JPH03253392A - Thermal recording body - Google Patents

Abstract

PURPOSE:To improve the keeping quality, especially solvent resistance, of a recorded picture by containing at least one sort of specific phthalide derivatives as a basic dye and by containing at least one sort of specific salicylic acid derivatives or their polyvalent metal salts as a coloration agent. CONSTITUTION:The title recording body is caused to contain at least one sort of phthalide derivatives expressed by formula I and to contain at least one sort of salicylic acid derivatives expressed by formula II or their polyvalent metal salts as a coloration agent. In the formula I, R1-R10 respectively represent a hydrogen atom, halogen atom, nitro group, saturated or unsaturated alkyl group which may be substituted, etc.; but they can form a hetero ring mutually or with an adjacent benzene ring. In the formula II, Ar represents a phenyl radical which may have a substituent, naphthyl radical which may have a substituent or complex aromatic ring group which may have a substituent; R represents an ether linkage, ester linkage, etc., X represents a hydrogen atom, alkyl group, etc., and (m) represents an integer of 1-3.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention has excellent characteristics for optical character (or mark) reading devices having a reading wavelength range in the infrared region, and furthermore, The present invention relates to a heat-sensitive recording medium with excellent storage stability.

``Prior Art'' Conventionally, thermosensitive recording materials have been used that record information transmitted through the medium of thermal energy by utilizing a color reaction between a colorless or light-colored basic dye and an organic or inorganic electron-accepting substance. Are known.

On the other hand, in recent years, along with the rationalization of administrative processing, the number of cases in which recorded images on recording media are read and processed using optical character reading devices (including mark reading) has increased significantly, and in particular, the number of cases in which optical character reading devices (including mark reading) are used to read and process recorded images on recording media has increased significantly. Optical character reading devices are increasingly being used. For example, in the distribution industry, POS systems are attracting attention as a powerful tool in order to quickly respond to consumer needs, and price tags with OCR characters, barcodes, etc. are processed by computer at the same time as cash register payment. Although efforts are being made to improve business efficiency, the reader uses a small, inexpensive device with a reading wavelength in the infrared region.

However, the recorded images (black colored image, blue colored image, red colored image, green colored image, etc.) obtained with general thermosensitive recording materials are in the visible region (
For optical character readers with a reading wavelength range in the near-infrared region (700-900 nm), it is possible to read as a lead color, but for optical character readers with a reading wavelength range in the near-infrared region (700-900 nm), could not be applied because it would function as a dropout color regardless of the color tone. For this reason, phthalide derivatives having a specific divinyl group are used as basic dyes suitable for optical character reading devices using near-infrared light (Japanese Patent Laid-Open Nos. 58-157779 and 62-24).
Furthermore, the combined use of metal salts of aromatic carboxylic acids and the like (Japanese Patent Application Laid-Open No. 63-257680) has been proposed for the purpose of improving the storage stability, particularly the light resistance, of the recorded images.

However, heat-sensitive recording materials using these phthalide derivatives generally have drawbacks such as fogging due to the influence of solvents and the like, and recorded images changing and fading.

Therefore, stationery and office supplies such as water-based ink pens, oil-based ink pens, fluorescent pens, ink ink, adhesives, glue, diazo developer, hand creams, hair tonics, etc.
When it comes into contact with cosmetics such as emulsions or packaging materials such as vinyl chloride film, the white paper may become colored or the colored parts may discolor, making it difficult for optical character reading devices to process them. The current situation is that the value of the product is significantly impaired.

``Problems to be Solved by the Invention'' The present invention is capable of reading characters using an optical character reading device having a reading wavelength range in the near-infrared region. The purpose is to obtain a heat-sensitive recording medium.

"Means for Solving the Problems" The present inventors have prepared a colorless or light-colored basic dye on a support and 1. In a heat-sensitive recording material provided with a recording layer containing a coloring agent capable of coloring upon contact with the basic dye, a phthalide derivative represented by the general formula [I] is contained as a basic dye in the recording layer. The present inventors have discovered that such objects can be achieved extremely efficiently by containing at least one salicylic acid derivative or its polyvalent metal salt represented by the following general formula [■] as a coloring agent. He has completed his invention.

(In the formula, RI-R1° are each a hydrogen atom; a halogen atom;
Nitro group: an optionally substituted saturated or unsaturated alkyl group; an optionally substituted cycloalkyl group; an optionally substituted alkoxyl group; an optionally substituted acyloxy group;
An optionally substituted aryl group; an optionally substituted aralkyl group; an optionally substituted phenoxy group; an optionally substituted thioalkoxyl group; or an amino group -"=R+!+
(R+z and Rlz are each a hydrogen atom; an optionally substituted saturated or unsaturated alkyl group; an optionally substituted cycloalkyl group; an optionally substituted aryl group; an optionally substituted aralkyl group; tetrahydrofurfuryl or an acyl group which may be substituted, but can form a heterocycle with each other or with adjacent benzene rings.), Ro represents a hydrogen atom or a lower alkyl group, a, b
, c, and d represent carbon atoms, of which 1 to 2 may be nitrogen atoms. Carbon atoms have hydrogen atoms as substituents: halogen atom: alkyl group; alkoxyl group: optionally substituted atom. or a nitro group may be bonded, and the a-b, b-c or c-d bond may form another aromatic ring.] [In the formula, Ar has a substituent; represents a phenyl group that may have a substituent, a naphthyl group that may have a substituent, or a heteroaromatic group that may have a substituent, and R has an ether bond, an ester bond, an amide bond, or an unsaturated bond. a branched or straight-chain alkylene group that may have an ether bond, an ester bond, or an agondo bond; an aralkylene group that may have an ether bond, an ester bond, or an ado bond; Or represents an arylene group. Further, X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxyl group, an aryloxy group, a nitro group, or a halogen atom, and m represents an integer of 1 to 3. ] "Function" The heat-sensitive recording material of the present invention has the above general formula (
A significant feature lies in the use of at least one phthalide derivative represented by I) and a salicylic acid derivative represented by general formula (n) or a polyvalent metal salt thereof as a coloring agent.

Such recording media have sufficient color density, and the colored images are extremely stable, and the recorded images will hardly change color even if they are exposed to sunlight for long periods of time or are stored at high temperatures or in high-temperature environments. This is extremely advantageous in terms of long-term preservation of records.

In particular, when the coloring layer is configured with such a combination, the disadvantages such as coloring of blank areas and discoloration of recorded images due to solvents, etc. are eliminated, and it is possible to read in the near-infrared region, which has extremely excellent characteristics. A thermosensitive recording medium is obtained.

As the divinylphthalyl derivative represented by the general formula (1) used in the heat-sensitive recording layer of the present invention, the following compounds are specifically exemplified.

