JPH0473185A - Recording material - Google Patents

Abstract

PURPOSE:To contrive the improvement of color producing ability and material and recording image preservability by using at least either salicylic acid derivative or its polyvalent metal salt specified as a developer. CONSTITUTION:In a recording material using a reaction between a colorless or monochromatic basic dye and a developer, at least either salicylic acid derivative or its polyvalent metal salt represented by the formula I is used as a developer. In the formula I, R is alkyl group, alkenyl group, cycloalkyl group, phenyl group or naphthyl group, all of which may have substituent, X is alkylene group which may have substituent, Y is alkyl group, cycloalkyl group, alkenyl group, aralkyl group, alkoxyl group, phenyl group, naphthyl group, phenoxy group, nitro group or halogen atom and m is zero or integer of 1-3.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a recording material, and particularly to a recording material that is excellent in color development, shelf life, and preservation of recorded images.

``Prior Art'' There are various types of recording materials that utilize a color reaction between a colorless or light-colored basic dye and an organic or inorganic coloring agent, with typical examples being pressure-sensitive recording materials, heat-sensitive recording materials, and electrically conductive heat-sensitive recording materials. are known.

These recording materials are required to have performances such as sufficient recording density and recording sensitivity, and excellent preservation of recorded images in external environments such as heat, humidity, light, and chemicals. However, at present, nothing that completely satisfies these requirements has been obtained.

-For example, thermal recording media has been diversified in its application fields and forms, along with recent remarkable advances in thermal recording methods.
It can be used not only as a recording medium for thermal facsimiles and thermal printers, but also as a POS (Point of 5ales).
Its use in new applications such as Rahel is also rapidly increasing. However, heat-sensitive recording materials generally have drawbacks such as fogging due to the influence of solvents and the like, and recorded images having varying colors. In particular, if it comes into contact with plastic film, the recorded image will fade significantly, or if it is stored in contact with diazo copy paper, especially diazo copy paper immediately after copying, it may have defects such as the Capri phenomenon being extremely likely to occur. Currently, there is a strong need for improvement.

``Problems to be Solved by the Invention'' In view of the current situation, the present inventors have particularly aimed at improving the above-mentioned defects found in recording materials that utilize the coloring reaction between basic dyes and coloring agents. The field of coloring agents was extensively studied. As a result, when at least one of the salicylic acid derivatives represented by the general formula (1) or its polyvalent metal salts is used as a coloring agent, it is possible to obtain records that are extremely excellent not only in color development and shelf life but also in the preservation of recorded images. They discovered that a material can be obtained and completed the present invention.

"Means for Solving the Problems" The present invention provides a recording material using a reaction between a colorless or light-colored basic dye and a coloring agent, in which salicylic acid represented by the following general formula (1) is used as the coloring agent. This is a recording material characterized by using at least one kind of a derivative or a polyvalent metal salt thereof.

[In the formula, R is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, a cycloalkyl group that may have a substituent, a phenyl group that may have a substituent , or a naphthyl group which may have a substituent, and X represents an alkylene group which may be branched. In addition, Y is an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group,
Represents an alkoxyl group, phenyl group, naphthyl group, phenoxy group, nitro group, or halogen atom, m is O or 1
Indicates an integer between ~3. ] "Action" The salicylic acid derivative used in the present invention can be synthesized by a known method, for example, by alkylating the corresponding hydroxysalicylic acid derivative, carboxylating the corresponding phenol derivative, etc. .

In the salicylic acid derivative represented by the general formula (1) of the present invention, substituents for the alkyl group or alkenyl group represented by R include a 01-2o alkoxyl group, a 02-2° alkoxyalkoxyl group, a C2- 6 alkenyloxy group, 07-2° aralkyloxy group, C6-2° aryl group, C8-2° aryloxy group, 07-2°
Preferably, 2o's alkoxyalkoxyl group, furyl group, tetrahydrofuryl group, etc., and the aromatic ring contained in these substituents further includes a CI~6 alkyl group, a C7~1° aralkyl group, a CI~6 aralkyl group, and a CI~6 alkyl group. Alkoxyl group, 07-I0
may have a substituent such as an aralkyloxy group, a hydroxyl group, or a halogen atom.

Substituents for the phenyl group or naphthyl group represented by R include a 01-2° alkyl group, a C2-6 alkenyl group, a C6-16 aryl group, a C7-8. aralkyl group of CI~2°, alkoxyl group of CI~2°, hydroxyalkoxyl group of 01~2°, alkoxyalkoxyl group of 02~2°, alkenyloxy group of C2~6, 03~6
alkenyloxydialkoxyl group, 06-+6 aryloxy group, 07-2o aryloxydialkoxyl group, C7-2. Aralkyloxy group, 02-. An alkylcarbonyloxy group of 02-7, an alkoxycarbonyl group of 02-7, a hydroxyl group, a halogen atom, etc. are preferable, and the aromatic ring contained in these substituents is further alkyl group of 01-6, an alkoxyl group of 01-6, or a halogen atom. It may have a substituent such as an atom.

Furthermore, substituents for the cycloalkyl group represented by R include 01 to . alkyl group, 01-. An alkoxyl group, a halogen atom, etc. are preferable.

In addition, X represents an alkylene group that may be branched,
Among these, alkylene groups with CI to 11, which may be divided into different techniques, are preferred, and methylene groups and ethylene groups are particularly preferred.

Further, Y represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an alkoxyl group, a phenyl group, a naphthyl group, a phenoxy group, a nitro group, or a halogen atom, and among these, especially a C1-6 alkyl group ,
A 07-I00 aralkyl group, a C1-alkoxyl group, a phenyl group, a phenoxy group, a chlorine atom, a bromine atom, or a fluorine atom are more preferable.

The polyvalent metal that forms a salt with the salicylic acid derivative represented by the general formula (1) is more preferably a divalent, trivalent or tetravalent metal, such as zinc, calcium, aluminum, magnesium, tin, or iron; In particular, zinc is most preferred.

The recording material using the salicylic acid derivative or its polyvalent metal salt according to the present invention has sufficient color density and the color image is extremely stable, so it cannot be exposed to sunlight for a long time or stored in a high temperature or high humidity environment. This is extremely advantageous in terms of long-term preservation of records, as the recorded images will hardly change color even if the image is exposed.

In particular, when applied to heat-sensitive recording media, it eliminates the disadvantages of white paper areas becoming colored due to solvents, etc., and recorded images discoloring and fading due to oils, fats, chemicals, etc., and exhibits extremely excellent properties as a coloring agent. It is something.

Specific examples of the salicylic acid derivative represented by the general formula (1) include the following.

