JPH0465286A - Recording material - Google Patents

Abstract

PURPOSE:To form a recording material extremely excellent in color forming properties and the preservability of a recording image by using at least one kind of a specific salicylic acid derivative or a polyvalent metal salt thereof as a developer. CONSTITUTION:In a recording material utilizing the reaction of a colorless-light- colored basic material with a developer, at least one kind of a salicylic acid derivative represented by formula I or a polyvalent metal salt is used as the developer. In the formula, R is a group which may have a substituent selected from an alkyl group, an alkenyl group, a cycloalkyl group, a phenyl group and a naphthyl group, X is an alkylene group which may have an ether bond, Y is an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an alkoxy group, a phenyl group, a naphthyl group, a phenoxy group, a nitro group or a halogen atom and m is 0 or an 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" Typical examples of recording materials that utilize a color reaction between a colorless or light-colored basic dye and an organic or inorganic coloring agent include pressure-sensitive recording materials, heat-sensitive recording materials, and current-carrying heat-sensitive recording materials. Various types 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 labels 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 changing and discoloring. 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 fogging which is 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 [I] or its polyvalent metal salts is used as a coloring agent, it is possible to obtain records that are extremely excellent not only in terms of color development and shelf life, but also in terms of 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 that uses a reaction between a colorless or light-colored basic dye and a coloring agent, in which salicylic acid represented by the following general formula [I] 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.

'll'1. ”’1.l’i.

[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, or a cycloalkyl group that may have a substituent. represents 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 have an ether bond.

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 m represents 0 or an integer of 1 to 3. ] "Action" The salicylic acid derivative used in the general formula [I] of the present invention can be synthesized by a known method, for example, a method of alkylating a corresponding hydroxysalicylic acid derivative, a method of carboxylating a corresponding phenol derivative. It can be obtained by etc.

In the salicylic acid derivative represented by the general formula [I] of the present invention, among the substituents represented by R, the substituent for the alkyl group or alkenyl group is particularly CI-! O alkoxyl group, 02~2° alkoxyalkoxyl group, 0
Preferred are alkenyloxy groups of 2 to 6, aryl groups of C1 to 2, aryloxy groups of C1 to 2, aryloxydialkoxyl groups of C6 to i, furyl groups, tetrahydrofuryl groups, etc., and these substituents include The aromatic rings included are further 01-6 alkyl groups, C1-6 alkoxyl groups,
Alternatively, it may have a substituent such as a halogen atom.

Also, among the substituents represented by R, substituents for phenyl or naphthyl groups include alkyl groups with CI~2°,
Alkenyl group of 02-6, aryl group of Ch-I□, C
1-1° aralkyl group, C3-2° alkoxyl M
, C, ~2° hydroxyalkoxyl group, 02-2° alkoxyalkoxyl group, 02-6 alkenyloxy group, C1-6 alkenyloxydialkoxyl group,
C6-1□ aryloxy group, C1-2° aryloxydialkoxy group, C1-1° aralkyloxy group, 02-7 alkoxycarbonyl group, 02-. An alkylcarbonyloxy group, a hydroxyl group, a halogen atom, etc. are preferable, and the aromatic ring contained in these substituents further has a substituent such as a C1-6 alkyl group, a CI-6 alkoxyl group, or a halogen atom. You can.

Furthermore, among the substituents represented by R, substituents for cycloalkyl groups include C3-6 alkyl groups, C3-6
An alkoxyl group, a halogen atom, etc. are preferable.

Further, X represents an alkylene group which may have an ether bond, and among these, a C3 to l□ alkylene group which may have an ether bond is preferable, and in particular,
A Cl-6 alkylene group which may have an ether bond is more preferred.

In general, Y represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an alkoxyl group, a phenyl group, a naphthyl group, a miphenoxy group, a nitro group, or a halogen atom, and among these, especially % C1 ~, More preferred are an alkyl group, a C7-I0 aralkyl group, a C1-h alkoxyl group, a phenyl group, a phenoxy group, a chlorine atom, a bromine atom, or a fluorine atom.

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 such as zinc, calcium, aluminum, magnesium, tin, iron, etc. Among these, zinc is particularly 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 [I] include the following.