3.3-bis[1,1-bis(4-dimethylaminophenyl)ethylene-2-yl)-4,5゜6,7-titrachlorophthalide, 3.3-bis[1,1-bis( 4-diethylaminophenyl)ethylene-2-yl)-4,5
, 6,7-titrachlorophthalide, 3,3-bis[1,
1-bis(2-methyl-4-diethylaminophenyl)
ethylene-2-yl)-4,,5,6,7-titrachlorophthalide, 3,3-bis[1,1-bis(2-methoxy-4-diethylaminophenyl)ethylene-2-yl)-4 , 5,6,7-titrachlorophthalide, 3,3-
Bis[1,1-bis(4-dimethylaminophenyl)-
1-propen-2-yl]4.5.6.7-titrachlorophthalide, 3゜3-bis[1,1-bis(4-dimethylaminophenyl)ethylene-2-yl]-5-pyrrolidino Phthalide, 3.3-bis[1,1-bis(4-dimethylaminophenyl)ethylene-2-yl]-6-pyrrolidinophthalide, 3.3-bis[1,1bis(4-dimethylaminophenyl) kunophenyl)ethylene-2-yl)-5,6-
Dichlorophthalide, 3゜3-bis[1,1-bis(4-
dimethylaminophenyl)ethylene-2-yl]phthalide, 3,3bis[1,■-bis(4-dimethylaminophenyl)ethylene-2-yl]-5-dimethylaminophthalide, 3,3-bis[1 , 1-bis(4-dimethylaminophenyl)ethylene-2-yl]6-dimethylaminophthalide, 3.3-bis[1,1-bis(4-dimethylaminophenyl)ethylene-2-yl]- 5-nitrophthalide, 3゜3-bis(1,1-bis(4-dimethylaminophenyl)ethylene-2-yl)-6-nitrophthalide, 3.3-bis[1,1-bis(4-jethylagonophenyl) ) Ethylene-2-yl-5-ethoxyphthalide, 3,3-bis[1,l-bis(4-diethylaminophenyl)ethylene-2-yl]-6-nitoxyphthalide, 3,3-bis[1,1-bis (4-dimethylaminophenyl)ethylene-2-yl2-5-methylphthalide, 3゜3-bis[1,1-bis(4-dimethylaminophenyl)ethylene-2-yl2-6-methylphthalide,
3,3-bis[1,1-bis(4-N-ethyl-N-benzylaminophenyl)ethylene 2-yl)-4,5,
6,7-titrachlorophthalide, 3,3-bis[1,1
-bis(4-N-methyl-N-p-tolylaminophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3,3-bis[1,1-bis(4 -dimethylaminophenyl)ethylene-2-yl2-56-penzophthalide, 3.3-bis[1,l-bis(4-dimethylaminophenyl)ethylene-2-yl]-4-azaphthalide, 3.3-bis[1゜1-bis(4-dimethylacunophenyl)ethylene-2-yl]-5-azaphthalide, 3,3-bis[1,l-bis(4-dimethylaminophenyl)ethylene-2-yl]-6-azaphthalide , 3゜3-bis[1,l-bis(4-dimethylaminophenyl)ethylene-2-yl]-7-azaphthalide, 3
．． 3-bis[1,1-bis(4-dimethylaminophenyl)ethylene-2-yl)-4,7-diazaphthalide,
3.3-bis(1,1-bis(4-dimethylaminophenyl)ethylene-2-yl)-5,6-benzo-4,7
-diazaphthalide, 3,3-bis[1,1-bis(4-
pyrrolidinophenyl)ethylene-2-yl]phthalide,
3゜3-bis(1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3,3-bis[1,1-bis( 4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7
-titrabromophthalide, 3,3-bis[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl]-5
-nitrophthalide, 3,3-bis[1,1-bis(4-
pyrrolidinophenyl)ethylene-2-yl]-6-nitrophthalide, 3.3-bis[1,1-bis(4pyrrolidinophenyl)ethylene-2-yl]-5-ethoxyphthalide, 3.3- Bis[l, 1-bis(4-pyrrolidinophenyl)ethylene-2-yl]-6-nitoxyphthalide, 3,3-bis[1゜1-bis(4-pyrrolidinophenyl)ethylene-2-yl]- 5-methylphthalide, 3.
3-bis[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl2-6-methylphthalide, 3,3-bis[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl2-5- Pyrrolidinophthalide, 3,3-bis[1,1-bis(4-pyrrolidinophenyl)ethylene-
2-yl]-6-pyrrolidinophthalide, 3,3-bis[
1,1-bis(4-pyrrolidinophenyl)ethylene-2
-yl)-5゜6-dichlorophthalide, 3.3-bis[
1,1bis(4-piperidinophenyl)ethylene-2-
yl]phthalide, 3.3-bis[1,1-bis(4-piperidinophenyl)ethylene-2-yl]5-dimethylaminophthalide, 3.3-bis[1,1-bis(4- piperidinophenyl) ethylene-2-yl2-6-dimethylaminophthalide, 3,3-bis[1,1-bis(4-
piperidinophenyl)ethylene-2-yl)-4,5,
6,7-titrachlorophthalide, 3,3-bis[l,1
-bis(4-morpholinophenyl)ethylene-2yl)
-4,5,6,7-titrachlorophthalide, 3,3-bis[1,1-bis(4-hexamethyleneiminophenyl)ethylene-2-yl]4,5,6,7-titrachlorophthalide do, 3,3-bis[1,1-bis(2-methyl-
4-pyrrolidinophenyl)ethylene-2-yl)-4,
5゜6.7-titrachlorophthalide, 3.3-bis[1
,1-bis(2-methoxy-4-pyrrolidinophenyl)
ethylene-2-yl)-4,5,6,7tetrachlorophthalide, 3,3-bis[1,1bis(4-pyrrolidinophenyl)-■-propen-2-yl)-4,5,6 ,7
-titrachlorophthalide, 3,3-bis[1,1-bis(1-methyl-1,2,3,4-tetrahydroquinolin-6-yl)ethylene-2-yl)-4,5,6° 7-
Titrachlorophthalide, 3,3-bis[1゜1-bis(
Julolidin-9-yl)ethylene-2-yl)-4,
5,6,7-titrachlorophthalide, 3,3-bis[1
,1-bis(4-pyrrolidinophenyl)ethylene-2-
yl]-5,6-dichloro-4,7-dibromophthalide, 3,3-bis[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl)-4,7-dichloro-5° 6
-dibromophthalide, 3,3-bis(1,1-bis(4
-pyrrolidinophenyl)ethylene-2-yl]-5-chloro4.6.7-dribromophthalide, 3.3-bis[1,1-bis(4-pyrrolidinophenyl)ethylene-
2-yl]-6-chloro4.5.7-1 ribromophthalide, 3,3-bis I:1-(4-ethylphenyl)-
1-(4-dimethylaminophenyl)ethylene-2-yl]4.5,6.7-titrachlorophthalide, 3゜3-
Bis(1-(4-methylphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7
-titrachlorophthalide, 3゜3-bis[1-phenyl-1-(4-dibenzylaminophenyl)ethylene-2
-yl)-4,5゜6.7-titrachlorophthalide, 3
．． 3-bis[1,1-bis(4-ethoxyphenyl)ethylene-2-yl)-4,5,6,7-titrabromophthalide, 3,3-bis(1-(4-ethoxyphenyl)
-1-(4-methoxyphenyl)ethylene 2-yl)-
4,5,6,7-Titrachlorophthalide, 3,3-bis(1-(4-cyclohexylphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6
, 7-titrachlorophthalide, 3.3-bis(1-(4
-cyclohexylphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3.3-bis[1-(4-allylphenyl)-1 -(4-diethylaminophenyl)ethylene-2-yl)-4,5,6゜7-titrachlorophthalide, 3.3-bis[1-(4-ethoxyphenyl)-1
-(2-dimethylaminophenyl)ethylene-2-yl)-4,5゜6.7-titrabromophthalide, 3,3-
Bis[1-(4-N-tetrahydrofurfuryl-N-methylaminophenyl)-1-(3-chloro-4ethoxyphenyl)ethylene-2-yl)-6-chloro-4,5
, 7-dripromophthalide, 3゜3-bis(1-(4-
phenoxyethylphenyl)-1-(4-N-methyl-
N-ethylaminophenyl) ethylene-2-yl2 5
-nitrophthalide, 3,3-bis(1-(4-chlorophenoxyethylphenyl)-1-(4-N-methyl-N
-ethylaminophenyl)ethylene-2-yl) = 6-
Nitrophthalide, 3,3-bis(1-(4-N-p-chlorophenyl-N-ethylaminophenyl)-1-(3
,4-dimethylphenyl)ethylene-2-ylyo5-
Ethoxyphthalide, 3゜3-bis(1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl]phthalide, 3.3-bis(1-(3-nitrophenyl) -1-(3-propargylphenyl)ethylene-2-yl)-4,5,6,7-titrafluorophthalide, 3.3-bis(1-[4-(β-dimethylaminoethyl aξ) ) phenyl)-1-(3-acetylphenyl)ethylene-2-yl)phthalide, 3,3-bis(1
-(4-(γ-diethylaminopropylamino)phenyl)-1-(3-(p-ethylbenzoyl)phenyl)
ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3.3-bis(1-(4-(p-chlorophenyl)phenyl)-1-(4-phenethylphenyl)ethylene-2- yl) phthalide, 3.3 bis(1-(2,
6-dimethyl-4-tert-methylphenyl)-1-
(4-aminophenyl)ethylene-2-yl)-4,5
, 6,7-titrabromophthalide, 3,3-bis(1-
(4-butoxyphenyl)-1-(4-(N-cyclohexyl-N-methylamino)phenyl]ethylene-2-
yl)-4,5,6,7-titrapromophthalide, 3.
3-bis(1-(2-methyl-4-(2-methylmercaptoethyl)phenyl)-1-(4-diallylaminophenyl)ethylene-2-yl)-5,6-dichloro-4,
7-dibromophthalide, 3.3-bis(1-(4-(3
,3,5-1-limethylcyclohexyl)phenyl)
-1-(4-(N-p-methylphenyl-N-ethylamino)phenyl]ethylene-2-yl)-4,5,6,
7tetrapromophthalide, 3.3-bis[1-(2-methyl-4-chloroethoxypropylphenyl)-1-(
2,6-diethyl-4-butylphenyl)ethylene-2
-yl2-5-chloro-4°6.7-)ribromophthalide, 3.3-bis(1-(4-(p-methylbenzoyloxy)phenyl)-1-(3,5-dimethylphenyl)ethylene-2- yl)-4,5,6-)dichlorophthalide, 3,3-bis(1-(4-methylmercaptophenyl)-1-(4-(N-p-tolylphenyl-
N-2-7”tenylamino)phenyl]ethylene-2-
yl)-4,5,6-)ribromophthalide, 3,3-bis(1-(2-methyl-4-pyrrolidinophenyl)-1
-(3-chloro-4-methylphenyl)-1-propen-2-yl)-4,5,6,7-titrachlorophthalide, 3,3-bis(1-(4-(o-methylphenylpropyl) phenyl)-1-(3-methyl-4-dibutylaminophenyl)-1-buten-2-yl)-4,5,6
, 7-titrachlorophthalide, 3.3-bis(1-(3
-Allyl-4-(p-ethylphenoxyethyl)phenyl)-1-(4-(N-ethoxypropyl-N-ethylamino)phenyl]ethylene-2-yl)-5,6-dichloro-4゜7-dibromophthalene do, 3.3-bis(1-
(2-methoxy-4-cyclohexylphenyl)-1-
[2-ethyl-4-(2-chloroethyl-2mercaptoethyl)phenyl]ethylene-2-yl)phthalide, 3
,3-bis(1-(4-cyclohexylethylphenyl)1(4-(N-tetrahydrofurfuryl-N-methallylamino)phenyl]ethylene-2-yl)-4,5,
6,7 tetrachlorophthalide, 3,3-bis(1-[4
-(3,3-dimethoxypropyl)phenyl]1- [
4-(N-p-chlorophenyl-N-isopropylaξ
]) Phenyl]ethylene-2-yl)-5-ethylphthalide, 3,3-bis[1-(3,5-dichloro-4-dimethylaminophenyl)-1-phenylethylene-2-
yl]-4゜5.6.7-titrapromophthalide, 3,
3-bis(1-(2-propionyl-4-pyrrolidinophenyl)-1-(2-chloro-4-ethoxyphenyl-
5-methylphenyl)ethylene-2-ylg-5-butoxyphthalide, 3,3-bis[1-(4-isoamylphenyl)-1-phenylethylene-2-yl-4-nitrophthalide, 3,3-bis(1- (4-α-naphthylphenyl)-1-[4-(N-3'-methylcyclohexyl-N-acetylamino)phenyl]ethylene-2-yl) = 4-nitrophthalide, 3.3-bis(1-(4-
(p-dimethylaminophenyl)phenyl]-1-(4
-morpholinophenyl)ethylene-2-yl)-5-diarylaminophthalide, 3.3-bis(1-(4-isopropoxyphenyl)-1-(4-piperidinophenyl)ethylene-2-yl) -4,5,6,7-titrachlorophthalide, 3,3-bis(1-(4-bromophenyl)-1-(1-methyl-1,2,3,4-tetrahydroquinolin-6-yl) ) ethylene-2-yl)'-4゜5
．． 6.7-Titrachlorophthalide, 3.3-bis(1-
(4-isopropoxyphenyl)-1-(2,2,4-
) riftyl-1,2-dihydroquinolin-6-yl)ethylene-2-yl]-4゜5.6.7-titrachlorophthalide, 3,3-bis(1-(2-acetylamino-4
-piperidinophenyl)-1-(2-acetoxy-4-
(3゜5-dimethylphenoxy)phenyl]ethylene-2-yl)phthalide, 3,3-bis[l-phenyl-1
-(4-dimethylaminophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3.3-
Bis[1-phenyl-1-(4-pyrrolidinophenyl)
ethylene-2-yl]-4.5.6.7-titrachlorophthalide, 3゜3-bis(1-(4-methoxyphenyl)=1=(4-dimethylaminophenyl)ethylene-2
-yl)-4,5,6,7-titrachlorophthalide, 3
．． 3-bis[1-(4-ethoxyphenyl)-l-(4
-dimethylaminophenyl)ethylene-2-yl]-4
．． 5,6.7-titrachlorophthalide, 3,3-bis(
1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3,3-bis(1-(4-phenoxy phenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3.3-bis(1-(4-ethoxyphenyl)-
1-(4-diethylaminophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3.3
-bis(1-(4-butoxyphenyl)-1-(4-piperidinophenyl)ethylene-2-yl)-4,5,6
, 7-titrachlorophthalide, 3.3-bis(1-(2
-Methyl-4-methoxyphenyl)-1-(4-diethylaminophenyl)ethylene-2-yl)-4゜5.6
．． 7-titrachlorophthalide, 3.3-bis[1-(2
-Methyl-4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7
-Titrachlorophthalide, 3,3-bis(1-(3-chloro-4-ethoxyphenyl)-1-(4-aminophenyl)ethylene-2-yl)-4,5,6,7-titrachloro Phthalide, 3,3-bis(1-(4-methoxyphenyl)-1-(2-methyl-4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6°7-titrachlorophthalide , 3.3-bis[1(4-ethoxyphenyl)-1-(3-ethoxy-4-diethylaminophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3.3 -bis(1-(3-methylphenyl)-1[4-(N-methyl-N-benzylamino)phenyl]ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3.3 -bis[1-[3,5-dichlorophenyl)-1-(4-hexamethyleneylinophenyl)ethylene-2-yl]-4.5,6.7-titrachlorophthalide, 3゜3-bis[1 -(4-ethoxyphenyl)-1(4-piperidinophenyl)ethylene-2-
yl]-5,6-penzophthalide, 3,3-bis(1-
(4-methylphenyl)-1-(julolidin-9-yl)ethylene-2-yl)-4,5,6゜7-titrachlorophthalide, 3.3-bis(1-(4-propoxyphthalide) Nyl)-1-(3-methyl4-pyrrolidinophenyl)
Ethylene-2-yl24. Fuziazaphthalide, 3.
3-bis[1-(4-n-butylphenyl)-1-(4
-dimethylaminophenyl)ethylene-2-yl) -
5゜6-benzo-4,7-diazaphthalide, 3.3-bis(1-(3-ethyl-4-ethoxyphenyl)1-(
4-dimethylaminophenyl)ethylene-2-ylio4-azaphthalide, 3,3-bis(1-(4-ethoxyphenyl)-1-(4-piperidinophenyl)ethylene-2-yl)-5-di -n-butylaminophthalide, 3
,3-bis[1-(4-ethoxyphenyl)-1-(4
-piperidinophenyl)ethylene-2-yl2-6-dinithylaminophthalide, 3.3-bis(1-(4-methoxyphenyl)-1-(4-dimethylaminophenyl)
Ethylene-2-yl-6-pyrrolidinophthalide, 3.
3-bis(1-(4-(N-methyl-N-β-dimethylaminoethyl)agonophenyl)-1-(4-fluorophenyl)ethylene-2-yl)-4-azaphthalide,
3.3bis(1-(4-(N-ethyl-N-β-chloroethylamino)phenyl)-1-(4-cyclohexyloxyphenyl)ethylene-2-yl)4-azaphthalide, 3.3 -bis[1,1-bis(4-n-7'tylphenyl)ethylene-2-yl]4.5,6.7-titrachlorophthalide and the like.

