ′ -Isopropoxypropyl) oxycarbonylamino] benzoic acid 219.4-[(2'-methoxyethoxyethyl) oxycarbonylamino] benzoic acid 220.4- (phenoxymethyloxycarbonylamino) benzoic acid 221.4 -(2'-phenoxyethyloxycarbonylamino) benzoic acid 222.4- [2 '-(4-chlorophenyl) oxyethyloxycarbonylamino] benzoic acid 223.4- [2'-(4-methoxyphenyl) oxy Ethyloxycarbonyl amino] benzoic acid 224.4-[(2′-phenoxy Tokishiechiru) oxy carbonylamino] benzoic acid 225.4 - [(2'-n-hexyl thioethyl) oxy carbonylamino] weaker Ikikosan

226.4-[(2′-Phenylthioethyl) oxycarbonylamino] benzoic acid 227.4- (2′-chloroethyloxycarbonylamino) benzoic acid 228.4- (5′-hexenyloxycarbonylamino) ) Benzoic acid 229.4- (benzyloxycarbonylamino) benzoic acid 230.4- (benzyloxycarbonylamino) 5-ethylbenzoic acid 231.4-[(4'-methylbenzyl) oxycarbonylamino] benzoic acid 232. 4-[(4'-chlorobenzyl) oxycarbonylamino] benzoic acid 233.4-[(2'-phenylethyl) oxycarbonylamino] benzoic acid 234.4- (phenyloxycarbonylamino) benzoic acid 235.4- [(2'-naphthyl) oxycarbonylamino] benzoic acid 36.4-[(4'-phenylphenyl) oxycarbonylamino] benzoic acid 237.4-[(3'-methylphenyl) oxycarbonylamino] benzoic acid 238.4-[(4'-ethylphenyl) oxycarbonyl Amino] benzoic acid 239.4-[(4'-cyclohexylphenyl) oxycarbonylamino] benzoic acid 240.4-[(4'-cumylphenyl) oxycarbonylamino] benzoic acid

241.4-[(4′-methoxyphenyl) oxycarbonylamino] benzoic acid 242.4-[(3′-ethoxyphenyl) oxycarbonylamino] benzoic acid 243.4-[(4′-n- Butoxyphenyl) oxycarbonylamino] benzoic acid 244.4-[(4'-phenoxyphenyl) oxycarbonylamino] benzoic acid 245.4-[(4'-acetylphenyl) oxycarbonylamino] benzoic acid 246.4- [(4'-Methoxycarbonylphenyl) oxycarbonylamino] benzoic acid 247.4-[(4'-ethylcarbonyloxyphenyl) oxycarbonylamino] benzoic acid 248.4-[(4'-ethylthiophenyl) oxy Carbonylamino] benzoic acid 249.4-[(4'-phenylthiof Nyl) oxycarbonylamino] benzoic acid 250.4-[(4′-fluorophenyl) oxycarbonylamino] benzoic acid 251.4-[(3′-fluorophenyl) oxycarbonylamino] benzoic acid 252.4- [ (4'-Chlorophenyl) oxycarbonylamino] benzoic acid 253.4-[(3'-chlorophenyl) oxycarbonylamino] benzoic acid 254.4-[(2'-chlorophenyl) oxycarbonylamino] benzoic acid 255.4- [(2'-Formylphenyl) oxycarbonylamino] benzoic acid 256.4-[(2'-cyanophenyl) oxycarbonylamino] benzoic acid 257.4-[(2 ', 4'-dimethylphenyl) oxycarbonylamino ] Benzoic acid 258.4-[(3 ', 5'-dimethylphenyl)] Alkoxycarbonyl amino] depreciation Ikikosan 259.4 - [(3'-nitro-4'-chlorophenyl) oxycarbonyl amino] benzoic acid 260.4- (n-butyl thiol carbonylamino) benzoic acid

261.4- (phenylthiolcarbonylamino) benzoic acid 262.4-[(2'-naphthylthiol) carbonylamino] benzoic acid 263.4-[(4'-methylphenylthiol) carbonylamino] benzoic acid 264.4- (n-heptylthiothiocarbonylamino) benzoic acid 265.4- (n-dodecylthiothiocarbonylamino) benzoic acid 266.4- (n-pentyloxythiocarbonylamino) benzoic acid 267.4- [ (4'-Chlorophenyl) oxythiocarbonylamino] benzoic acid 268.4- (N-methyl-N-phenyloxycarbonylamino) benzoic acid

In the heat-sensitive recording material of the present invention, the benzoic acid derivative represented by the general formula (1) and the polyvalent metal salt of the derivative may be used alone or in combination of two or more kinds.