3-(phenoxycarbonylmethoxy)salicylic acid, 4
-(phenoxycarbonylmethoxy)salicylic acid, 5-
(Phenoxycarbonylmethoxy)Salicyl! , 3-(
2-phenoxycarbonylethoxy) salicylic acid, 4-
(2-phenoxycarbonylethoxy)salicylic acid, 5
-(2-phenoxycarbonylethoxy)salicylic acid,
3-(1-methyl-1-phenoxycarbonylmethoxy)
Salicylic acid, 4-(1-methyl-1-phenoxycarbonylmethoxy) salicylic acid, 5-(1-methyl-1-phenoxycarbonylmethoxy) salicylic acid, 3-(3-
Phenoxycarbonylpropoxy) salicylic acid, 4-(
3-phenoxycarbonylpropoxy) salicylic acid, 5
-(3-phenoxycarbonylpropoxy) salicylic acid, 3-(1-ethyl-1-phenoxycarbonylmethoxy) salicylic acid, 4-(1-ethyl-1-phenoxycarbonylmethoxy) salicylic acid, 5-(1-ethyl-1
-phenoxycarbonylmethoxy)salicylic acid, 4-(
4-phenoxycarbonylbutoxy) salicylic acid, 5-
(4-phenoxycarbonylbutoxy)salicylic acid, 4
-(1-propyl-1-phenoxycarbonylmethoxy) salicylic acid, 5-(l-propyl-1-phenoxycarbonylmethoxy) salicylic acid, 4-(5-phenoxycarbonylpentyloxy) salicylic acid, 5-(5-phenoxycarbonylpentyloxy) ) salicylic acid, 4-
(1-Butyl-1-phenoxycarbonylmethoxy) salicylic acid, 5-(1-butyl 1-phenoxycarbonylmethoxy) salicylic acid, 4-(7-phenoxycarbonyldecyloxy) salicylic acid, 5-(7-phethoxycarbonylhebutyl) oxy)salicylic acid, 4-CIO-phenoxycarbonyldecyloxy)salicylic acid, 5-(
10-phenoxycarbonyldecyloxy)salicylic acid, 4-(11-phenoxycarbonylundecyloxy)salicylic acid, 5-(11-phenoxycarbonylundecyloxy)salicylic acid, 4-'(o-tolyloxycarbonylmethoxy)salicylic acid, 4- (m-)lyloxycarbonylmethoxy)salicylic acid, 4-(p-tolyloxycarbonylmethoxy)salicylic acid, 5-(p-
tolyloxycarbonylmethoxy)salicylic acid, 4(2
-o-tolyloxycarbonylethoxy) salicylic acid,
4-(2-m-)lyloxycarbonylethoxy)salicylic acid, 4-(2-p-)lyloxycarbonylethoxy)salicylic acid, 5-(2-p-)lyloxycarbonylethoxy)salicylic acid, 4-(2-p-)lyloxycarbonylethoxy)salicylic acid, , 4-xylyloxycarbonylmethoxy) salicylic acid, 5-(2,4-xylyloxycarbonylmethoxy) salicylic acid, 4-(
2,6-xylyloxycarbonylmethoxy) salicylic acid, 4-(3,5-xylyloxycarbonylmethoxy) salicylic acid, 4- C2-(2゜4-xylyloxycarbonyl) ethoxy] salicylic acid, 5- (1- (2
, 4-xylyloxycarbonyl)ethoxy]salicylic acid, 4-(2-(2,6-xylyloxycarbonyl)
ethoxy]salicylic acid, 4- (2-(3,5-xylyloxycarbonyl)ethoxy]salicylic acid, 4- (
2゜3.6-)limethylphenoxycarbonylmethoxy)salicylic acid, 5-(2,3,6-1limethylphenoxycarbonylmethoxy)salicylic acid, 4-(2,3,
5-trimethylphenoxycarbonylmethoxy)salicylic acid, 4-(2-(2,3゜6-drimethylphenoxycarbonyl)ethoxy)salicylic acid, 5-(2-(
2,3,6-trimethylphenoxycarbonyl)ethoxy]salicylic acid, 4-(2-(2,3,5-trimethylphenoxycarbonyl)ethoxy)salicylic acid, 4-
(ptert-butylphenoxycarbonylmethoxy)
Salicylic acid, 5-(p-tert-butylphenoxycarbonylmethoxy) salicylic acid, 4-(2~Pter
t-Butylphenoxycarbonyl ethoxy) salicylic acid, 5-(2-P tert-butylphenoxycarbonyl ethoxy) salicylic acid, 4-(p-amylphenoxycarbonylmethoxy) salicylic acid, 4-(2-p-amylphenoxycarbonyl ethoxy) salicylic acid, 4 −
(p-isopropylphenoxyluponylmethoxy) salicylic acid, 4-(2-p-isopropylphenoxyluponylmethoxy) salicylic acid, 4-(p-tert-octylphenoxycarbonylmethoxy) salicylic acid, 4
-(P-pentadecylphenoxycarbonylmethoxy)
Salicylic acid, 4-(p-allylphenoxycarbonylmethoxy) salicylic acid, 5-(p-allylphenoxycarbonylmethoxy) salicylic acid, 4-(2-p-allylphenoxycarbonyl ethoxy) salicylic acid, 5-(2-p
-allylphenoxycarbonylethoxy) salicylic acid,
4(O-phenylphenoxycarbonylmethoxy) salicylic acid, 4-(m-phenylphenoxycarbonylmethoxy) salicylic acid, 4-(P-phenylphenoxycarbonylmethoxy) salicylic acid, 5-(p-phenylphenoxycarbonylmethoxy) salicylic acid, 4-( 2-o
-phenylphenoxycarbonylethoxy) salicylic acid, 4-(2-m-phenylphenoxycarbonylethoxy) salicylic acid, 4-(2-p-phenylphenoxycarbonylethoxy) salicylic acid, 5-(2-p-phenylphenoxycarbonylethoxy) salicylic acid, 4-
(2-(0-methoxyphenylphenoxy)carbonylmethoxy]salicylic acid, 4-(4-(p-methoxyphenyl)phenoxycarbonylmethoxy)salicylic acid, 5
-(4-(p-methoxyphenyl)phenoxycarbonylmethoxy)salicylic acid, 4(2[2-(o-methoxyphenyl)phenoxycarbonyl]ethoxy)salicylic acid, 4-(2-(4-(p-methoxyphenyl)phenoxy) Carbonylfethoxy)salicylic acid, 5-(2
-C4-(p-methoxyphenyl)phenoxycarbonylfethoxy)salicylic acid, 4-(4-(p-chlorophenyl)phenoxycarbonylmethoxy)salicylic acid,
5-[4(p-chlorophenyl)phenoxycarbonylmethoxy]salicylic acid, 4-(0-hensylphenoxycarbonylmethoxy)salicylic acid, 4-(p-benzylphenoxycarbonylmethoxy)salicylic acid, 5-(P-
benzylphenoxycarbonylmethoxy) salicylic acid,
4-(2-o-benzylphenoxycarbonylethoxy)salicylic acid, 4-(2-p-benzylphenoxycarbonylethoxy)salicylic acid, 5-(2-p-benzylphenoxycarbonylethoxy)salicylic acid, 4-
(p-cumylphenoxycarbonylmethoxy) salicylic acid, 4-(2-p-cumylphenoxycarbonyl ethoxy) salicylic acid, 4[4-(p-methoxycumyl)phenoxycarbonylmethoxy] salicylic acid, 5-(4-(
p-methoxycumyl) phenoxycarbonylmethoxy]
Salicylic acid, 4(2-(4-(p-methoxycumyl)phenoxycarbonyl]ethoxy)salicylic acid, 5-(2
(4-(p-methoxycumyl)phenoxycarbonyl)
ethoxy)salicylic acid, 4-(4-(pchlorobenzyl)phenoxycarbonylmethoxy)salicylic acid, 5-