Note that these phthalide derivatives can be used alone or in combination.

In addition, in the salicylic acid derivative represented by the general formula [■], Ar is a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a heteroaromatic group which may have a substituent. Among these, a phenyl group which may have a substituent is particularly preferred. Substituents for this phenyl group include hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, alkoxyl group, alkylthio group, aryloxy group, aralkyloxy group, arylcarbonyl group, and aryloxycarbonyl group. , an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, a nitro group, a hydroxyl group, or a halogen atom, and among these, a hydrogen atom, a C8-6 alkyl group, a C
0-6 alkoxyl group, 07-. . an aralkyl group of
More preferred are C7-10 aralkyloxy groups, chlorine atoms, bromine atoms, and fluorine atoms.

Further, in the salicylic acid derivative represented by the general formula [II], R is an ether bond or an ester bond.

A branched or linear alkylene group that may have an amide bond or an unsaturated bond, a cycloalkylene group that may have an ether bond, an ester bond, or an amide bond, an ether bond, an ester bond, or an amide bond. This represents an aralkylene group or an arylene group, which may have an ether bond, and C8-1. An alkylene group is preferred.

Furthermore, in general formula [11), X is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxyl group, an aryloxy group,
It represents a nitro group or a halogen atom, and among these, a hydrogen atom, an alkyl group with CI~2°, a cycloalkyl group with C1~, an alkenyl group with C2-6, and C1~. Aralkyl group, C5-2° alkoxyl group, phenyl group, naphthyl group, phenoxy group, nitro group, or halogen atom are preferred, particularly hydrogen atom, C4-6 alkyl group, C7-I0 aralkyl group, CI- , alkoxyl group, phenyl group, phenoxy group, chlorine atom, bromine atom,
Or a fluorine atom is more preferable.

The polyvalent metal that forms a salt with the salicylic acid derivative represented by the general formula (I[) is preferably a divalent, trivalent or tetravalent metal, with zinc, calcium, aluminum, magnesium, tin, and iron being particularly preferred. preferable.

Specific examples of the salicylic acid derivative represented by the above general formula [II] include the following.