The benzoic acid derivative represented by the general formula (1) can be prepared by a known method, for example, Bull. Soc. Chi
m. Fr. , 1189 (1955). That is, it can be produced by reacting the aminobenzoic acid derivative represented by the general formula (2) with the compound represented by the general formula (3) (chemical formula 4).

[0048]

[Chemical 4] (In the formula, Y ₁ , Y ₂ and R ₂ are the same as above)

The reaction of the aminobenzoic acid derivative represented by the general formula (2) with the compound represented by the general formula (3) is usually benzene, toluene, xylene, pentane, hexane, heptane, octane, cyclohexane, etc. Hydrocarbon solvents, ester solvents such as ethyl acetate, butyl acetate and amyl acetate, ether solvents such as diethyl ether, dioxane and tetrahydrofuran, halogenated hydrocarbon solvents such as dichloromethane, chloroform, dichloroethane, chlorobenzene and dichlorobenzene. ,methanol,
It is preferable to use an organic solvent such as an alcohol solvent such as ethanol, isopropanol, butanol, pentanol, octanol, cyclohexanol, methyl cellosolve or ethyl cellosolve, or water as a solvent. Of course, two or more kinds of the above solvents may be mixed and used. The amount of the reaction solvent used is not particularly limited,
It is self-evident that using too much is not preferable in terms of production efficiency, and the use of an excessively small amount requires a long time for the reaction, which is not preferable in terms of production efficiency, and is usually not preferable. Is preferably used in an amount of 0.5 times to 200 times, and more preferably 1 to 100 times, the weight of the compound represented by the general formula (2).

The amount of the compound represented by the general formula (3) used is usually 0.9 to 1.5 mol, and 1 to 1 mol relative to 1 mol of the compound represented by the general formula (2). 0.2 mol is more preferable. The reaction temperature is usually preferably -20 ° C to the boiling point of the solvent, more preferably 0 ° C to the boiling point of the solvent. Although the reaction time varies depending on the reaction temperature, it usually requires several minutes to several hours, but the reaction can be monitored by a known analytical means such as high performance liquid chromatography. Although the compound represented by the general formula (2) acts as a dehalogenating agent even if a base is not present as a dehalogenating agent in the reaction system, the desired benzoic acid derivative can be produced. It is preferable to carry out the reaction in the presence of a base. As such a base, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide and potassium hydroxide can be mentioned as preferable bases. A plurality of these inorganic bases may be combined and used. After completion of the reaction, the reaction product can be obtained by performing a usual post-treatment operation, and if desired, the purity can be further increased by a known purification method such as recrystallization or column chromatography.

In the polyvalent metal salt of the benzoic acid derivative represented by the general formula (1) according to the present invention, the polyvalent metal salt is preferably a sparingly water-soluble or water-insoluble divalent or trivalent salt.
It is a valent or tetravalent metal salt, more preferably a divalent or trivalent metal salt. Specific examples of the polyvalent metal salt, zinc, cadmium, mercury, magnesium, calcium, barium, nickel, tin, lead, gallium, chromium, copper, molybdenum, tungsten, zirconium, strontium, manganese, cobalt, titanium, aluminum, Mention may be made of iron salts, preferably zinc,
It is a salt of magnesium, calcium, barium, nickel, manganese, cobalt or aluminum, more preferably a salt of zinc, magnesium, nickel or manganese, and a zinc salt is a particularly preferable metal salt. Further, in the polyvalent metal salt of the benzoic acid derivative represented by the general formula (1), the divalent, trivalent and tetravalent metal salts are usually alkalis of the benzoic acid derivative represented by the general formula (1). From an aqueous solution of a metal salt (for example, a metal salt of sodium, potassium, lithium, etc.) and an aqueous solution of a corresponding water-soluble divalent, trivalent, or tetravalent metal compound, a sparingly water-soluble or water-insoluble solution is obtained by a metathesis method. It is produced as a polyvalent metal salt of a benzoic acid derivative. At this time, if desired, heating may be performed or an organic solvent may coexist.