(4-(p-chlorobenzyl)phenoxycarbonylmethoxy]salicylic acid, 4-(2-[4-(p-chlorobenzyl)phenoxycarbonyl]ethoxy) salicylic acid, 5-(2-(4-(p-chlorobenzyl)phenoxy) carbonyl]ethoxy)salicylic acid, 4-(o-methoxyphenoxycarbonylmethoxy)salicylic acid, 4-(
m-methoxyphenoxycarbonylmethoxy) salicylic acid, 4-(p-methoxyphenoxycarbonylmethoxy) salicylic acid, 5-(P methoxyphenoxycarbonylmethoxy) salicylic acid, 4-(2-o-methoxyphenoxycarbonylmethoxy) salicylic acid, 4-(2 -m-
methoxyphenoxycarbonylmethoxy) salicylic acid,
4-(2-p-methoxyphenoxycarbonylmethoxy) salicylic acid, 5-(2-p-methoxyphenoxycarbonylmethoxy) salicylic acid, 4-(2,6-dimethoxyphenoxycarbonylmethoxy) salicylic acid, 4-(
3,5-dimethoxyphenoxycarbonylmethoxy)salicylic acid, 5-(3,5-dimethoxyphenoxycarbonylmethoxy)salicylic acid, 4-(2-(2,6-dimethoxyphenoxycarbonyl)ethoxy)salicylic acid, 4-(2-(3) ,5-dimethoxyphenoxycarbonyl)ethoxy]salicylic acid, 5-[2-(3,5-dimethoxyphenoxycarbonyl)ethoxy]salicylic acid, 4-(3,4,5-)dimethoxyphenoxycarbonylmethoxy)salicylic acid, 5-(3 , 4,5-1-dimethoxyphenoxycarbonylmethoxy) salicylic acid,
4-(2-(3,4,5-)dimethoxyphenoxycarbonyl)ethoxy]salicylic acid, 5-(2-(3,4
゜5-trimethoxyphenoxycarbonyl)ethoxy]
Salicylic acid, 4-(o-ethoxyphenoxycarbonylmethoxy) salicylic acid, 5-(o-ethoxyphenoxycarbonylmethoxy) salicylic acid, 4-(2-o-ethoxyphenoxycarbonyl ethoxy) salicylic acid, 5-
(2-o-Ethoxyphenoxycarbonylethoxy) salicylic acid, 4-(p-isopropoxyphenoxycarbonylmethoxy) salicylic acid, 5-(p-isopropoxyphenoxycarbonylmethoxy) salicylic acid, 4-(
2-p-isopropoxyphenoxycarbonyl ethoxy) salicylic acid, 5-(2-p-isopropoxyphenoxycarbonyl ethoxy) salicylic acid, 4-(p-butoxyphenoxycarbonylmethoxy) salicylic acid, 5-(
p-Butoxyphenoxycarbonylmethoxy) salicylic acid, 4-(2-p-butoxyphenoxycarbonyl ethoxy) salicylic acid, 5-(2-p-butoxyphenoxycarbonyl ethoxy) salicylic acid, 4-(p-hexyloxyphenoxycarbonylmethoxy) salicylic acid , 4
-(2-p-hexyloxyphenoxycarbonyl ethoxy) salicylic acid, 4-(p-octyloxyphenoxycarbonylmethoxy) salicylic acid, 4-(2-p-octyloxyphenoxycarbonyl ethoxy) salicylic acid, 4(p-dodecyloxyphenoxy) carbonylmethoxy) salicylic acid, 4-(2-p-dodecyloxyphenoxycarbonylethoxy) salicylic acid, 4-(p-
octadecyloxyphenoxycarbonylmethoxy) salicylic acid, 4-(2-p-octadecyloxyphenoxycarbonyl ethoxy) salicylic acid, 4-(2-methoxy-4-methylphenoxycarbonylmethoxy) salicylic acid, 5-(2-methoxy-4-methylphenoxy) carbonylmethoxy) salicylic acid, 4- [2-(2-methoxy-4-methylphenoxycarbonyl)ethoxy] salicylic acid, 5- (2-(2-methoxy-4-methylphenoxycarbonyl) ethoxy) salicylic acid, 4-
4-(2-hydroxyethoxy)phenoxycarbonylmethoxy]salicylic acid, 5(4-(2-hydroxyethoxy)phenoxycarbonylmethoxy)salicylic acid, 4
- [4-(2-methoxyethoxy)phenoxycarbonylmethoxy]salicylic acid, 5- (4-(2-methoxyethoxy)phenoxycarbonylmethoxy)salicylic acid, 4- (2-(4-(2-methoxyethoxy)phenoxycarbonyl) ethoxy) salicylic acid, 5-[2-
[4-(2-methoxyethoxy)phenoxycarbonyl]ethoxy)salicylic acid, 4-(p-allyloxyphenoxycarbonylmethoxy)salicylic acid, 5-(p-
Allyloxyphenoxycarbonylmethoxy) salicylic acid, 4-(2-vinyloxyethoxy)phenoxycarbonylmethoxy] salicylic acid, 4-(m-phenoxyphenoxycarbonylmethoxy) salicylic acid, 4-(p
-phenoxyphenoxycarbonylmethoxy) salicylic acid, 5-(p-phenoxyphenoxycarbonylmethoxy) salicylic acid, 4(2-m-phenoxyphenoxycarbonyl ethoxy) salicylic acid, 4-(2-p-phenoxyphenoxycarbonyl ethoxy) salicylic acid, 5(
2-p-phenoxyphenoxycarbonyl ethoxy)salicylic acid, 4-C4-(p-)lyloxy(phenoxycarbonylmethoxy)salicylic acid, 5-(4-(p-tolyloxy)phenoxycarbonylmethoxy)salicylic acid, 4-(4-(p-)lyloxy(phenoxycarbonylmethoxy)salicylic acid, Methoxyphenoxy)phenoxycarbonylmethoxy]salicylic acid, 5-(4-(p-methoxyphenoxy)phenoxycarbonylmethoxy)salicylic acid, 4-C4-(p-chlorophenoxy)phenoxycarbonylmethoxy]salicylic acid, 5[4-(p-
Chlorophenoxy)phenoxycarbonylmethoxy]salicylic acid, 4- (4-(2phenoxyethoxy)phenoxycarbonylmethoxy)salicylic acid, 5- (4-
(2-phenoxyethoxy)phenoxycarbonylmethoxy]salicylic acid, f-(2-[4-(2-phenoxyethoxy)phenoxycarbonyl]ethoxy)salicylic acid, 5-(2-(4-(2-phenoxyethoxy)phenoxycarbonyl) ethoxy) salicylic acid, 4-C4-
(2-p-1-lyloxyethoxy)phenoxycarbonylmethoxy]salicylic acid, 5- (4-(2-p-)
lyloxyethoxy) phenoxycarbonylmethoxy]
Salicylic acid, 4-(2-C4-(2-p-tolyloxyethoxy)phenoxycarbonyl]ethoxy) salicylic acid, 5(2-(4-(2-P-)lyloxyethoxy)
phenoxycarbonyl]ethoxy)salicylic acid, 4-(
4-(2-p-methoxyphenoxyethoxy)phenoxycarbonylmethoxy]salicylic acid, 5-(4-(2
-p-methoxyphenoxyethoxy)phenoxycarbonylmethoxy]salicylic acid, 4- (2-[4-(2-
p-Methoxyphenoxyethoxy)phenoxycarbonyl]ethoxy)salicylic acid, 5-[2-(4-(2-
p-Methoxyphenoxyethoxy)phenoxycarbonyl]ethoxy)salicylic acid, 4-(4-(2-p-chlorophenoxyethoxy)phenoxycarbonylmethoxy)salicylic acid, 5-(4-(2-p-chlorophenoxyethoxy)phenoxycarbonylmethoxy) ] Salicylic acid, 4-(2-(4-(2-pchlorophenoxyethoxy)phenoxycarbonyl]ethoxy)salicylic acid, 5
-(2-(4(2-p-chlorophenoxyethoxy)phenoxycarbonyl]ethoxy)salicylic acid, 4-(.