4-phenylsulfonylmethoxysalicylic acid, 5-phenylsulfonylmethoxysalicylic acid, 4(2-phenylsulfonylethoxy)salicylic acid, 5-(2-phenylsulfonylethoxy)salicylic acid, 4-(3-phenylsulfonylpropyloxy)salicylic acid, 5-( 3-phenylsulfonylpropyloxy) salicylic acid, 4-(
4-phenylsulfonylbutyloxy) salicylic acid, 5
-(4-phenylsulfonylbutyloxy) salicylic acid, 4-(5-phenylsulfonylpentyloxy) salicylic acid, 5-(5-phenylsulfonylpentyloxy) salicylic acid, 4-(6-phenylsulfonylhexyloxy) salicylic acid, 5-( 6-phenylsulfonylhexyloxy) salicylic acid, 14-(8-phenylsulfonyloctyloxy) salicylic acid, 5- (8-phenylsulfonyloctyloxy) salicylic acid, 4-(10-
Phenylsulfonyldecyloxy) salicylic acid, 5-(
10-phenylsulfonyldecyloxy) salicylic acid,
4-(12-phenylsulfonyldodecyloxy)salicylic acid, 5-(12-phenylsulfonyldodecyloxy)salicylic acid, 4(18-phenylsulfonyloctadecyloxy)salicylic acid, 5-(1B-phenylsulfonyloctadecyloxy)salicylic acid, 4-( 1-methyl-1-phenylsulfonylmethoxy) salicylic acid,
5-(1-Methyl-1-phenylsulfonylmethoxy) salicylic acid, 4-(1,1-dimethyl 1-phenylsulfonylmethoxy) salicylic acid, 5-(1,1-dimethyl-1-phenylsulfonylmethoxy) salicylic acid, 4
-(5-phenylsulfonyl-3-oxapentyloxy)salicylic acid, 5-(5-phenylsulfonyl-
3-oxapentyloxy)salicylic acid, 4-(8-
Phenylsulfonyl-3,6-thioxaroctyloxy)salicylic acid, 5-(8-phenylsulfonyl-3,
6-Shioxaroctyloxy)salicylic acid, 4-(1
1-Phenylsulfonyl-3°6.9-trioxa-undecyloxy)salicylic acid, 5-(11-phenylsulfonyl-3,6°9-trioxa-undecyloxy)salicylic acid, 4-(7-phenylsulfonyl-3 ，
5-dioxa-hebutyloxy)salicylic acid, 5-(7
-phenylsulfonyl-3,5-dioxa-heptyloxy)salicylic acid, 4-(9-phenylsulfonyl-5)
-oxa-nonyloxy) salicylic acid, 5-(9-phenylsulfonyl-5-oxa-nonyloxy) salicylic acid, 4-(3-phenylsulfonyl-1-propenyloxy) salicylic acid, 5- (3-phenylsulfonyl-
l-propenyloxy) salicylic acid, 4-(4-phenylsulfonyl-2-butenyloxy) salicylic acid, 5-
(4-phenylsulfonyl-2-butenyloxy) salicylic acid, 4-(2-phenyl-3-phenylsulfonylpropyloxy) salicylic acid, 5-(2-phenyl-3
-phenylsulfonylpropyloxy)salicylic acid, 4
-(4-phenylsulfonylmethylbenzyloxy) salicylic acid, 5-(4-phenylsulfonylmethylbenzyloxy) salicylic acid, 4-(3-phenylsulfonylmethylbenzyloxy) salicylic acid, 5-(3-phenylsulfonylmethylbenzyloxy) salicylic acid , 4-
(4-phenylsulfonylphenoxy)salicylic acid, 5
-(4-phenylsulfonylphenoxy)salicylic acid,
4-(3-phenylsulfonylphenoxy) salicylic acid, 5-(3-phenylsulfonylphenoxy) salicylic acid, 4-(2-cyclohexyl-3-phenylsulfonylpropyloxy) salicylic acid, 5-(2-cyclohexyl-3-phenyl) Sulfonylpropyloxy) salicylic M, 4-(2-phenylsulfonylacetoxyethoxy) salicylic acid, 5-(2-phenylsulfonylacetoxyethoxy) salicylic acid, 4-(3-phenylsulfonylacetoxypropyloxy) salicylic acid, 5-(3
-phenylsulfonylacetoxypropyloxy) salicylic acid, 4-(3-phenylsulfonylpropionyloxymethoxy) salicylic acid, 5-(3-phenylsulfonylpropionyloxymethoxy) salicylic acid, 4-(
2-methoxycarbonyl-2-phenylsulfonylethoxy) salicyl M, 5-(2-methoxycarbonyl-2
-phenylsulfonylethoxy)salicylic acid, 4-(2
-phenylsulfonylacetylaminoethoxy) salicylic acid, 5-(2-phenylsulfonylacetylaminoethoxy) salicylic acid, 4-(3-phenylsulfonylpropionylaminomethoxy) salicylic acid, 5-(3-phenylsulfonylpropionylaminomethoxy) salicylic acid, 4- (5-phenylsulfonyl-3-thio-pentyloxy) salicylic acid, 5-(5-phenylsulfonyl-3-thio-pentyloxy) salicylic acid, 4- (
2-(3-phenylsulfonylpropionyl)ethoxy]salicylic acid, 5-(2-(3-phenylsulfonylpropionyl)ethoxy)salicylic acid, 4-(p-)lylsulfonylmethoxy)salicylic acid, 5-(p-tolylsulfonylmethoxy) Salicylic acid, 4-(2-p-tolylsulfonylethoxy) salicylic acid, 5-(2-p-tolylsulfonylethoxy) salicylic acid, 4-(3-p-
) lylsulfonylpropyloxy) salicylic acid, 5-(
3-p-)lylsulfonylprobyloxy) salicylic acid, 4-(4-p-tolylsulfonylbutyloxy)salicylic acid, 5-(4-p-)lylsulfonylbutyloxy)salicylic acid, 4-(5-p-) Lylsulfonylpentyloxy)salicylic acid, 5-(5-p-tolylsulfonylpentyloxy)salicylic acid, 4-(6-p-
tolylsulfonylhexyloxy) salicylic acid, 5-(
6-p-Tolylsulfonyhexyloxy) salicylic acid, 4-(8-P-Tolylsulfonyloctyloxy)
Salicylic acid, 5-(8-p-tolylsulfonyloctyloxy) salicyl 111F, 4-(10-p-)lylsulfonyldecyloxy) salicylic acid, 5-(10-p-
-) lylsulfonyldecyloxy) salicylic acid, 4-(
12-p-)lylsulfonyldodecyloxy)salicylic acid, 5-(12-p-)lylsulfonyldodecyloxy)salicylic acid, 4-(1B-p-tolylsulfonyloctadecyloxy)salicylic acid, 5-(1B-p-)lyl Sulfonyloctadecyloxy) salicylic acid, 4-(
1-Methyl-1-p-tolylsulfonylmethoxy)salicylic acid, 5-(1-methyl-1-p-)lylsulfonylmethoxy)salicylic acid, 4-(1,1-dimethyl-1-
p-)lylsulfonylmethoxy)salicylic acid, 5-(1
, 1-dimethyl-1-P-tolylsulfonylmethoxy)
Salicylic acid, 4-(5-p-tolylsulfonyl-3-oxapentyloxy)salicylic acid, 5-(5-p-)
Lylsulfonyl-3=oxapentyloxy) salicylic acid, 4-(8-P-tolylsulfonyl-3,6-thioxaoctyloxy) salicylic acid, 5-(8-p-
1-lylsulfonyl-3,6-thioxaoctyloxy)salicylic acid, 4-(11-p-)lylsulfonyl-3
,6,9-)trioxa-undecyloxy)salicylic acid, 5-(11-p-)solsulfonyl-3,6,9-trioxa-undecyloxy)salicylic acid, 4-(7
-p-Tolylsulfonyl-3,5-dioxa-hebutyloxy)salicylic acid, 5-(7-p-)lylsulfonyl-3゜5-dioxa-hebutyloxy)salicylic acid, 4
-(9-p-)trusulfonyl-5-oxanonyloxy)salicylic acid, 5-(9-p-tolylsulfonyl-
5-oxa-nonyloxy)salicylic acid, 4-(3-p
-)solsulfonyl-1-propenyloxy)salicylic acid, 5-(3-p-tolylsulfonyl-1-propenyloxy)salicylic acid, 4-(4-P-tolylsulfonyl-2-butenyloxy)salicylic acid, 5-(4- p-
) lylsulfonyl-2-butenyloxy) salicylic acid,
4-(2-phenyl-3-p-)lylsulfonylpropyloxy)salicylic acid, 5-(2-phenyl-3-p-
) Lylsulfonylprobyloxy) salicylic acid, 4-(
4-p-)Tolylsulfonylmethylbenzyloxy)salicylic acid, 5-(4-p-Tolylsulfonylmethylbenzyloxy)salicylic acid, 4-(3-p-Tolylsulfonylmethylbenzyloxy)salicylic acid, 5-(3-
p-)lylsulfonylmethylbenzyloxy)salicylic acid, 4-(4-p-)lylsulfonylphenoxy)salicylic acid, 5-(4-p-)lylsulfonylphenoxy)
Salicylic acid, 4-(3-p-tolylsulfonylphenoxy)salicylic acid, 5-(3-p-tolylsulfonylphenoxy)salicylic acid, 4-(2-cyclohexyl-
3-p-)lylsulfonylbrobyloxy)salicylic acid, 5-(2-cyclohexyl-3-p-)lylsulfonylbropyloxy)salicylic acid, 4-(4-p-tolylsulfonylcyclohexyloxy)salicylic acid, 5- (
4-p-)lylsulfonylcyclohexyloxy)salicylic acid, 4-(2-o-)lylsulfonylethoxy)salicylic acid, 5-(2-o-)lylsulfonylethoxy)
Salicylic acid, 4-(2-m-tolylsulfonylethoxy)salicylic acid, 5-(2-m-tolylsulfonylethoxy)salicylic acid, 4-(2-p-ethylphenylsulfonylethoxy)salicylic acid, 5-(2-p-ethyl phenylsulfonylethoxy) salicylic acid, 4-(2-p
-propylphenylsulfonylethoxy) salicylic acid,
5-(2-p-propylphenylsulfonylethoxy)