As the aqueous solution of the alkali metal salt of the benzoic acid derivative represented by the general formula (1), a plurality of different aqueous solutions of the alkali metal salt of the benzoic acid derivative represented by the general formula (1) are used. For example, 4- (n-butyloxycarbonylamino) benzoic acid and 4- (n-octyloxycarbonylamino) benzoic acid may be mixed with an aqueous solution of an alkali metal salt of each of them, or 3- (phenyloxycarbonylamino). ) A polyvalent metal salt prepared by using a mixed aqueous solution of respective aqueous solutions of alkali metal salts of benzoic acid and 4- (cyclohexyloxycarbonylamino) benzoic acid can also be preferably used in the heat-sensitive recording material of the present invention. it can. As the water-soluble metal compound,
For example, sulfates such as zinc sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, chlorides such as zinc chloride, magnesium chloride, calcium chloride, barium chloride, nickel chloride, cobalt chloride, aluminum chloride, zinc acetate, manganese acetate, etc. An acetic acid salt etc. are mentioned. The polyvalent metal salt of the benzoic acid derivative represented by the general formula (1) produced as described above may form a solvate such as a hydrate depending on production conditions. The product can also be suitably used for the heat-sensitive recording material of the present invention. Of course, it is also possible to produce a polyvalent metal salt of a benzoic acid derivative by removing a solvent such as water from the solvate by a known method, for example, by drying, and, of course, the benzoate derivative of the unsolvate. The polyvalent metal salt can also be suitably used in the heat-sensitive recording material of the present invention.

The heat-sensitive recording material of the present invention contains an electron-donating color-forming compound and an electron-accepting compound, and is a benzoic acid derivative represented by the general formula (1) and / or a large amount of the derivative. It is characterized by containing at least one valent metal salt. More specifically describing the constitution of the heat-sensitive recording material of the present invention, the present invention provides an electron-donating color-forming compound and a benzoic acid derivative represented by the general formula (1) as an electron-accepting compound and / or the derivative thereof. Is a heat-sensitive recording material containing at least one polyvalent metal salt. The heat-sensitive recording material of the present invention is further provided with a known formulation (addition of a heat-fusible compound, etc.) for producing a known heat-sensitive recording material, as described later. In the heat-sensitive recording material of the present invention, usually 100 parts by weight of the electron-donating color forming compound is used in an amount of 50 to 50 parts by weight.
It is desirable to use 700 parts by weight, preferably 100 to 500 parts by weight. Furthermore, in the heat-sensitive recording material of the present invention,
As the electron-accepting compound, in addition to the benzoic acid derivative represented by the general formula (1) and / or the polyvalent metal salt of the derivative, another electron-accepting compound may be used in combination.

Examples of the colorless or light-colored electron-donating color-forming compound used in the present invention include triarylmethane compounds, diarylmethane compounds, rhodamine-lactam compounds, fluorane compounds, indolylphthalide compounds, pyridine. System compounds, spiro compounds, fluorene compounds and the like. Some specific examples of these compounds include 3,3-bis (4-dimethylaminophenyl) as a triarylmethane compound.
-6-Dimethylaminophthalide [alias, crystal violet lactone], 3,3-bis (4-dimethylaminophenyl) phthalide, 3- (4-dimethylaminophenyl) -3- (1,3-dimethylindole-3) -Ill)
Phthalide, 3- (4-dimethylaminophenyl) -3-
(2-Methylindol-3-yl) phthalide, 3,3
-Bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3- (1-methylpyrrol-3-yl) -6-
Dimethylaminophthalide, 3,3-bis [2,2-bis (4-dimethylaminophenyl) ethenyl] -4,5,
6,7-tetrachlorophthalide and the like. Examples of the diarylmethane compound include 4,4-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, and N-2,4,5-trichlorophenyl leuco auramine. Rhodamine-lactam compounds include rhodamine-B-anilinolactam, rhodamine- (4-nitroanilino) lactam, rhodamine-B- (4-chloroanilino) lactam and the like.

Examples of the fluorane compound include 3,6-dimethoxyfluorane, 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, and 3-diethylamino-7-methoxyfluorane. Diethylamino-7-chlorofluorane, 3-
Diethylamino-6-methyl-7-chlorofluorane,
3-diethylamino-6,7-dimethylfluorane, 3
-N-cyclohexyl-N-n-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-
Chloroanilino) fluorane, 3-diethylamino-7
-(3-chloroanilino) fluorane, 3-diethylamino-7- (2,3-dichloroanilino) fluorane,
3-diethylamino-7- (3-trifluoromethylanilino) fluorane, 3-di-n-butylamino-7-
(2-chloroanilino) 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-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-di-n-octylamino-6-methyl-7-anilinofluorane, 3-N-ethyl-N-methylamino-6-methyl-7-anilinofluorane, 3-
N-n-propyl-N-methylamino-6-methyl-7
-Anilinofluorane, 3-N-n-propyl-N-ethylamino-6-methyl-7-anilinofluorane, 3
-N-isopropyl-N-methylamino-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-Nn-butyl-Nn-
Propylamino-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-Nn-hexyl-N-ethylamino- 6-methyl-7-anilinofluorane, 3-Nn-octyl-N-ethylamino-6-
Methyl-7-anilinofluorane, 3-N-cyclohexyl-N-methylamino-6-methyl-7-anilinofluorane, 3-N-cyclohexyl-N-n-propylamino-6-methyl-7- Anilino Fluoran, 3-N
-Cyclohexyl-N-n-butylamino-6-methyl-7-anilinofluorane, 3-N-cyclohexyl-
N-n-pentylamino-6-methyl-7-anilinofluorane, 3-N-cyclohexyl-N-n-hexylamino-6-methyl-7-anilinofluorane, 3-N
-Cyclohexyl-Nn-heptylamino-6-methyl-7-anilinofluorane,