Benzyloxyphenoxycarbonylmethoxy) salicylic acid, 4-(P-benzyloxyphenoxycarbonylmethoxy) salicylic acid, 5-(p-benzyloxyphenoxycarbonylmethoxy) salicylic acid, 4-(2-o
-hensyloxyphenoxycarbonylethoxy)salicylic acid, 4-(2-p-benzyloxyphenoxycarbonylethoxy)salicylic acid, 5-(2-p-benzyloxyphenoxycarbonylethoxy)salicylic acid, 4
- (4-(p-methylhensyloxy)phenoxycarbonylmethoxy)salicylic acid, 5-[4-(p-methylbenzyloxy)phenoxycarbonylmethoxy]salicylic acid, 4-(2-(4(p-methylbenzyloxy) phenoxycarbonyl]ethoxy)salicylic acid, 5
- (2-(4(P-methylhensyloxy)phenoxycarbonylfethoxy)salicylic acid, 4-(4-(p
methoxybenzyloxy)phenoxycarbonylmethoxy]salicylic acid, 5-[4-(p-methoxyhensyloxy)phenoxycarbonylmethoxy]salicylic acid, 4
- (2-C4-(p-methoxybenzyloxy)phenoxycarbonylfethoxy)salicylic acid, 5- (2
-(4-(p-methoxybenzyloxy)phenoxycarbonylfethoxy)salicylic acid, 4-[4-(p-chlorohensyloxy)phenoxycarbonylmethoxy]
Salicylic acid, 5-(4-(p-chlorobenzyloxy)
phenoxycarbonylmethoxy]salicylic acid, 4-(
2-[4-(p-chlorohensyloxy)phenoxycarbonylfethoxy)salicylic acid, 5-(1(4-C
T)-chlorobenzyloxy)phenoxycarbonyl]
ethoxy) salicylic acid, 4-(p-acetoxyphenoxycarbonylmethoxy) salicylic acid, 5-(p-acetoxyphenoxycarbonylmethoxy) salicylic acid, 4(
2-p-acetoxyphenoxycarbonylethoxy) salicylic acid, 5-(2-p-acetoxyphenoxycarbonylethoxy) salicylic acid, 4(P-methoxycarbonylphenoxycarbonylmethoxy) salicylic acid, 5-(
p-methoxycarbonylphenoxycarbonylmethoxy) salicylic acid, 4-(2-p-methoxycarbonylphenoxycarbonyl ethoxy) salicylic acid, 5-(2p-
methoxycarbonylphenoxycarbonylethoxy) salicylic acid, 4-(o-hydroxyphenoxycarbonylmethoxy) salicylic acid, 4-(m-hydroxyphenoxycarbonylmethoxy) salicylic acid, 4-(p-hydroxyphenoxycarbonylmethoxy) salicylic acid, 5-
(P-hydroxyphenoxycarbonylmethoxy) salicylic acid, 4-(2-o-hydroxyphenoxycarbonyl ethoxy) salicylic acid, 4-(2-m-hydroxyphenoxycarbonyl ethoxy) salicylic acid, 4-(2-
p-hydroxyphenoxycarbonyl ethoxy) salicylic acid, 5-(2-p-I=F'roxyphenoxycarbonyl ethoxy) salicylic acid, 4-(o-chlorophenoxycarbonylmethoxy) salicylic acid, 4-(m-chlorophenoxycarbonyl methoxy) ) salicylic acid, 4-(p
-chlorophenoxycarbonylmethoxy)salicylic acid,
5-(p-chlorophenoxycarbonylmethoxy) salicylic acid, 4-(2-o-chlorophenoxycarbonyl ethoxy) salicylic acid, 4-(2-m chlorophenoxycarbonyl ethoxy) salicylic acid, 4-(2-p-chlorophenoxy carbonyl ethoxy) ) salicylic acid, 5-(
2-p-chlorophenoxycarbonyl-ethoxy) salicylic acid, 4-(4-o-chlorophenoxycarbonylbutoxy) salicylic acid, 5-(4-o-chlorophenoxycarbonylbutoxy) salicylic acid, 4-(2,4-dichlorophenoxycarbonylmethoxy) Salicylic acid, 5-(2
,4-dichlorophenoxycarbonylmethoxy)salicylic acid, 4-(2,5-dichlorophenoxycarbonylmethoxy)salicylic acid, 4-(2,6-dichlorophenoxycarbonylmethoxy)salicylic acid, 4-(2-
(2,4-dichlorophenoxycarbonyl)ethoxy]
Salicylic acid, 5-[2-(24-dichlorophenoxycarbonyl)ethoxy]salicylic acid, 4-(2-(2,5
-dichlorophenoxycarbonyl)ethoxy]salicylic acid, 4-C2-(2,6-dichlorophenoxycarbonyl)ethoxy]salicylic acid, 4-(2,4,6-dichlorophenoxycarbonylmethoxy)salicylic acid, 5
- (2,4,6 trichlorophenoxycarbonylmethoxy) salicylic acid, 4- (2-(2,4,6-1-dichlorophenoxycarbonyl)ethoxy) salicylic acid,
5(2-(2,4,6-)dichlorophenoxycarbonyl)ethoxy]salicylic acid, 3-(hexyloxycarbonylmethoxy)salicylic acid, 4-(hexyloxycarbonylmethoxy)salicylic acid, 5-(hexyloxycarbonylmethoxy)salicylic acid, 4-(2-octyloxycarbonylethoxy) salicylic acid, 4-(dodecyloxycarbonylmethoxy) salicylic acid, 5-(dodecyloxycarbonylmethoxy) salicylic acid, 4-(tetradecyloxycarbonylmethoxy) salicylic acid, 4-
(2-pentadecyloxycarbonylethoxy) salicylic acid, 5-(2-pentadecyloxycarbonylethoxy) salicylic acid, 4(octadecyloxycarbonylmethoxy) salicylic acid, 4-(3,7-dimethyl-2.6
-Octadenyloxycarbonylmethoxy)salicylic acid, 4-(9-octadecenyloxycarbonylmethoxy)salicylic acid, 5-(9-octadecenyloxycarbonylmethoxy)salicylic acid, 4(3-oxapentyloxycarbonylmethoxy) Salicylic acid, 5-(3-oxapentyloxycarbonylmethoxy) salicylic acid, 4
-(3-oxapentadecyloxycarbonylmethoxy)salicylic acid, 5-(3-oxapentadecyloxycarbonylmethoxy)salicylic acid, 4-(3,6dioxaoctyloxycarbonylmethoxy)salicylic acid, 5-
(3,6-Shioxaoctyloxycarbonylmethoxy) salicylic acid, 4-(2allyloxyethoxycarbonylmethoxy) salicylic acid, 5-(2-allyloxyethoxycarbonylmethoxy) salicylic acid, 3-(2-benzyloxyethoxycarbonylmethoxy) salicylic acid,
4-(2-benzyloxyethoxycarbonylmethoxy)salicylic acid, 4-(2-(2-benzyloxyethoxycarbonyl)ethoxy)salicylic acid, 5-(2-
Benzyloxyethoxycarbonylmethoxy) salicylic acid, 4-(2-phenethyloxyethoxycarbonylmethoxy) salicylic acid, 4- (2-(2-phenethyloxyethoxycarbonyl)ethoxy) salicylic acid, 5-
(2-phenethyloxyethoxycarbonylmethoxy)
Salicylic acid, 3-(benzyloxycarbonylmethoxy) salicylic acid, 4-(benzyloxycarbonylmethoxy) salicylic acid, 5-(hensyloxycarbonylmethoxy) salicylic acid, 4-(2-benzyloxycarbonyl ethoxy) salicylic acid, 5-(2- benzyloxycarbonylethoxy) salicylic acid, 4-(α-methylbenzyloxycarbonylmethoxy) salicylic acid, 3-(phenethyloxycarbonylmethoxy) salicylic acid, 4-
(phenethyloxycarbonylmethoxy) salicylic acid,
5-(phenethyloxycarbonylmethoxy)salicylic acid, 4-(2-phenethyloxycarbonylethoxy)
Salicylic acid, 5-(2-phenethyloxycarbonyl ethoxy) salicylic acid, 4-(diphenylmethoxycarbonylmethoxy) salicylic acid, 4-(triphenylmethoxycarbonylmethoxy) salicylic acid, 4-(α,α-dimethylphenethyloxycarbonylmethoxy) salicylic acid, 4-(α-ethylbenzyloxycarbonylmethoxy) salicylic acid, 4-(3-phenylpropoxycarbonylmethoxy) salicylic acid, 5-(3-phenylpropoxycarbonylmethoxy) salicylic acid, 4-(cumyloxycarbonylmethoxy) salicylic acid, 4-(2-cumyloxycarbonylethoxy)salicylic acid, 4-(α-
methylphenethyloxycarbonylmethoxy) salicylic acid, 4-(2-naphthylmethoxycarbonylmethoxy)
Salicylic acid, 5-(2-naphthylmethoxycarbonylmethoxy) salicylic acid, 4-(2-(2-naphthyl)ethoxycarbonylmethoxy) salicylic acid, 4-(1-naphthylmethoxycarbonylmethoxy) salicylic acid, 4-
(2-(1-naphthyl)ethoxycarbonylmethoxy)