Salicylic acid, 4-(2-p-isopropylphenylsulfonyl ethoxy) salicylic acid, 5-(2-p-isopropylphenylsulfonyl ethoxy) salicylic acid, 4-(
2-p-hexylphenylsulfonylethoxy) salicylic acid, 5-(2-p-hexylphenylsulfonylethoxy) salicylic acid, 4-(2-p-methoxyphenylsulfonylethoxy) salicylic acid, 5-(2-p-methoxyphenylsulfonylethoxy) ) salicylic acid, 4-(2
-o-methoxyphenylsulfonylethoxy) salicylic acid, 5-(2-o-methoxyphenylsulfonylethoxy) salicylic M, 4-(2-m-methoxyphenylsulfonylethoxy) salicylic acid, 5-(2-m-methoxyphenylsulfonylethoxy) ) Salicylic acid, '4-(2
-p-Ethoxyphenylsulfonylethoxy) salicylic acid, 5- (2-p-ethoxyphenylsulfonylethoxy) salicylic acid, 4-(2-p-isopropyloxyphenylsulfonylethoxy) salicylic acid, 5- (2-p-ethoxyphenylsulfonylethoxy) salicylic acid,
-p-isopropyloxyphenylsulfonylethoxy) salicylic acid, 4-(2-P-butyloxyphenylsulfonylethoxy) salicylic acid, 5-(2-p-butyloxyphenylsulfonylethoxy) salicylic acid, 4
-(2-p-hexyloxyphenylsulfonylethoxy) salicylic acid, 5-(2-P-hexyloxyphenylsulfonylethoxy) salicylic acid, 4-(3-p-methoxyphenoxypropyloxy) salicylic acid, 5-(
3-p-methoxyphenoxypropyloxy) salicylic acid, 4- (3-p-isopropyloxyphenoxypropyloxy) salicylic acid, 5- (3-p-isopropyloxyphenoxypropyloxy) salicylic acid, 4
-(3-tert-butyloxyphenoxypropyloxy) salicylic acid, 5- (3-tert-butyloxyphenoxypropyloxy) salicylic acid, 4-(4-
P-methoxyphenoxybutyloxy) salicylic acid, 5
-(4-p-methoxyphenoxybutyloxy) salicylic acid, 4-(4-p-isopropyloxyphenoxybutyloxy) salicylic acid, 5-(4-p-isopropyloxyphenoxybutyloxy) salicylic acid, 4-(2
-p-biphenylsulfonylethoxy) salicyl Ml,
5-(2-P-biphenylsulfonylethoxy) salicyl M, 4-(2-o-biphenylsulfonylethoxy)
Salicylic acid, 5-(2-o-biphenylsulfonylethoxy) salicylic acid, 4-(2-m-biphenylsulfonylethoxy) salicylic acid, 5-(2-m-biphenylsulfonylethoxy) salicylic acid, 4-(2-p-phenoxyphenyl) sulfonylethoxy) salicylic acid, 5-(
2-p-phenoxyphenylsulfonylethoxy) salicylic acid, 4-(2-p-chlorophenylsulfonylethoxy) salicylic acid, 5-(2-p-chlorophenylsulfonylethoxy) salicylic acid, 4-(3-p-chlorophenylsulfonylpropyl) oxy) salicylic acid, 5-(
3-p-Chlorphenylsulfonylpropyloxy) salicylic acid, 4-(4-p-chlorophenylsulfonylbutoxy) salicylic acid) Ltta, 5-(4-p-chlorophenylsulfonylbutoxy) salicylic acid, 4-(2-o
-Chlorphenylsulfonylethoxy)salicyl L5-
(2-o-chlorophenylsulfonylethoxy) salicylic fa, 4-(2-p-promophenylsulfonylethoxy) salicylic acid, 5-(2-p-bromophenylsulfonylethoxy) salicylic acid, 4(2-p-fluorophenylsulfonyl) ethoxy) salicylic acid, 5-(2-p
-fluorophenylsulfonylethoxy) salicylic acid,
4-(2p-cyclohexylphenylsulfonylethoxy) salicylic acid, 5-(2-p-cyclohexylphenylsulfonylethoxy) salicylic 14-(2-P-allylphenylsulfonylethoxy) salicylic acid, 5-
(2-p-allylphenylsulfonylethoxy) salicylic acid, 4-(2-p-benzylphenylsulfonylethoxy) salicylic acid, 5(2-p-benzylphenylsulfonylethoxy) salicylic acid, 4-(2-p-methylthiophenylsulfonylethoxy) ) salicylic acid, 5-(2
-p-methylthiophenylsulfonylethoxy) salicylic acid, 4- (2-p-benzyloxyphenylsulfonylethoxy) salicylic acid, 5-(2-p-benzyloxyphenylsulfonylethoxy) salicylic acid, 4-
(2-p-phenethyloxyphenylsulfonylethoxy) salicylic acid, 5-(2-p-phenethyloxyphenylsulfonylethoxy) salicylic acid, 4-(2-p-
methyloxycarbonylphenylsulfonylethoxy)
Salicylic acid, 5-(2-p-methyloxycarbonylphenylsulfonylethoxy) salicylic acid, 4-(2-p
-acetylphenylsulfonylethoxy) salicylic acid,
5-(2-p-acetylphenylsulfonylethoxy)
Salicylic acid, 4-(2-p-benzoylphenylsulfonylethoxy) salicylic acid, 5-(2-p-benzoylphenylsulfonylethoxy) salicylic M, 4-(2-
p-acetyloxyphenylsulfonylethoxy) salicylic acid, 5-(2-p-acetyloxyphenylsulfonylethoxy) salicylic acid, 4-(2-p-nitrophenylsulfonylethoxy) salicylic acid, 5-(2-p-
Nitrophenylsulfonylethoxy) salicylic acid, 4-
(2-p-hydroxyphenylsulfonylethoxy)
Salicylic acid, 5-(2-p-hydroxyphenylsulfonyl ethoxy) salicylic acid, 4-(2-m-hydroxyphenylsulfonylethoxy) salicylic acid, 5(2-m
-hydroxyphenylsulfonyl ethoxy) salicylic acid, 4- (2-(3,5-dimethylphenylsulfonyl) ethoxy) salicylic acid, 5- (2-(3,5-dimethylphenylsulfonyl) ethoxy) salicylic acid, 4-
[2-(3,4,5-trimethylphenylsulfonyl)ethoxy]salicylic acid, 5-(2-(3,4,5-
Trimethylphenylsulfonyl)ethoxy]salicylic acid, 4-[2-(3,5-dichlorophenylsulfonyl)ethoxy]salicylic acid, 5-(2-(3,5-dichlorophenylsulfonyl)ethoxy)salicylic acid, 4-
(2-(3,4,5-trichlorophenylsulfonyl)ethoxy)salicylic acid, 5-[2-(3,4,5-)
dichlorophenylsulfonyl)ethoxy]salicylic acid,
4-(2-(3-chloro-4-methylphenylsulfonyl)ethoxy)salicylic acid, 5-(2-(3-chloro-4-methylphenylsulfonyl)ethoxy)salicylic acid, 4[2-(1-naphthylsulfonyl)] Ethoxy]
Salicylic acid, 5-[2-(1-naphthylsulfonyl)
ethoxy]su-11cylic acid, 4- (2-(4-methyl-
1-naphthylsulfonyl)ethoxy]salicylic acid, 5-
(2-(4-methyl-1-naphthylsulfonyl)ethoxy)salicylic acid, 4-[2(4-methoxy-1-naphthylsulfonyl)ethoxy]salicylic acid, 5-C2-(
4-methoxy1-naphthylsulfonyl)ethoxy]salicylic acid, 4-(2-(4-hensyloxy-l-naphthylsulfonyl)ethoxy)salicylic acid, 5-[2(4
-benzyloxy-1-naphthylsulfonyl)ethoxy]salicylic acid, 4-(2-(1-naphthylsulfonyl)ethoxy)salicylic acid, 5-(2-(1-naphthylsulfonyl)ethoxy)salicylic acid, 4-(2-(6) −
Methyl-2-naphthylsulfonyl)ethoxy]salicyl[5-[2-(6-methyl-2-naphthylsulfonyl)]
Ethoxy]salicylic acid, 4-[2-(6-medoxy-2-naphthylsulfonyl)ethoxy]salicylic acid, 5(
2-(6-medoxy-2-naphthylsulfonyl)ethoxy]salicylic acid, 4-(2-(6-benzyloxy-
2-naphthylsulfonyl)ethoxy]salicylic acid, 5-
C2-(6-benzyloxy-2-naphthylsulfonyl)ethoxy]salicylic acid, 4-(2-(2-pyridylsulfonyl)ethoxy)salicylic acid, 5-(2-(
2-pyridylsulfonyl)ethoxy]salicylic acid, 3-
Methyl-4-(2-p-tolylsulfonylethoxy)salicylic acid, 3-methyl-5-(2-p-)lylsulfonylethoxy)salicylic acid, 3,5-dimethyl-4-(2
-p-)lylsulfonylethoxy) salicylic acid, 3-cyclohexyl-4-(2-p-)lylsulfonylethoxy)salicylic acid, 3-allyl-4-(2-p-tolylsulfonylethoxy)salicylic acid, 3-α,α -dimethylbenzyl-4-(2-p-)lylsulfonylethoxy)
Salicylic acid, 3-phenyl-4-(2-p-tolylsulfonylethoxy) salicylic acid, 3-acetyloxy-4
-(2-p-tolylsulfonylethoxy)salicylic acid,
3-phenoxy-4-(2-p-)lylsulfonyl ethoxy) salicylic acid, 4-lyol-5-(2-p-)lylsulfonyl ethoxy) salicylic acid, 5-chloro-4-(
2-p-Tolylsulfonylethoxy) salicylic acid, 4-
Bromo-5-(2p-)lylsulfonylethoxy)salicylic acid, 5-bromo-4-(2-p-tolylsulfonylethoxy)salicylic acid, 3,5-dichloro-4-(2-
p-)lylsulfonylethoxy) salicylic acid, 3-methoxy-5-(2-p-'r-lylsulfonylethoxy)
salicylic acid, 5-nitro-4-(2-p-)lylsulfonylethoxy)salicylic acid, and the like.