3-N-cyclohexyl-Nn-octylamino-6-methyl-7-anilinofluorane, 3-
N-cyclohexyl-N-n-decylamino-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-anilinofluorane, 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.

The indolyl phthalide compound is
3,3-bis (1-ethyl-2-methylindole-3
-Yl) phthalide, 3,3-bis (1-octyl-2-
Methylindol-3-yl) phthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3
-(2-Ethoxy-4-dibutylaminophenyl) -3
-(1-Ethyl-2-methylindol-3-yl) phthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-octyl-2-methylindole-
3-yl) phthalide 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 and 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-methylindol-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- There is azaphthalide.

Examples of the spiro compound include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran and 3-
Benzyl-spiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxybenzo) spiropyran, 3-propyl-spiro-dibenzopyran and the like.

As the fluorene compound, 3 ', 6'
-Bisdiethylamino-5-diethylaminospiro (isobenzofuran-1,9'-fluorene) -3-one,
3 ', 6'-bisdiethylamino-7-diethylamino-2-methylspiro (1,3-benzoxazine-4,
9'-fluorene) and the like. These electron-donating color-forming compounds may be used alone or in combination of two or more for the purpose of adjusting the color tone of a color image and obtaining a multicolor heat-sensitive recording material.

As described above, in the heat-sensitive recording material of the present invention, as the electron-accepting compound, other than the benzoic acid derivative represented by the general formula (1) and / or the polyvalent metal salt of the derivative, other An electron accepting compound can also be used in combination. In this case, the proportion of the benzoic acid derivative represented by the general formula (1) or / and the polyvalent metal salt of the derivative in the total electron-accepting compound is usually 10% by weight or more, preferably 20% by weight or more. , And more preferably, 30 wt% or more is desirable. A heat-sensitive recording material formed by using these other electron-accepting compounds in combination is also preferable because the stability of a color image (wet heat resistance, water resistance, oil resistance, etc.) is also excellent. Examples of the electron-accepting compound other than the benzoic acid derivative represented by the general formula (1) and / or the polyvalent metal salt of the derivative include organic electron-accepting compounds such as phenol derivatives, organic acids or their metal salts, complexes, and urea derivatives. Inorganic electron-accepting compounds such as organic compounds or acid clay.

Some specific examples of these compounds are 4-tert-butylphenol, 4-tert-octylphenol, 4-phenylphenol, 1-naphthol, 2-naphthol, hydroquinone, resorcinol, 4-tert-octyl. Catechol, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 2,2-bis (4'-hydroxyphenyl)
Propane [also known as bisphenol A], 1,1-bis (4'-hydroxyphenyl) cyclohexane, 2,2-
Bis (4'-hydroxy-3'-methylphenyl) propane, 1,4-bis (4'-hydroxycumyl) benzene, 1,3,5-tris (4'-hydroxycumyl) benzene, 4,4 -(M-Phenylenediisopropylidene) bisphenol, 4,4- (p-phenylenediisopropylidene) bisphenol, 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, 2,4′-dihydroxydiphenyl Sulfone, 4-hydroxy-4'-methyldiphenyl sulfone, 4-hydroxy-4'-chlorodiphenyl sulfone, 4-hydroxy-4'-n-propoxydiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone 4-hydroxy-4 '
-N-butoxydiphenyl sulfone, 3,4-dihydroxy-4'-methyldiphenyl sulfone, 2,4-
Dihydroxydiphenyl sulfone, 2-methoxy-
4'-hydroxydiphenyl sulfone, 2-ethoxy-2'-hydroxydiphenyl sulfone, bis (2-
Hydroxy-5-tert-butylphenyl) sulfone,
Bis (2-hydroxy-5-chlorophenyl) sulfone, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 1,7-di (4-hydroxyphenylthio) -3,5-dioxaheptane, 1,5-di A phenol derivative such as (4-hydroxyphenylthio) -3-oxapentane,