Salicylic acid, 4-(o-methylbenzyloxycarbonylmethoxy) salicylic acid, 5-(o-methylhensyloxycarbonylmethoxy) salicylic acid, 3-(p-methylbenzyloxycarbonylmethoxy) salicylic acid, 4
-(ρ-Methylhensyloxycarbonylmethoxy) salicylic acid, 5-(p-methylbenzyloxycarbonylmethoxy) salicylic acid, 4-(p-isopropylbenzyloxycarbonylmethoxy) salicylic acid, 4-(p-
Methylphenethyloxycarbonylmethoxy) salicylic acid, 4-(p-benzylbenzyloxycarbonylmethoxy) salicylic acid, 4-(p-phenethylbenzyloxycarbonylmethoxy) salicylic acid, 3(p-methoxybenzyloxycarbonylmethoxy) salicylic acid, 4-
(P-methoxybenzyloxycarbonylmethoxy) salicylic acid, 5-(p-methoxybenzyloxycarbonylmethoxy) salicylic acid, 4-(3,4-dimethoxybenzyloxycarbonylmethoxy) salicylic acid, 4-(
P-Butoxybenzyloxycarbonylmethoxy) salicylic acid, 4-(p-methoxyphenethyloxycarbonylmethoxy) salicylic acid, 5-(p-methoxyphenethyloxycarbonylmethoxy) salicylic acid, 4-(3,4
-dimethoxyphenethyloxycarbonylmethoxy) salicylic acid, 4-(p-methoxyphenyl)butoxycarbonylmethoxy] salicylic acid, 4-(p-benzyloxybenzyloxycarbonylmethoxy) salicylic acid, 5-(p-benzyloxybenzyloxycarbonylmethoxy) ) Salicylic acid, 4-(p-phenethyloxybenzyloxycarbonylmethoxy) salicylic acid, 5-(P
-phenethyloxyhenzyloxycarbonylmethoxy) salicylic acid, 4-(o-hydroxyhensyloxycarbonylmethoxy) salicylic acid, 5-(o-hydroxyhensyloxycarbonylmethoxy) salicylic acid, 4-
(p-hydroxyhensyloxycarbonylmethoxy)
Salicylic acid, 4-(4-hydroxy 3-methoxybenzyloxycarbonylmethoxy) salicylic acid, 4-(o-
Chlorohensyloxycarbonylmethoxy) salicylic acid, 4-(p-chlorobenzyloxycarbonylmethoxy) salicylic acid, 5-(p-chlorobenzyloxycarbonylmethoxy) salicylic acid, 4-(cinnamyloxycarbonylmethoxy) salicylic acid, 5-(cinnamyloxycarbonylmethoxy) salicylic acid, miloxycarbonylmethoxy) salicylic acid, 4-(2-phenoxyethoxycarbonylmethoxy) salicylic acid, 4-
(2-(2-phenoxyethoxycarbonyl)ethoxy)salicylic acid, 5-(2phenoxyethoxycarbonylmethoxy)salicylic acid, 4-((1-methyl-2-phenoxyethoxy)carbonylmethoxy)salicylic acid, 4
(2-(1-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 4-[2-(2-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 5-C2
-(2-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 4-(2m-tolyloxyethoxycarbonylmethoxy)salicylic acid, 5-(2-m-tolyloxyethoxycarbonylmethoxy)salicylic acid, 4-(
2P-Tolyloxyethoxycarbonylmethoxy) salicylic acid, 5-(2-p-Tolyloxyethoxycarbonylmethoxy) salicylic acid, 4-[2(2-methyl-1-
naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 4-(2-p-cumylphenoxyethoxycarbonylmethoxy)salicylic acid, 4-(2-(2-p-cumylphenoxyethoxycarbonyl)ethoxy)salicylic acid, 5-(2- p-cumylphenoxyethoxycarbonylmethoxy) salicylic acid, 3-(2-p-methoxyphenoxyethoxycarbonylmethoxy) salicylic acid, 4
-(2-p-methoxyphenoxyethoxycarbonylmethoxy)salicylic acid, 4-[2-(2-p-methoxyphenoxyethoxycarbonyl)ethoxy]salicylic acid,
5-(2-p~methoxyphenoxyethoxylponylmethoxy)salicylic acid, 4-C2-(4-methoxy-
1-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 4-(2-p-henzyloxyphenoxyethoxycarbonylmethoxy)salicylic acid, 4-(2-(
2-p-Hensyloxyphenoxyethoxycarbonyl)ethoxy]salicylic acid, 5-(2-p-penzyloxyphenoxyethoxycarbonylmethoxy)salicylic acid, 4-(2-p-phenethyloxyphenoxyethoxycarbonylmethoxy) Salicylic acid, 5-(2-p-phenethyloxyphenoxyethoxycarbonylmethoxy) salicylic acid, 4-(2-p-hydroxyphenoxyethoxycarbonylmethoxy) salicylic acid, 4-[2-(
2-p-hydroxyphenoxyethoxycarbonyl)ethoxy]salicylic acid, 5-(2-p-hydroxyphenoxyethoxycarbonylmethoxy)salicylic acid, 4-
C2-(4-hydroxyl-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 4-(2-(2
-(4hydroxy-1-naphthyloxy)ethoxycarbonyl]ethoxy)salicylic acid, 5-C2-(4-hydroxy-1-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 4-[2-(5-hydroxy-1)
-Naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 5-C2-(6-hydroxy-1-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 4
- C2-(3-hydroxy-2-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 5-(1-(
6-hydroxy-2-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 4-C2-(7-hydroxy-2-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 4-(2-pchlorophenoxyethoxycarbonylmethoxy)salicylic acid, 4 -[2-(2-
p-chlorophenoxyethoxycarbonyl)ethoxy]
Salicylic acid, 5-(2-p-chlorophenoxyethoxycarbonylmethoxy) salicylic acid, 4-C2-(2,
4-dibromo-1-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 4-(2-(24-dichloro-1-naphthyloxy)ethoxycarbonylmethoxy)
Salicylic acid, l-[2-(1bromo-2-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid, 5-
C2-(6-furomo-2-naphthyloxy)ethoxycarbonylmethoxy]salicylic acid5. l[2-(4-chloro1-naphthyloxy)ethoxycarbonylmethoxy]
Salicylic acid, 5-(2-(4-chloro-2-naphthyloxy)ethoxycarbonylmethoxy) salicylic acid, 4-(
5-phenoxy-3-oxapentyloxycarbonylmethoxy) salicylic acid, 4-C2-(5-phenoxy-3-oxapentyloxycarbonyl)ethoxy] salicylic acid, 5-(5-phenoxy-3-oxapentyloxycarbonylmethoxy) Salicylic acid, 4 (furfuryloxycarbonylmethoxy) salicylic acid, 4- (
2-(furfuryloxycarbonyl)ethoxy]salicylic acid, 5-(furfuryloxycarbonylmethoxy)salicylic acid, 4-(tetrahydrofurfuryloxycarbonylmethoxy)salicylic acid, 5-(tetrahydrofurfuryloxycarbonylmethoxy)salicylic acid, 4-( cyclopentyloxycarbonylmethoxy) salicylic acid,
5-(cyclopentyloxycarbonylmethoxy)salicylic acid, 4-(cyclohexyloxycarbonylmethoxy)salicylic acid, 4-C2-(cyclohexyloxycarbonyl)ethoxy]salicylic acid, 5-(cyclohexyloxycarbonylmethoxy)salicylic acid, 3-methyl-5 -(phenoxycarbonylmethoxy)salicylic acid,
3.5-dimethyl-4-(phenoxycarbonylmethoxy)salicylic acid, 3-cyclohexyl-4-(phenoxycarbonylmethoxy)salicylic acid, 3-allyl-4-
(phenoxycarbonylmethoxy)salicylic acid, 3-cumyl-4-(phenoxycarbonylmethoxy)salicylic acid, 3-phenyl-4-(phenoxycarbonylmethoxy)salicylic acid, 3phenoxy-4-(phenoxycarbonylmethoxy)salicylic acid, 4-chloro-5 -(phenoxycarbonylmethoxy)salicylic acid, 5-chloro4
-(phenoxycarbonylmethoxy)salicylic acid, 3,
5-dichloro-4-(phenoxycarbonylmethoxy)
Salicylic acid, 3-methoxy-5 (phenoxycarbonylmethoxy) salicylic acid, and other salicylic acid derivatives and/or polyvalent metal salts thereof may be used in combination of two or more compounds, if necessary.