Of course, the present invention is not limited to these salicylic acid derivatives and/or their polyvalent metal salts, and two or more kinds of compounds can be used in combination if necessary.

In the present invention, the amounts of the divinylphthalide derivative represented by the general formula [■] and the salicylic acid derivative represented by the general formula [II] and/or its polyvalent metal salt are not particularly limited. -Generally, 50 to 700 parts by weight, preferably 100 parts by weight of the salicylic acid derivative and/or its polyvalent metal salt per 100 parts by weight of the divinylphthalide derivative.
The amount is adjusted within a range of about 500 parts by weight.

In the present invention, by using a salicylic acid derivative represented by the general formula [II] and/or its polyvalent metal salt as a coloring agent, a heat-sensitive recording material having excellent color development properties and particularly excellent storage stability of recorded images can be obtained. However, these characteristics can be further improved by using a separate metal compound.

Such metal compounds include divalent, trivalent, or tetravalent metals such as zinc, magnesium, barium, calcium, aluminum, tin, titanium, nickel, cobalt,
Metal oxides and hydroxides selected from manganese, iron, etc.
sulfides, halides, carbonates, phosphates, silicates,
Examples include sulfates, nitrates, and halogen complex salts, and among these, zinc compounds are particularly preferred.

Specific examples of metal compounds include zinc oxide, zinc hydroxide, zinc aluminate, zinc sulfide, zinc carbonate, zinc phosphate, zinc silicate, aluminum oxide, magnesium oxide, titanium oxide, aluminum hydroxide, and silicate. Examples include aluminum acid, aluminum phosphate, magnesium aluminate, magnesium hydroxide, magnesium carbonate, magnesium phosphate, and the like. Of course, two or more of these metal compounds can also be used in combination.

The amount of the metal compound used is not necessarily limited, but is usually 1 to 500 parts by weight, preferably 1 to 100 parts by weight of the salicylic acid derivative represented by the general formula [II] and/or its polyvalent metal salt. It is desirable to adjust the amount within the range of about 5 to 300 parts by weight.

In the heat-sensitive recording material of the present invention, a specific divinylphthalide derivative and a specific salicylic acid derivative as described above are used in combination as a coloring agent, but if necessary, various known colorless or light-colored bases may be used. A color dye can be used in combination. Specific examples of such basic dyes include:
For example, the following are exemplified.

3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3.3-bis(p-dimethylaminophenyl)phthalide, 3-(4-dimethylaminophenyl)-3-(4-diethylamino -2-methylphenyl)-6-dimethylaminophthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-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-dimethyla5-nophthalide, 3.3-bis(9-ethylcarbazol-3-yl)-6-dimethylaminophthalide, 3.3-bis(2-phenylindol-3-yl)-6-dimethylaminophthalide 3-(p-dimethylaminophenyl)-3-(1-methylpyrrole-3-
yl)-6-dimethylaminophthalide, 3-(p-dibenzylaminophenyl)-3-(1,2-dimethylindol-3-yl)-7-azaphthalide, 3-(4-diethylamino-2- ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-7-azaphthalide, 3゜3-bis(1-ethyl-2-methylindol-3-yl)phthalide, N-butyl- 3-(screw)
Triarylmethane dyes such as 4-(N-methylanilino)phenylcomethyl)carbazole, 4゜4'-bis(dimethylamino)benzhydrylbenzyl ether,
N-halophenyl-leukoolamine, N-2,4,5
-) Diphenylmethane dyes such as dichlorophenyl leuco auramine, 4,4'-bis(dimethylamino)benzhydryl-p-toluenesulfinic acid ester, 3.
Thiazine dyes such as 7-bis(diethylamino)-10-benzoylphenoxazine, benzoylleucomethylene blue p-nitrobenzoylleucomethylene blue, 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3-phenylspirodinaphtho Piran,
3-benzylspirodinaphthopyran, 3-methylnaphtho(6'-methoxybenzo)spiropyran, 3-propylspirodibenzopyran, di-β-naphthospiropyran,
Spiro dyes such as 3-methyl-di-β-naphthospiropyran, lactam dyes such as rhodamine-B-anilinolactam, rhodamine (p-nitroanilino) lactam, rhodamine (0-chloroanilino) lactam, 3-diethylamino -6-methylfluorane, 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-6
-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-two-chlorofluorane, 3-diethylamino [no 6゜7-dimethylfluorane] Oran, 3-(N-ethyl-p-toluidino)-7-
Methylfluoran, 3-diethylamino-7-(N-acetyl-N-methylamino)fluoran, 3-diethylamino-7-N-methylamino)fluoran, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino -7-(N-methyl-N-benzyl 4)
) Fluoran, 3-diethylamino-7-(N-β-chloroethyl-N-methylac))fluoran, 3-diethylamino-7-diethylaminofluoran, 4-benzylamino-8-diethylaminobenzo(a) fluoran, 3- (4(4-dimethylaminoanilino)anilino]-7-chloro-6-methylfluorane, 8-C4-
(4-dimethylaminoanilino)anilinolactam (a
) Fluorane, 3-(N-ethyl-P-1-luidino)
-6-methyl-7-phenylaminofluorane, 3-(
N-ethyl-p-toluidino)6-methyl-7-(p-
) luidino) fluoran, 3-diethylamino-6-methyl-7-phenylaminofluoran, 3-diptylamino-6-methyl-7-phenylaminofluoran, 3
-dipentylamino-6-methyl-7-phenylaminofluorane, 3-diethylamino-7-(2-carbomethoxy-phenylamino)fluoran, 3-(N-ethyl-N-isoamylamino)-6-methyl-7 -phenylaminofluorane, 3-(N-cyclohexyl-N-
(Methylamino)-6-methyl-7-phenylaminofluorane, 3-pyrrolidino-6-methyl-7-phenylaminofluorane, 3-piperidino-6-methyl-7-phenylaminofluorane, 3-diethylaminofluorane 6 -Methyl-7-xylidinofluorane, 3-diethylamino-7-(o-chlorophenylamino)fluoran, 3-
Dibutylamino-7-(0-chlorophenolago))fluorane, 3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-phenylaminofluorane, 3-(N-methyl-N -propylamino)-6-
Methyl-7-phenylaminofluorane, 3-pyrrolidino-6-methyl-7-p-butylphenylaminofluorane 1.3-(N-ethyl-N-isobutylamino)-
6-Methyl-7-phenylaminofluorane, 3-(N
-Methyl-N-n-hexylamino)-6-methyl-7
-phenylaminofluorane, 3-(N-ethyl-N-
n-hexylamino)-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-N-cyclopentylamino)-6-methyl-7-phenylaminofluorane, 3-(N-(3-ethoxy propyl)-N-methylamino)-6-methyl-7-phenylagonofluorane,
3-[N-ethyl-N-(3-ethoxypropyl)aminoco-6-methyl-fuphenyla ξnofluorane, 3
-diethylamino-7-(m-(trifluoromethyl)
Phenylaminocofluorane, 3-diethylamino-7
-(0-fluorophenylamino))fluoran, 3-dibutylamino-7-(o-fluorophenylamino)fluoran, 3-diethylamino-6-chloro-7-phenylaminofluoran, 3-(N-ethyl- N-p-)
lylamino)-7-methylfluorane, 3-(N-ethyl-N-tetrahydrofurfuryl ξ))-6-methyl-7-anirithufluorane, 3-(N-cyclopentyl-N-ethyl fluorane))- 6-Methyl-7-anilitufluorane, 3-(N-ethyl-N-p-)lylamino)-
Fluoran dyes such as 6-methyl-7-anilite fluorane, 3,6-bis(dimethylamino)fluorene-9
-spiro-3'-(6'dimethyla[))phthalide,
3-diethylamino-6-(N-allyl-N-methylaminofluorene-9-spiro-3'-(6'-dimethylamino)phthalide, 3,6-bis(dimethylamino)
-spiro[fluorene-9,6'-6' H-chromeno(4,3-b)indole), 3,6-bis(dimethylago))-3'-methyl-spiro[fluorene-9,
6'-6'H-chromeno(4,3-b).