Salicylic acid, 3-isopropylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-tert-
Butyl salicylic acid, 3,5-di-α-methylbenzyl salicylic acid, 3-methyl-5-α-methylbenzyl salicylic acid, 4- [2 ′-(4-methoxyphenyloxy) ethyloxy] salicylic acid, 2-hydroxy-3- Naphthoic acid, 2-hydroxy-6-naphthoic acid, phthalic acid monobenzyl ester, phthalic acid monophenyl ester, 4
-Organic acids such as nitrobenzoic acid, 3-nitrobenzoic acid, 2-nitrobenzoic acid and 4-chlorobenzoic acid or metal salts thereof (for example, nickel, zinc, aluminum,
Metal salts such as calcium), zinc thiocyanate antipyrine complex, complexes such as molybdate acetylacetone complex, phenylthiourea, di (3-trifluoromethylphenyl) thiourea, 1,4-di (3′-chlorophenyl) -3- Preferred compounds include organic electron-accepting compounds such as urea derivatives such as thiosemicarbazide, and inorganic electron-accepting compounds such as acid clay, attapulgite, activated clay, aluminum chloride, zinc chloride and zinc bromide. These electron-accepting compounds may be used alone or in combination of two or more kinds.

In the heat-sensitive recording material of the present invention, a heat-fusible compound (melting point: about 7) is used as a sensitizer for the purpose of improving color developing sensitivity.
It is preferable to add a compound having a melting point of 0 to 150 ° C., more preferably a melting point of about 80 to 130 ° C.) in order to obtain a heat sensitive recording material compatible with high speed recording. In this case, it is usually desirable to use 10 to 700 parts by weight of the heat-fusible compound, preferably 20 to 500 parts by weight, based on 100 parts by weight of the electron-donating color forming compound. Specific examples of such a heat-fusible compound include, for example, caproic acid amide, capric acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, stearyl urea, stearic acid anilide, N-ethylcarbazole, 4-methoxydiphenylamine. Nitrogen-containing compounds such as 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, glutaric acid diphenacyl ester, di (4-methylphenyl) carbonate, terephthalic acid dibenzyl ester, and other ester compounds,
Hydrocarbon compounds such as 4-benzylbiphenyl, m-terphenyl, fluorene, fluoranthene, 2,6-diisopropylnaphthalene, and 3-benzylacenaphthene,

2-benzyloxynaphthalene, 2-
(4'-methylbenzyloxy) naphthalene, 1,4-
Diethoxynaphthalene, 1,2-diphenoxyethane,
1,2-bis (3'-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, 4
-(4'-methylphenoxy) biphenyl, 1,4-bis (2'-chlorobenzyloxy) benzene, 4,4 '
-Di-n-butoxydiphenyl sulfone, 1,2-diphenoxybenzene, 1,4-bis (2'-chlorophenoxy) benzene, 1,4-bis (4'-methylphenoxy) benzene, 1,4-bis (3'-methylphenoxymethyl) benzene, 4-chlorobenzyloxy- (4 '
-Ethoxybenzene), 4,4'-bis (phenoxy)
Ether compounds such as diphenyl ether, 4,4′-bis (phenoxy) diphenyl thioether, 1,4-bis (4′-benzylphenoxy) benzene, 1,4-bis [(4′-methylphenyloxy) methoxymethyl] benzene And so on. These heat-fusible compounds may be used alone or in combination of two or more kinds.

The heat-sensitive recording material of the present invention can be manufactured by a known method without using a special method. Generally, an electron-donating color-forming compound, an electron-accepting compound, and a benzoic acid derivative represented by the general formula (1) and / or a polyvalent metal salt of the derivative are each ball-milled in a water-soluble binder. By a means such as a sand mill, a horizontal sand mill, an attritor, a colloidal mill, etc., it is usually pulverized and dispersed to a particle size of 3 μm or less, preferably 1.5 μm or less, and mixed to prepare a coating liquid for a recording layer. . At this time, among the pigments described later, metal compounds such as zinc oxide, zinc carbonate, calcium carbonate,
When magnesium carbonate, barium carbonate, barium sulfate, titanium oxide, aluminum hydroxide, magnesium hydroxide or the like is used as a pigment, a benzoic acid derivative represented by the general formula (1) or / and a polyvalent metal salt of the derivative, By dispersing the pigment of a metal compound together, it is possible to obtain a heat-sensitive recording material having higher storage stability of a color image, which is preferable in some cases.

Specific examples of such water-soluble binders include polyvinyl alcohol, sulfonated polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, and styrene-anhydrous. Maleic acid copolymer, isobutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylamide, methylol-modified polyacrylamide, starch derivative, casein, gelatin, methylcellulose,
Examples include carboxymethyl cellulose, gum arabic, and carboxyl group-modified polyvinyl alcohol.