In the present invention, by using a salicylic acid derivative represented by the general formula CI) and/or its polyvalent metal salt as a coloring agent, a recording material with excellent color development and raw storage stability, especially storage stability of recorded images, can be obtained. However, these characteristics can be further improved by using a metal compound in combination.

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 aluminum silicate. , 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 to be used is not necessarily limited, but is usually 1 to 500 parts by weight, preferably 1 to 500 parts by weight, based on 100 parts by weight of the salicylic acid derivative represented by general formula (1) 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 recording material of the present invention, various known coloring agents other than those of the present invention, such as salicylic acid derivatives, phenol derivatives, phenol resins, and acid clay, can be used in combination within a range that does not impair the desired effect.

Specific examples of such known coloring agents include the following. Inorganic coloring agents such as acid clay, activated clay, acpal guide, bentonite, colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, calcined kaolin, talc; oxalic acid, maleic acid, tartaric acid,
Aliphatic carboxylic acids such as citric acid, succinic acid, and stearic acid; 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-tert-butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-5-(α,
α-dimethylbenzyl) salicylic acid) L12.3.5-di(α-methylbenzyl) salicylic acid, 2-hydroxy-
1-hensyl-3-naphthoic acid, 4-(2-p-methoxyphenoxyethoxy)salicylic acid, 4-(3-p-
Aromatic carboxylic acids such as (tolylsulfonylpropyloxy) salicylic acid; 4,4'-isopropylidene diphenol (bisphenol A), 4,4'-isopropylidene bis(2-chlorophenol), 44'-isopropylidene bis(2) , 6-dichlorophenol), 4.4
'-Isopropylidene bis(26-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(4hydroxyphenyl)-4-methylpentane, 44'-cyclohexylidenebisphenol, 44'-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(4methyl-6-
tert-butylphenol), 22'dihydroxydiphenyl, methyl-bis(4hydroxyphenyl)
Acetate, ethyl-bis(4-hydroxyphenyl)
Acetate, butyl-bis(4-hydroxyphenyl)
Acetate, benzyl-bis(4-hydroxyphenyl) acetate, 4.4'-(P-phenylene diisopropylidene) diphenol, 4.4'-(m-phenylene diisopropylidene) diphenol, 4-hydroxydiphenyl sulfone , 44'-dihydroxydiphenylsulfone, 4-hydroxy4'-methyl-diphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-3',4'-tetramethylenediphenylsulfone, 3.3' -diallyl-4,
4'-Dihydroxydiphenylsulfone, bis(4hydroxyphenyl)acetic acid-2-phenoxyethyl ester, p-hydroxy-N-(2-phenoxyethyl)henzensulfonamide, dimethyl 4-hydroxyphthalate, 1, 5-bis(4-hydroxyphenylthio)-3-
Oxa-penkune, 1,7-bis(4-hydroxyphenylthio)3,5-dioxa-hebutane, 1,8-bis(4-hydroxyphenylthio)-3,6-thioxaoctane, (4-hydroxy phenylthio)acetic acid-2-(
Phenolic compounds such as 4-hydroxyphenylthio)ethyl ester; p-phenylphenol-
One or more organic coloring agents such as formalin resin, phenolic resin such as p-butylphenol-acetylene resin;
aluminum, calcium, titanium, manganese, tin,
Salts with polyvalent metals such as nickel; metal complex compounds such as antipyrine complexes of zinc thiocyanate, etc.

In the recording material of the present invention, various colorless or light-colored basic dyes are known to be used in combination with the above-mentioned specific salicylic acid or its metal salt.
For example, the following are exemplified.

3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(4dimethylaminophenyl)-3-(4-diethylamino- 2-Methylphenyl)-6-(dimethylamino)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylami/phenyl)-3 -(2-methylindol-3yl)phthalide, 3,3-bis(1,2-dimethylindole-3
-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazol-3-yl) )-6-dimethylaminophthalide, 3
゜3-bis(2-phenylindol-3-yl)6-
Triarylmethane dyes such as dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1-methylpyrrol-3-yl)-6-dimethylaminophthalide, 4
．． 4'-bis-dimethylaminohenzhydrylhenzyl ether, N-halophenyl-leucoolamine, N-2
, 4゜Diphenylmethane dyes such as 5-trichlorophenylleucoauramine, 3,3-bis(1,1bis(4
-pyrrolidinophenyl)ethylene-2-yl)-4,5
, 6,7-titrabromophthalide, 3,3-bis(1-
(4-methoxyphenyl)1-(4-dimethylaminophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, 3,3-bis(1-(4-methoxyphenyl/l/ ) Divinyl phthalide dyes such as -1-(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, hendiyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, etc. thiazine dyes, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-
Spiro dyes such as phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho(6'-methoxyhenzo)spiropyran, 3-probyl-spirodihenzopyran, rhodamine B-anilinolactam, rhodamine Lactam dyes such as (P-nitroanilino)lactam and rhodamine (0-chloroanilino)lactam, 3-dimethylamino-7-medoxyfluorane, 3-diethylamino-6-medoxyfluorane, 3-diethylamino-7-med xifluorane, 3-
Diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3-(N-
Ethyl-P-toluidino)-7-methylfluorane, 3
-diethylamino-7-(N-acetyl-N-methylamino)fluorane, 3-diethylamino-7-N-methylaminofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-(N
-Methyl-N-benzylamino)fluoran, 3-diethylamino-7-(N-chloroethyl-N-methylamine)fluoran, 3-diethylamino-7-N-diethylaminofluorane, 4-hensylamino-8-diethylamino-benzo [a] Fluorane, 3-C4-(4-
dimethylaminoanilino)anilino]-7-chloro-6
-Methylfluorane, 8-(4-(4-dimethylaminoanilino)anilino)-benzo(a)fluorane, 3(
N-ethyl-p-)luidino)-6-methyltophenylaminofluorane, 3-(N-ethyl-p-)luidino)-6-methyl-7-(p-toluidino)fluorane,
3-diethylamino-6-methyl-7-phenylaminofluorane, 3-dibutylamino-6-methyl-7-phenylaminofluorane, 3-diethylamino-7-(2
-carbomethoxy-phenylamino)fluorane, 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-diethylamino-
6-methyl-7-xylidinofluorane, 3-diethylamino-7-(o-chlorophenylamino)fluoran,
3-dibutylamino-7-(0-chlorophenylamino)fluorane, 3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-phenylaminofluorane, 3-(N-methyl-N- n-propylamine) 6-methyl-7-phenylaminofluorane, 3(N
-ethyl-N-isobutylamino)-6methyl-7-phenylaminofluorane, 3-(N-methyl-N-n-
hexylamino)-6-methyl-7-phenylaminofluorane, 3-dipentylamino-6-methyl-7-phenylaminofluorane, 3-(N-(3-ethoxypropyl)N-methylaminoco-6-methyl- Phenylaminofluorane, 3-(N-ethyl-N-(3-
ethoxypropyl)aminoco-6-methylfuphenylaminofluorane, 3-diethylamino-7-[m-(
trifluoromethyl)phenylaminofluorane, 3-
Diethylamine-7 (o'-fluorophenylamino)
Fluoran, 3-dibutylamino-7-(O-fluorophenylamino)fluoran, 3-diethylamino-6
Chloro 7-phenylaminofluorane, 3-(N-ethyl-N-n-hexylamino)-6methyl-7-phenylaminofluorane, 3-(N-ethyl-N-cyclopentylamino)-6-methyl Fluorane dyes such as -7-phenylaminofluorane, 3,6-bis(dimethylamino)fluorene-9-spiro-3'-(6'
-dimethylamino)phthalide, 3-diethylamino-6
-(N-allyl-N-methylamino)fluorene-9-
spiro-3'-(6'-dimethylamino)phthalide,
3.6-bis(dimethylamino)-spiro[fluorene-9,6'-6' H-chromeno(4,3-b)indole L3,6-bis(dimethylamino)-3'-methyl-spiro[fluorene -9,6'-6' H-chromeno(4,3-b)indole), 3,6-bis(diethylamino)-3'-methyl-spiro[fluorene-9
, 6'6'H-chromeno(4,3-b)indole] and the like. Of course, the dyes are not limited to these dyes, and two or more types of dyes can be used in combination. Furthermore, among the recording materials of the present invention, for example, in the case of heat-sensitive recording bodies, various thermofusible substances can be used as recording sensitivity improvers in order to obtain high-speed recording properties. Examples of such thermofusible substances include caproic acid amide, capric acid amide, palmitic 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 amide, benzanilide, linoleic acid anilide, N-ethyl capric acid amide, N-butyl lauric acid amide, N-octadecyl acetamide, N-oleacetamide, N-oleylbenzamide, N-stearylcyclohexylamide , polyethylene glycol, ■-hensyloxynaphthalene, 2-hensyloxynaphthalene, 1-hydroxynaphthoic acid phenyl ester, ■, 2-diphenoxyethane, 14-diphenoxybutane, 1,2-bis(3- Methylphenoxy)ethane, 1,2-bis(4-methoxyphenoxy)ethane, 1
-phenoxy-2-(4-chlorophenoxy)ethane,
1-phenoxy-2-(4-methoxyphenoxy)ethane, 1-(2-methylphenoxy)-2-(4-methoxyphenoxy)ethane, dibenzyl terephthalate, dihenzyl oxalate, di(4-methylhensyl oxalate) ), p-hensyloxybenzoic acid hensyl ester, P-benzylbiphenyl, 15-bis(P-methoxyphenoxy)-3-oxa-penkune, 1,4-bis(
2vinyloxyethoxy) Hensen, p-biphenyl-
Examples include compounds such as P-)lyl ether and hensyl-P-methylthiophenyl ether.