indole), 3,6-bis(diethylamino)-3'
Examples include fluorene dyes such as -methyl-spiro [fluorene-9,6'-6'H-chromeno(4,3-b)indole]. Of course, the dyes are not limited to these dyes, and it is also possible to use two or more dyes in combination.

In addition, when these basic dyes are used together with the divinylphthalide derivative represented by the general formula (1), 0.2 parts of the above general basic dyes are added to 1 part by weight of the divinylphthalide derivative. It is preferable to mix it in an amount of up to 20 parts by weight.

Further, in the heat-sensitive recording material of the present invention, various known coloring agents can be used in combination within a range that does not impede the desired effect. Specific examples of such known coloring agents include the following.

Benzoic acid, 4-tert-butylbenzoic acid, 4-chlorobenzoic acid, 4-nitrobenzoic acid, phthalic acid, gallic acid,
Salicylic acid, 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3.5
-diter t-butylsalicylic acid, 3-methyl-5
-Benzylsalicylic acid, 3-phenyl-5-(α, α-
Aromatic carboxylic acids such as dimethylbenzyl)salicylic acid, 3,5-di(α-methylbenzyl)salicylic acid, and 2-hydroxy-1-benzyl-3-naphthoic acid; 4,4'
Isopropylidene diphenol (bisphenol A),
4.4'-isopropylidene bis(2-chlorophenol), 4.4'-isopropylidene bis(2,6-dichlorophenol), 4.4'-isopropylidene bis(
2,6-dibromophenol), 4,4'-isopropylidene bis(2-methylphenol), 4,4'-isopropylidene bis(2,6-dimethylphenol),
4゜4'-isopropylidene bis(2tert-butylphenol), 4.4'-5ec-butylidene diphenol, 2.2'-bis(4-hydroxyphenyl)-4
-Methylpentane, 4,4'-cyclohexylidenebisphenol, 4,4'-cyclohexylidenebis(2-
methylphenol), 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, α-naphthol, β-naphthol, methyl-4-
Hydroxybenzoate, benzyl-4-hydroxybenzoate, 2,2'-thiobis(4,6-dichlorophenol), 4-tert-octylcatechol, 2
．． 2'-methylenebis(4-chlorophenol), 2.
2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-dihydroxydiphenyl, methyl-bis(4-hydroxyphenyl)acetate, ethyl-bis(4-hydroxyphenyl)acetate, benzyl-bis (4-hydroxyphenyl)acetate, 4,4'(p-phenylenediisopropylidene)
Dipheno-71/, 4.4'-(m-phenylene diisopropylidene) diphenol, 4-hydroxydiphenylsulfone, 4.4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-methyl-diphenylsulfone, 4- Hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy-3'4'-tetramethylene diphenyl sulfone, 2,2'-diallyl-4,
A phenolic compound such as 4'-dihydroxydiphenylsulfone; one or more organic coloring agents such as phenolic resins such as p-phenylphenol-formalin resin and p-butylphenol-acetylene resin; and further, these organic coloring agents. and salts with polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, and nickel; metal complex compounds such as antipyrine complexes of zinc thiocyanate, and the like.

Furthermore, in the heat-sensitive recording material of the present invention, various thermofusible substances can be used as a recording sensitivity improver in order to obtain high-speed recording performance. Such thermofusible substances include, for example, caproic acid amide, capric acid amide, balmitic acid amide, stearic acid amide, oleic acid amide, erucic acid amide, linoleic acid amide, linoleic acid amide, N-methylstearic acid amide, and stearic acid amide. Acid anilide, N-methyloleic acid anilide, benzanilide, linoleic acid anilide, N-ethyl capric acid amide, N-
Butyllauric acid amide, N-octadecyl acetamide, N-oleicacetamide, N-oleylbenzamide, N-stearylcyclohexylamide, polyethylene glycol, 1-benzyloxynaphthalene, 2-
Benzyloxynaphthalene, 1-hydroxynaphthoic acid phenyl ester, 1,2-diphenoxyethane, 1°4-diphenoxybutane, 1,2-bis(3-methylphenoxy)ethane, 1,2-bis(4-methoxy) phenoxy)ethane, 1-phenoxy-2-(4-chlorophenoxy)ethane, 1-phenoxy-2-(4-methoxyphenoxy)ethane, 1-(2-methylphenoxy)-
2-(4-methoxyphenoxy)ethane, terephthalic acid dibenzyl ester, oxalic acid dibenzyl ester, oxalic acid di(4-methylbenzyl) ester, p-benzyloxybenzoic acid benzyl ester, p-benzylbiphenyl, 1.5 -bis(p-methoxyphenoxy)-3
-oxa-pentane, 1,4 bis(2-vinyloxyethoxy)benzene, p-biphenyl P-)lyl ether,
Examples include compounds such as benzyl-p-methylthiophenyl ether.

Preparation of coating liquids containing these generally uses water as a dispersion medium,
ball mill, attritor, vertical or horizontal sand mill,
It is prepared by dispersing the dye, coloring agent, and thermofusible substance together or separately using a stirring/pulverizing machine such as a colloid mill.

Such coating liquids usually contain starches and binders as binders.
Hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, gum arabic, polyvinyl alcohol, styrene/maleic anhydride copolymer salt, styrene/acrylic acid copolymer salt, styrene/butadiene copolymer emulsion, etc. have a total solid content. It is blended in an amount of about 10 to 40% by weight, preferably about 15 to 30% by weight.

Furthermore, various auxiliary agents can be added to the coating liquid.
For example, dispersants such as dioctyl sulfosuccinate sodium salt, dodecylbenzenesulfonate sodium salt, lauryl alcohol sulfate sodium salt, fatty acid metal salts, ultraviolet absorbers such as triazole type, other antifoaming agents, fluorescent dyes, Examples include colored dyes.

In addition, to prevent sticking of the heat-sensitive recording material due to contact with recording equipment or recording heads, stearate wax, polyethylene wax, carnauba wax, microcrystalline wax, carboxy-modified paraffin wax, zinc stearate, calcium stearate, etc. are dispersed. Liquids, emulsions, etc. can also be added.

In addition, inorganic pigments such as kaolin, clay, talc, calcium carbonate, magnesium carbonate, bottom clay, titanium oxide, diatomaceous earth, fine particulate anhydrous silica, activated clay, and styrene microballs are used to improve dust adhesion to the recording head. , nylon powder polyethylene powder, urea/formalin resin filler, raw starch granules, and other organic pigments can also be added.

The support is manufactured by coating on a suitable support such as paper, plastic film, laminated paper, base paper, woven fabric sheet, molded product, etc. Further, the amount of the coating liquid forming the recording layer applied to the support is not particularly limited, and is usually 2 to 12 g/rrf, preferably 3 to 10 g/rrf in terms of dry weight.
It is adjusted within a range of degrees.

Note that it is also possible to provide an overcoat layer on the recording layer for the purpose of protecting the recording layer or imparting writing suitability, etc. It is also possible to provide a protective layer on the back side of the support, or to provide an undercoat layer on the support. Of course, it is also possible to provide a support, and various known techniques in the field of heat-sensitive recording material production, such as applying an adhesive to the back surface of the support, can be added.

"Example" The present invention will be described in more detail with reference to Examples below, but the present invention is of course not limited to these.

Further, unless otherwise specified, parts and percentages in the examples indicate parts by weight and percentages by weight, respectively.