Further, in the recording layer of the heat-sensitive recording material of the present invention, a pigment, a water-insoluble binder, a metal soap, a wax, a surfactant, an ultraviolet absorber, a hindered phenol, an antifoaming agent, etc. may be added, if necessary. Added. As pigments, zinc oxide, zinc carbonate, calcium carbonate, magnesium carbonate,
Barium carbonate, barium sulfate, titanium oxide, talc, wax, kaolin, diatomaceous earth, aluminum hydroxide, magnesium hydroxide, alumina, silica, amorphous silica,
Urea-formalin filler, polyethylene particles, cellulose filler and the like are used. As the water-insoluble binder, synthetic rubber latex or synthetic resin emulsion is generally used, and styrene-butadiene rubber latex, acrylonitrile-butadiene latex, methyl acrylate-butadiene rubber latex, vinyl acetate emulsion, etc. are known, and necessary. Used accordingly.

As the metal soap, higher fatty acid metal salts are used, and zinc stearate, calcium stearate,
Aluminum stearate, zinc oleate and the like are used. Examples of the wax 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, a sulfosuccinic acid-based alkali metal salt [for example, di (n-hexyl) sulfosuccinic acid,
Sodium salt of di (2-ethylhexyl) sulfosuccinic acid and the like], fluorine-containing surfactant and the like. Examples of ultraviolet absorbers include cinnamic acid derivatives, benzophenone derivatives, and benzotriazolylphenol derivatives.

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.
1,3-tris (2-methyl-4-hydroxy-5-te
rt-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, 2, 2'-methylene-bis (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis (6-tert-butyl-4-ethylphenol), 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 can be mentioned.

In the heat-sensitive recording material of the present invention, the method for 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 gravure coater, a curtain coater, and a wire bar, and dried to form a recording layer. can do. The coating amount of the coating liquid is not particularly limited, and is generally adjusted to a dry weight of 1.5 to 12 g / m ² , preferably 2.5 to 10 g / m ² . As the support, paper, plastic sheet, synthetic paper or the like is used. If necessary, a protective layer may be provided on the front surface and / or the back surface of the heat-sensitive recording layer, or an undercoat layer may be provided between the support and the heat-sensitive recording layer. Various known techniques in the method of manufacturing a heat-sensitive recording material, such as application, can be applied.

[0074]

EXAMPLES The present invention will be described in more detail below with reference to production examples and examples, but the present invention is not limited thereto. In the following,% represents% by weight. Production Example 1 (Production of Zinc Salt of Exemplified Compound No. 135) 137 g of 3-aminobenzoic acid and sodium hydrogen carbonate 84
To a solution of methanol (700) in which g was suspended, 160 g of phenyl chloroformate was added dropwise at room temperature over 2 hours. After the dropping was completed, the mixture was further stirred at room temperature for 1 hour, and then a mixed aqueous solution of concentrated hydrochloric acid 30 g and water 1200 ml was added,
The precipitated crystals were filtered and dried to obtain the desired 3- (phenyloxycarbonylamino) benzoic acid 205 g as colorless crystals. Yield 80%, melting point 252-254
° C. 25.7 g of this 3- (phenyloxycarbonylamino) benzoic acid was gradually added to a mixed solution of water (400 ml) and methanol (600 ml) containing 8.4 g of sodium hydrogen carbonate at room temperature to dissolve it. An aqueous solution (1200 ml) containing 14.9 g of zinc sulfate heptahydrate
Was added dropwise at room temperature over 1 hour. After the dropping, the mixture was stirred for 4 hours at room temperature, and the precipitated crystals were filtered, washed with water and dried to obtain 26.0 g of colorless crystals, which was the target 3
A zinc salt of-(phenyloxycarbonylamino) benzoic acid was obtained. Melting point 300 ° C or higher.

Production Example 2 (Production of Zinc Salt of Exemplified Compound No. 201) 137 g of 4-aminobenzoic acid and sodium hydrogen carbonate 84
In a solution of methanol (700 ml) in which g was suspended, n-
210 g of nonyl chloroformate was added dropwise at room temperature over 2 hours. After completion of the dropping, the mixture was further stirred at room temperature for 2 hours, a mixed aqueous solution of concentrated hydrochloric acid 30 g and water 1200 ml was added, and the precipitated crystals were filtered and dried to obtain the desired 4- (n).
-Nonyloxycarbonylamino) benzoic acid 250 g
Was obtained as colorless crystals. Yield 81%, melting point 176 ~
178 ° C. This 4- (n-nonyloxycarbonylamino) benzoic acid (30.7 g) was added to sodium hydrogencarbonate 8.4.
To a mixed solution of water (400 ml) containing g and methanol (600 ml) was gradually added at room temperature to dissolve. An aqueous solution containing 124.9 g of zinc sulfate heptahydrate (12
(00 ml) at room temperature over 1 hour. After dropping
After stirring at room temperature for 4 hours, the precipitated crystals were filtered off,
After washing with water and drying, the desired zinc salt of 4- (n-nonyloxycarbonylamino) benzoic acid was obtained as 31 g of colorless crystals. Melting point 257-259 [deg.] C.