There is no particular limitation on the amount of the thermofusible substance used, but it is generally from 50 to 100 parts by weight of the basic dye.
It is desirable to adjust the amount to 700 parts by weight, preferably in the range of 100 to 500 parts by weight.

Various representative recording materials using the salicylic acid derivative represented by the general formula (1) and/or its polyvalent metal salt of the present invention and the basic dye as described above will be specifically explained below. Pressure recording bodies are described, for example, in U.S. Patent Box 2,505,47.
No. 0, No. 2,505,471, No. 2゜505, 489
No. 2,548,366, No. 2,712,507, No. 2,730,456, No. 2,730.457,
There are various forms of pressure-sensitive recording as described in No. 3,418,250, No. 3,924,027, No. 4,010,038, etc., and the present invention is directed to pressure-sensitive recording of these various forms. It is something that can be applied to the body. Generally, at least one of the salicylic acid derivatives or polyvalent metal salts thereof of the present invention is dispersed in various binders such as styrene-butadiene copolymer Latinx, polyvinyl alcohol, etc., along with other colorants and pigments as necessary. A coloring agent sheet (so-called bottom sheet) is produced by applying the coloring agent coating liquid onto a suitable support such as paper, plastic sheet, resin coated paper, or the like.

On the other hand, the color former sheet (so-called top sheet) used in combination with the above color former sheet is a synthetic oil such as alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, etc.; cottonseed oil; , vegetable oil such as castor oil, animal oil, mineral oil, or a mixture thereof. , contained in microcapsules by various encapsulation methods such as 1n-situ method,
It is manufactured by coating a dispersion in a binder on a suitable support such as paper, plastic sheet, resin-coated paper, etc. Of course, there are so-called cow sheets in which one side of the support is coated with the above-mentioned coloring agent coating liquid and the other side is coated with a dye dispersion or dye capsule dispersion, and furthermore, dye capsules and coloring agent are coated on the same side of the support. A so-called single-piece pressure-sensitive copying sheet in which dye capsules and a coloring agent coexist on the same surface by applying a coating liquid containing a mixture of dye capsules and a coloring agent coating liquid on top of a dye capsule dispersion liquid. As mentioned above, various forms such as the above are included.

The amount of basic dye and coloring agent used varies depending on various conditions such as the desired coating amount, the form of the pressure-sensitive recording medium, the encapsulation method, the composition of the coating liquid including various auxiliaries, and the coating method. It may be selected as appropriate depending on the conditions.

For example, heat-sensitive recording materials are disclosed in Japanese Patent Publication Nos. 44-3680 and 442.
No. 7880, No. 45-14039, No. 48-4383
No. 0, No. 49-69, No. 49-70, No. 52-20
142, etc., and the salicylic acid derivative or its polyvalent metal salt of the present invention can be applied to these various types of heat-sensitive recording materials. Generally, a coating liquid obtained by dispersing a basic dye and the salicylic acid derivative of the present invention or its polyvalent metal salt in a medium in which a binder is dissolved or dispersed is applied to paper, plastic film, synthetic paper, and even woven fabric sheets. The heat-sensitive recording material of the present invention is produced by coating it on a suitable support such as a molded product. The ratio of basic dye and coloring agent used in the recording layer is not particularly limited, but is generally 50 to 100 parts by weight of dye.
About 700 parts by weight, preferably about 100 to 500 parts by weight, of the coloring agent is used.

In addition, for the purpose of improving coloring ability, matting the surface of the recording layer, improving writing properties, etc., an inorganic pigment is generally added in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight, per 1 part by weight of a coloring agent. They can be used in combination in parts by weight, and various auxiliary agents such as dispersants, ultraviolet absorbers, thermofusible substances, antifoaming agents, fluorescent dyes, and coloring dyes can also be used in combination as necessary.

As mentioned above, the heat-sensitive recording material of the present invention is generally produced by coating a support with a coating liquid in which fine particles of a basic dye and a coloring agent are dispersed. It is of course possible to coat two separately dispersed coating liquids on the support, or to manufacture the coating by impregnation or rolling.

There are no particular restrictions on the preparation method or application method of the coating liquid, and the amount applied is generally 2 to 1 on dry weight.
Approximately 2g/m2 is applied. Furthermore, it is of course possible to provide an overcoat layer on the recording layer for the purpose of protecting the recording layer, or to provide an undercoat layer on the support, and various known techniques in the field of heat-sensitive recording material manufacturing can be added as appropriate. It is. Examples of binders include starches, celluloses, proteins, gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer salts, styrene-butadiene copolymer emulsions, acetic acid and maleic anhydride copolymer salts, and polyvinyl alcohol. Acrylates and the like are appropriately selected and used. Such a binder is blended in an amount of about 10 to 40% by weight, preferably about 15 to 30% by weight, based on the total solid content of the coating liquid.

The electrically conductive heat-sensitive recording material is manufactured, for example, by the method described in JP-A-49-11344 and JP-A-50-48930. Generally, a coating liquid in which a conductive substance, a basic dye, and a coloring agent are dispersed together with a binder is applied to a suitable support such as paper, or a conductive substance is applied to the support to form a conductive layer.
It is manufactured by applying a coating liquid containing a dye, a coloring agent, and a binder dispersed thereon. Incidentally, if both the dye and the coloring agent do not melt in the preferred temperature range of 70 to 120''C, sensitivity to Joule heat can be adjusted by using an appropriate thermofusible substance in combination.

"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 % in the examples indicate parts by weight and % by weight, respectively.

Example 1 6 parts of 3-(N-ethyl-N-isoamylamino)-6methyl-7-phenylaminofluorane were dissolved in 100 parts of isopropylated naphthalene, 25 parts of big skin gelatin with an isoelectric point of 8 and Arabica. 350 with 25 parts of rubber dissolved
of warm water (50°C) and emulsified and dispersed. Add 1000 parts of warm water to this emulsion, adjust the pH to 4 with acetic acid, cool it to 10°C, and add 2 parts of geltaraldehyde.
10 parts of a 5% aqueous solution was added to harden the capsules. This capsule-containing coating liquid was coated on one side of a 45 g/m'' base paper so that the dry weight was 5 g/I11'' to obtain a color former sheet.