Example 1 ■ Preparation of liquid A 3.3-bis[1-(4-methoxyphenyl) ■-(4
-dimethylagonophenyl)ethylene-2-yl)-4
,5,6,7-titrachlorophthalide
10 parts methylcellulose 5% aqueous solution
5 parts water
40 parts of this composition was sand milled to an average particle size of 3.
It was ground to μm.

■ Preparation of Solution B 4-(3-p-)lylsulfonylbrobyloxy)salicylic acid 20 parts Zinc oxide
20 parts methylcellulose 5% aqueous solution 5 parts water
55 parts of this composition was ground in a sand mill to an average particle size of 3 μm.

■ Liquid C 1.2-bis(3-methylphenoxy)ethane 20 parts Methyl cellulose 5% aqueous solution 5 parts water
55 parts and 20 pairs of powder were ground in a sand mill to an average particle size of 3 μm.

■ Formation of recording layer 55 parts of liquid A, 100 parts of liquid B, 80 parts of liquid C, 15 parts of silicon oxide pigment (oil absorption: 180 m1/100 g), and 50 parts of 20% oxidized starch aqueous solution were mixed and stirred to form a heat-sensitive recording layer. A coating liquid was obtained. The obtained coating liquid was applied onto a 50 g/rrf base paper so that the dry weight was 6 g/m'' and dried to obtain a heat-sensitive recording paper.

Example 2 In the preparation of Solution B of Example 1, 4-(3-p-tolylsulfonylpropyloxy)salicylic acid was replaced with 4-
A thermosensitive recording paper was obtained in the same manner as in Example 1 except that (3-p-methoxybenzenesulfonylpropyloxy) salicylic acid was used.

Example 3 In the preparation of Example 10B solution, zinc salt of 4-(3-p-tolylsulfonylpropyloxy) salicylic acid was used instead of 20 parts of 4-(3-p-tolylsulfonylpropyloxy) salicylic acid and 20 parts of zinc oxide. A thermosensitive recording paper was obtained in the same manner as in Example 1 except that 20 parts of water and 20 parts of water were used.

Examples 4 to 5 In the preparation of solution A of Example 1, 3.3-bis[1-(4
-methoxyphenyl)-1-(4-dimethylaminophenyl)ethylene-2-yl)-4゜5.6.7-Other than using the following compound instead of 7-titrachlorophthalide,
Two types of thermal recording paper were obtained in the same manner as in Example 1.

Example 4; 3,3-bis[1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-titrachlorophthalide Example 5 ;3,3-bis[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide Example 6 ■ Preparation of solution D 3-dibutylamino- 6-Methyl-7-phenylated fluorane 10 parts Methylcellulose 5% aqueous solution 5 parts water
40 parts of this composition was ground in a sand mill to an average particle size of 3 μm.

■ Formation of recording layer 22 parts of liquid A, 80 parts of liquid B, 80 parts of liquid C, 55 parts of liquid D, 15 parts of silicon oxide pigment (oil absorption 180 m1/100 g), 50 parts of 20% oxidized starch aqueous solution, and 10 parts of water. A coating liquid for a heat-sensitive recording layer was obtained by mixing and stirring. 50g/of the obtained coating liquid
It was coated onto n-r base paper to a dry weight of 6 g/m'' and dried to obtain thermal recording paper.

Example 7 In the preparation of Solution B of Example 6, 4-(3-p-tolylsulfonylpropyloxy)salicylic acid was replaced with 4-
A thermosensitive recording paper was obtained in the same manner as in Example 6 except that (3-p-methoxybenzenesulfonylpropyloxy) salicylic acid was used.

Example 8 In preparing Solution B of Example 6, 4-(3-p-tolylsulfonylpropyloxy) salicylic acid was used instead of 20 parts of 4-(3-p-tolylsulfonylpropyloxy) salicylic acid and 20 parts of zinc oxide. A thermosensitive recording paper was obtained in the same manner as in Example 6 except that 20 parts of zinc salt and 20 parts of water were used.

Examples 9 to 10 In preparing solution A of Example 6, 3.3-bis[1-(4
-Methoxyphenyl)-1-(4-dimethylaminophenyl)ethylene-2-yl)-4゜5.6.7-Processed in the same manner as in Example 6, except that the following compound was used in place of 7-titrachlorophthalide. Two types of thermal recording paper were obtained.

Example 9; 3.3-bis(1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-titrachlorophthalide Example 10 ;3.3-bis[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide Comparative Examples 1 to 2 In the Bfili product of Example 1 , 2 types of heat-sensitive cells were prepared in the same manner as in Example 1, except that 20 parts of the following compound and 20 parts of water were used instead of 20 parts of 4-(3-p-tolylsulfonylpropyloxy)salicylic acid and 20 parts of zinc oxide. I got the recording paper.

Comparative Example 1: 4,4'-isopropylidene diphenol Comparative Example 2: Zinc salt of p-nitrobenzoic acid The following quality tests were conducted on the 12 types of thermal recording paper thus obtained, and the results were summarized as It is listed in the table.

[Color development in near-infrared region]

Printed with a heat-sensitive mini fax tester (manufactured by NTT Corporation, MP continuous printing tester), measured the recorded image and the reflectance (%) of the background part with a spectrophotometer at a wavelength of 830□, and then printed it on a PC.
Five values were calculated. Note that the PC3 value is the value at 830□.

As one of the indicators indicating the recording density of the recorded image, the above
Although the PCS value is described, the PC3 value is calculated using the following formula.

Reflectance before color development - Reflectance PC3 value after color development = Reflectance before color development The PC5 value required for a recorded image varies depending on the type of optical character reading device used, so it cannot be determined generally. , approximately in the range of 0.7 to 1.0, preferably in the range of 0.75 to 1.0 at the reading wavelength.

[Light resistance in near-infrared region]

After the recording paper obtained in the color development test was exposed to sunlight for 56 hours, the PC3 value was measured and calculated in the same manner as above.
The results are listed in Table 1.

[Plasticizer resistance in near-infrared region]

The recording paper obtained in the color development test was stacked on a vinyl chloride film and left to stand at room temperature for 20 hours, and then the PC5 value was measured and calculated in the same manner as above, and the results are listed in Table 1.

[Solvent resistance in near-infrared region]

Apply ethanol and cottonseed oil to the colored surface of the recording paper obtained in the color development test, and measure the PC3 value in the same manner as above.
The calculations were made and the results are listed in Table 1.

"Effect" As is clear from the results in Table 1, all of the heat-sensitive recording bodies of the present invention are excellent recording bodies that have optical readability in the near-infrared region, and the recorded images obtained have light resistance. It was a heat-sensitive recording material with extremely excellent plasticizer resistance and chemical resistance, and a high commercial value.

Table 1

Claims (2)

[Claims] (1) A colorless or light-colored basic dye on the support,
In a heat-sensitive recording material provided with a recording layer containing a coloring agent capable of coloring upon contact with the basic dye, a phthalide derivative represented by the general formula [I] is added as a basic dye in the recording layer. 1. A heat-sensitive recording material comprising at least one salicylic acid derivative represented by the following general formula [II] or a polyvalent metal salt thereof as a coloring agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼d [I] [In the formula, R_1 to R_1_0 are each a hydrogen atom; a halogen atom; a nitro group; an optionally substituted saturated or unsaturated alkyl group: an optionally substituted Cycloalkyl group; optionally substituted alkoxyl group; optionally substituted acyloxy group; optionally substituted aryl group; optionally substituted aralkyl group; optionally substituted phenoxy group; optionally substituted thio Alkoxyl group; or amino group ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (R_1_2, R_1_3
each a hydrogen atom; an optionally substituted saturated or unsaturated alkyl group; an optionally substituted cycloalkyl group; an optionally substituted aryl group; an optionally substituted aralkyl group; a tetrahydrofurfuryl group or a substituted acyl group, which may form a heterocycle with each other or with adjacent benzene rings. ), and R_1_1 represents a hydrogen atom or a lower alkyl group. Although a, b, c, and d represent carbon atoms, one or two of them may be nitrogen atoms. A hydrogen atom; a halogen atom; an alkyl group; an alkoxyl group; an optionally substituted amino group; or a nitro group may be bonded to the carbon atom as a substituent, and a-b,
The b-c or c-d bonds may form other aromatic rings. ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, Ar is a phenyl group that may have a substituent, a naphthyl group that may have a substituent, or a naphthyl group that may have a substituent. R is a branched or linear alkylene group which may have an ether bond, an ester bond, an amide bond or an unsaturated bond, and may have an ether bond, an ester bond or an amide bond. Indicates a cycloalkylene group, an aralkylene group that may have an ether bond, an ester bond, or an amide bond, or an arylene group. Further, X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxyl group, an aryloxy group, a nitro group, or a halogen atom, and m represents an integer of 1 to 3. ] (2) The heat-sensitive recording material according to claim (1), wherein at least one salicylic acid derivative represented by the general formula [II] or a polyvalent metal salt thereof and a metal compound are used in combination as a coloring agent.