Production Example 3 (Production of Zinc Salt of Exemplified Compound No. 234) According to the method described in Production Example 1, except that phenyl chloroformate was used in place of n-nonyl chloroformate in Production Example 1. , 4- (phenyloxycarbonylamino) benzoic acid (melting point 244 to 246 ° C.) was prepared, and a zinc salt of 4- (phenyloxycarbonylamino) benzoic acid was prepared according to the method described in Preparation Example 1. Melting point 300 ° C or higher.

Examples 1 to 21 100 g of solution A, 250 g of solution C, and D prepared by the following method
Liquid 250g dispersion and 30% paraffin wax 23g
Is mixed with a high-quality paper, and the dry coating amount is 5.0 ±
The heat sensitive recording paper was prepared by coating and drying so that the coating amount was 0.5 g / m ² . In addition, the electron-donating color-forming compound in the liquid A and the benzoic acid derivative represented by the general formula (1) in the liquid C and / or the polyvalent metal salt of the derivative used in each Example are listed in Table 1. (Table 1, Table 2 and Table 3). [Preparation Method of Dispersion Liquid] (Composition of Liquid A) Electron-donating color forming compound 10 g 10% Polyvinyl alcohol aqueous solution (Kuraray-117) 10 g Water 80 g Total 100 g (Composition of Liquid B) Electron-accepting compound 20 g Light calcium carbonate (Okutama) Industry, TP-123) 40 g 10% aqueous polyvinyl alcohol solution (Kuraray-117) 60 g Water 130 g Total 250 g (C liquid composition) Benzoic acid derivative represented by the general formula (1) or / and a polyvalent metal salt of the derivative. 20 g Light calcium carbonate (Okutama industry, TP-123) 40 g 10% polyvinyl alcohol aqueous solution (Kuraray-117) 60 g Water 130 g Total 250 g (D liquid composition) Heat-fusible compound (2-benzyloxynaphthalene) 20 g 10% Poly vinyl alcohol solution (Kuraray -117) 10 g water 22 g meter 250g above A liquid, B liquid, C solution, the solution D, a sand grinding mill, respectively, average particle size, dispersion to be less than 1.5 microns, to prepare a dispersion.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

Examples 22 to 27 Liquid A 100 g, liquid B 250 g, liquid C 250 g, liquid D 25
Mix 0 g of the dispersion and 23 g of 30% paraffin wax, and apply this to a fine paper with a dry coating amount of 5.0 ± 0.5 g.
It was applied so as to be / m ² and dried to prepare a heat-sensitive recording paper. In addition, bisphenol A was used as the electron-accepting compound in the liquid B. Further, the electron-donating color-forming compound in the liquid A and the benzoic acid derivative represented by the general formula (1) in the liquid C and / or the polyvalent metal salt of the derivative used in each of the examples are shown in Table 2 ( It is shown in Table 4).

[0082]

[Table 4]

Comparative Examples 1 to 4 A dispersion of 100 g of liquid A, 250 g of liquid B and 250 g of liquid D were mixed with 23 g of 30% paraffin wax, and the dry coating amount thereof was 5.0 ± 0.5 g on high-quality paper. It was applied so as to be / m ² and dried to prepare a heat-sensitive recording paper. Incidentally, the electron-donating color-forming compound and B in the liquid A used in each comparative example were used.
The electron-accepting compounds in the liquid are shown in Table 3 (Table 5).

[0084]

[Table 5]

Comparative Examples 5 to 6 Zinc stearate (Comparative Example 5) instead of the benzoic acid derivative represented by the general formula (1) or / and the polyvalent metal salt of the derivative in the liquid C according to the present invention. Alternatively, zinc benzoate (Comparative Example 6) was used, and the electron-donating color-forming compound in the liquid A was 3-di-n-butylamino-6-methyl-7.
-Anilinofluorane is used, bisphenol A is used as the electron-accepting compound in solution B, and solution A 100
g, B liquid 250 g, C liquid 250 g, and D liquid 250 g dispersion liquid and 30% paraffin wax 23 g were mixed, and the dry coating amount of this was set to 5.0 ± 0.5 g / m ^2. Was coated and dried to prepare a heat-sensitive recording paper.