On the other hand, 45 g of a coloring agent coating liquid was prepared by dispersing 20 parts of zinc salt of 4-(phenoxycarbonylmethoxy)salicylic acid, 80 parts of kaolin, and 30 parts of styrene-butadiene copolymer emulsion (50% solids) in 200 parts of water. /m2 base paper was coated with a dry weight of 5 g/m2 to obtain a coloring agent sheet.

When the thus prepared color forming agent sort and color forming agent sheet were stacked so that the capsule-coated surface and the color forming agent-coated surface faced each other, and writing and pressure were applied, a black image was instantly obtained. Ta. This image had high density and excellent light resistance.

Examples 2 to 4 In the preparation of the coloring agent sheet of Example 1, the following coloring agent was used instead of 20 parts of zinc salt of 4(phenoxycarbonylmethoxy)salicylic acid, but in the same manner as in Example 1. Three types of coloring agent sheets were obtained.

Example 2: 20 parts of zinc salt of 4-(p-)lyloxycarbonylmethoxy)salicylic acid Example 3: 20 parts of zinc salt of 4-(2-p-methoxyphenoxycarbonylethoxy)salicylic acid Example 4: 3, 10 parts of zinc salt of 5-bis(α-methylhensyl)salicylic acid 10 parts of zinc salt of 4-(phenoxycarbonylmethoxy)salicylic acid When coloring is performed in the same manner as in Example 1 using these coloring agent sheets, in both cases A black image was instantly obtained. All of these images had high density and excellent light resistance.

Example 5 ■ Preparation of liquid A 3-dibutylamino-6-methyl-7-phenylaminofluorane 10 parts 1.2-di(3
-Methylphenoxy)ethane 20 parts Methyl cellulose 5% aqueous solution 20 parts water
110 parts of this composition was ground in a sand mill until the average particle size was 1 μm.

■ Preparation of B solution 4-Zinc salt of (phenoxycarbonylmethoxy)salicylic acid 30 parts Methyl cellulose 5% aqueous solution 60 parts water
110 parts of this composition was ground in a sand mill until the average particle size was 2 μm.

Formation of recording layer 160 parts of liquid A, 200 parts of liquid B, silicon oxide pigment (oil absorption:
180 m1/100 g), 150 parts of a 20% oxidized starch aqueous solution, and 210 parts of water were mixed and stirred to prepare a coating liquid. The obtained coating liquid was applied to 50 g/a” base paper with a dry weight of 6.0
A heat-sensitive recording paper was obtained by coating and drying so as to give a ratio of "g/va".

Examples 6 to 15 and Comparative Examples 1 to 3 The procedure was the same as in Example 5 except that the following compound was used instead of the zinc salt of 4-(phenoxycarbonylmethoxy)salicylic acid in the preparation of Solution B of Example 5. Thirteen types of thermal recording papers were obtained.

Example 6: Zinc salt of 4-(2-p-tolyloxycarbonyl ethoxy)salicylic acid Example 7: Zinc salt of 4-(p-methoxyphenoxycarbonylmethoxy) salicylic acid Example 8: 4-(4-o-chloro Zinc salt of 4-(4-(2-vinyloxyethoxy)phenoxycarbonylmethoxy) salicylic acid Example 10: 4-(1-(2-phenoxyethoxy)phenoxycarbonylmethoxy) ) Zinc salt of salicylic acid Example 11: Zinc salt of 4-(tetradecyloxycarbonylmethoxy) salicylic acid Example 12: Zinc salt of 5-(benzyloxycarbonylmethoxy) salicylic acid Example 13: 5-(p-methoxyphenoxycarbonyl Zinc salt of 4-(p-methoxyphenoxycarbonylmethoxy)salicylic acid Example 14: Calcium salt of 4-(p-methoxyphenoxycarbonylmethoxy) salicylic acid Example 15: Magnesium salt of 4-(p-methoxyphenoxycarbonylmethoxy) salicylic acid Comparative example 1: 4,4'- Isopropylidene diphenol Comparative Example 2: Zinc salt of 3,5-di(α-methylhensyl)salicylic acid Comparative Example 3: Zinc salt of 4-pentadecyloxysalicylic acid Example 16 In place of Solution B of Example 5, the following C A thermosensitive recording paper was obtained in the same manner as in Example 5 except that the liquid was used.

■ Lacquer preparation 4-(phenoxycarbonylmethoxy) salicylic acid
30 parts zinc oxide
30 parts methylcellulose 5% aqueous solution 60 parts water
80 parts of this composition was ground in a sand mill until the average particle size was 2 μm.

Examples 17 to 25 and Comparative Examples 4 to 5 Eleven types of lacquer were prepared in the same manner as in Example 16, except that the following compounds were used instead of 4-(phenoxycarbonylmethoxy)salicylic acid in the C lacquer preparation of Example 16. A thermosensitive recording paper was obtained.

Example 17: 4-(2-p-)lyloxylponylethoxy)salicylic acidExample 18: 4-(p-methoxyphenoxycarbonylmethoxy)salicylic acidExample 19: 4-(p-isopropoxyphenoxycarbonylmethoxy)salicylic acid Example 20: 4-C4-(2-methoxyethoxy)
phenoxycarbonylmethoxy]salicylic acid Example 21: 4-(4-(2-p-methoxyphenoxyethoxy)phenoxycarbonylmethoxy)salicylic acid Example 22: 4-(2-octyloxycarbonylethoxy)salicylic acid Example 23: 4-( 2-phenoxyethoxycarbonylmethoxy) salicylic acid Example 24: 5-(P-methoxyphenoxycarbonylmethoxy) salicylic acid Example 25: Zinc salt of 4-(p-methoxyphenoxycarbonylmethoxy) salicylic acid Comparative Example 4: 3,5-di (α-Methylhensyl)salicylic acid Comparative Example 5: 4-Pentadecyloxysalicylic acid The 26 types of thermal recording paper thus obtained were recorded using a thermal facsimile (Hitachi HIFAX-700 model), and the color density was measured using a Maches densitometer. (RD-914 model)
The results are shown in Tables 1 and 2.

In addition, after leaving the thermal recording paper after recording under a high temperature drying condition of 60°C for 20 hours, and after leaving it under a high humidity condition of 40°C and 290% RH for 20 hours, the color density of each recorded image was checked again using Macbeth. The heat resistance and moisture resistance of the recorded image were evaluated using a densitometer, and the results are shown in Tables 1 and 2.

Furthermore, in order to evaluate chemical resistance, a vinyl chloride film was layered on the colored side of thermal recording paper after recording and left at room temperature for 20 hours (plasticizer resistance), and when ethanol was applied to the colored side ( The degree of fog in the blank area and the degree of fading of the recorded image was evaluated for each case (alcohol resistance) and when cottonseed oil was applied to the coloring surface (oil resistance), and the results are shown in Tables 1 and 2.

"Effects" As is clear from the results in Tables 1 and 2, the recording material according to the present invention has a high color density (and is excellent in the storage stability of recorded images, especially in that it is free from fading of colored areas and background fog due to chemicals). Met.

Claims (4)

[Claims] (1) In a recording material that utilizes the reaction between a colorless or light-colored basic dye and a coloring agent, at least one salicylic acid derivative represented by the following general formula [I] or its polyvalent metal salt is used as the coloring agent. A recording material characterized by using. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cyclo which may have a substituent. It represents an alkyl group, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent, and X represents an alkylene group which may be branched. In addition, Y is an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group,
Represents an alkoxyl group, phenyl group, naphthyl group, phenoxy group, nitro group, or halogen atom, m is 0 or 1
Indicates an integer between ~3. ] (2) The recording material according to claim (1), in which at least one salicylic acid derivative represented by the general formula [I] or a polyvalent metal salt thereof and a metal compound are used together as a coloring agent. (3) Claim (1) or (
2) Recording materials described. (4) Claim (1) or (
2) Recording materials described.