The thermal recording papers produced in the examples and comparative examples were evaluated by the following methods. The results of the storage stability test of the uncolored part are shown in Table 4 (Tables 6 and 7).
The results of the storage stability test of the colored image are shown in Table 5 (Tables 8 and 9). [Evaluation Method of Thermosensitive Recording Paper] (Storage Stability Test of Uncolored Part) The whiteness of the uncolored part (background) immediately after application of each thermal recording paper prepared in Examples and Comparative Examples was measured by a color difference meter (Σ- 80, manufactured by Nippon Denshoku). The thermal recording papers prepared in Comparative Example 3 and Comparative Example 4 were already stained with black gray immediately after coating. As the storage stability test, a moist heat resistance test and an oil resistance test were conducted, and the whiteness of the uncolored portion of each thermosensitive recording paper after each test was examined. Moisture and heat resistance test: Each thermosensitive recording paper was stored at 40 ° C. and 90% relative humidity for 24 hours, and the whiteness was measured using a color difference meter. Oil resistance test: Each thermosensitive recording paper was overlaid with a capsule coated paper containing dioctyl phthalate, passed through a pressure roll, and stored at 25 ° C for 1 week. Was measured using. The larger the value, the higher the whiteness and the better the storage stability of the uncolored part. In addition, as a writing resistance test, after writing the uncolored portion with a highlighter pen, the
The whiteness of the uncolored portion after being left for 2 hours was visually observed. ○ indicates a state with no stain and high whiteness, and × indicates a state in which it was stained black gray.

(Colored Image Storage Stability Test) Each of the thermosensitive recording papers prepared in Examples and Comparative Examples was subjected to a Macbeth densitometer (TR-524 type) using a thermosensitive paper coloring device (TH-PMD manufactured by Okura Electric Co., Ltd.). ), The color density measured using
After forming a colored image of 9, a storage stability test was performed. As the storage stability test, a moist heat resistance test and an oil resistance test were conducted to examine the image storage stability of each thermal recording paper after each test. Moisture and heat resistance test: Each of the thermosensitive recording papers was stored at 40 ° C. and 90% relative humidity for 24 hours, and the color image density was measured using a Macbeth densitometer to obtain the residual ratio of the color image. Oil resistance test: Each thermosensitive recording paper was overlaid with a dioctyl phthalate-containing capsule-coated paper, passed through a pressure roll, and then stored at 25 ° C. for 1 week.
It measured using the Macbeth densitometer and calculated | required the residual rate of the color image. The larger the value, the better the storage stability of the color image. In addition, as a writing resistance test, after writing the colored portion with a highlighter pen, the degree of residual rate of the colored portion was visually observed after standing at 25 ° C. for 72 hours. ◎ indicates that there is no color fading, ○ indicates that the color is a little decolored, ×
Indicates the state of being erased.

[0088]

[Table 6]

[0089]

[Table 7] As is clear from Table 4, the heat-sensitive recording material of the present invention containing the benzoic acid derivative represented by the general formula (1) or / and the polyvalent metal salt of the derivative is compared with the conventional heat-sensitive recording material. The whiteness of the uncolored part (background) immediately after application and the storage stability (moisture and heat resistance, oil resistance and writing instrument resistance) of the uncolored part are very excellent.

[0090]

[Table 8]

[0091]

[Table 9] As is apparent from Table 5, the heat-sensitive recording material of the present invention containing the benzoic acid derivative represented by the general formula (1) or / and the polyvalent metal salt of the derivative is compared with the conventional heat-sensitive recording material. In addition, the storage stability (moisture and heat resistance, oil resistance, and writing instrument resistance) of the colored image is very excellent.

[0092]

The present invention provides a heat-sensitive recording material containing an electron-donating color-forming compound and an electron-accepting compound,
To provide a heat-sensitive recording material having very excellent storage stability of an uncolored portion and a colored image by containing a benzoic acid derivative represented by the general formula (1) or / and a polyvalent metal salt of the derivative. Is what makes it possible.

 ─────────────────────────────────────────────────── (72) Inventor Kiyoharu Hasegawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Kayo Yoshikawa 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Within the corporation

Claims (1)

[Claims] 1. A heat-sensitive recording material containing an electron-donating color-forming compound and an electron-accepting compound, which comprises a benzoic acid derivative represented by the general formula (1) (Chemical Formula 1) or / and a polyvalent metal salt of the derivative. A heat-sensitive recording material containing at least one. [Chemical 1] (In the formula, X ₁ and X ₂ represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group, an aralkyl group or an aryl group, Y ₁ and Y ₂ represent an oxygen atom or a sulfur atom, and 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)