4-benzoyloxymethoxysalicylic acid, 5-benzoyloxymethoxysalicylic acid, 4-(2-benzoyloxyethoxy)salicylic acid, 5-(2-benzoyloxyethoxy)salicylic acid, 4-(3-benzoyloxypropyloxy)salicylic acid, 5-( 3-benzoyloxypropyloxy) salicylic acid, 4-(4-benzoyloxybutyloxy) salicylic acid, 5-(4-benzoyloxybutyloxy) salicylic acid, 4-(5-benzoyloxypentyloxy) salicylic acid, 5-(5-
Benzoyloxypentyloxy)salicylic acid, 4-(
6-benzoyloxyhexyloxy) salicylic acid, 5
-(6-benzoyloxyhexyloxy) salicylic acid, 4-(8-benzoyloxyoctyloxy) salicylic acid, 5(8-benzoyloxyoctyloxy) salicylic acid, 4-(10-benzoyloxydecyloxy)
Salicylic acid, 5-(10-benzoyloxydecyloxy) salicylic acid, 4-(12-benzoyloxydodecyloxy) salicylic acid, 5-(12-benzoyloxydodecyloxy) salicylic acid, 4-(18-benzoyloxyoctadecyloxy) salicylic acid, 5-(18-
benzoyloxyoctadecyloxy) salicylic acid, 4
-(5-benzoyloxy-3-oxa-pentyloxy) salicylic acid, 5-(5-benzoyloxy-3-oxa-pentyloxy) salicylic acid, 4-(8-benzoyloxy-3,6-thioxaoctyloxy) salicylic acid , 5-(8-benzoyloxy-3,6-thioxaoctyloxy)salicylic acid, 4m(11-benzoyloxy-3°6.9-trioxa-undecyloxy)
Salicylic acid, 5-(11-benzoyloxy-3,6°9-trioxa-undecyloxy) salicylic acid, 4-
(7-penzoyloxy-3,5-dioxa-hebutyloxy) salicylic acid, 5-(7-penzoyloxy-3
, 5-dioxa-hebutyloxy)salicylic acid, 4-(
9-benzoyloxy-5-oxa-nonyloxy)salicylic acid, 5-(9-benzoyloxy-5-oxa-
nonyloxy) salicylic acid, 4-(3-p-methylbenzoyloxypropyloxy) salicylic acid, 5-(3-
p-Methylbenzoyloxypropyloxy) salicylic acid, 4-(3-o-methylbenzoyloxypropyloxy) salicylic acid, 5-(3-.

methylbenzoyloxypropyloxy) salicylic acid,
4-(3-m-methylbenzoyloxypropyloxy) salicylic acid, 5-(3-m-methylbenzoyloxypropyloxy) salicylic acid, 4-(4-p-methylbenzoyloxybutyloxy) salicylic acid, 5-(
4-p-methy)Lthenzoyloxybutyloxy) salicylic acid, 4-(3-p-ethylbenzoyloxypropyloxy) salicylic acid, 5-(3-p-ethylbenzoyloxypropyloxy) salicylic acid, 4-(3p-
tert-butylbenzoyloxypropyloxy) salicylic acid, 5 (3p tert-butylbenzoyloxypropyloxy) salicylic acid, 4- (3-p
-hexylbenzoyloxypropyloxy) salicylic acid, 5-(3-p-hexylbenzoyloxypropyloxy) salicylic acid, 4-(3-p-dodecylbenzoyloxypropyloxy) salicylic acid, 5-(3-p-
Dodecylbenzoyloxypropyloxy) salicylic acid, 4-(3-p-pentadecylbenzoyloxypropyloxy) salicylic acid, 5-(3-p-pentadecylbenzoyloxypropyloxy) salicylic acid, 4-(
3-p-vinylbenzoyloxypropyloxy) salicylic acid, 5-(3-p-vinylbenzoyloxypropyloxy) salicylic acid, 4-(3-p-allylbenzoyloxypropyloxy) salicylic acid, 5-(3-p-vinylbenzoyloxypropyloxy) salicylic acid,
-Allylbenzoyloxypropyloxy)salicylic acid, 4-(2-p-phenylbenzoyloxyethoxy)
Salicylic acid, 5-(2-p-phenylbenzoyloxyethoxy) salicylic acid, 4-(3-p-phenylbenzoyloxypropyloxy) salicylic'fl! , 5-
(3-p-phenylbenzoyloxypropyloxy)
Salicylic acid, 4-(3-.

phenylbenzoyloxypropyloxy)su') cylic acid, 5-(3-o-phenylbenzoyloxypropyloxy)salicylic acid, 4-(3-p(p-tolyl)
Benzoyloxypropyloxyfusalicylic acid, 5-(
3-p-(p-tolyl)benzoyloxypropyloxyfusalicylic acid, 4-(3-p-benzylbenzoyloxypropyloxy)salicylic acid, 5-(3-p-benzylbenzoyloxypropyloxy)salicylic acid,
4- (2-p-methoxybenzoyloxyethoxy)
Salicylic acid, 5-(2-p-methoxybenzoyloxyethoxy) salicylic acid, 4-(3-p-methoxybenzoyloxypropyloxy) salicylic acid, 5-(3-p-
Methoxybenzoyloxypropyloxy)salicylic acid, 4-(3-.

Methoxybenzoyloxypropyloxy) salicylic acid, 5-(3-o-methoxybenzoyloxypropyloxy) salicylic acid, 4-(3-m-methoxybenzoyloxypropyloxy) salicylic acid, 5-(3-m-methoxybenzoyloxypropyloxy) ) salicylic acid,
4- (4-p-methoxybenzoyloxybutyloxy) salicylic acid, 5- (4-p-methoxybenzoyloxybutyloxy) salicylic acid, 4- (6-p-methoxybenzoyloxyhexyloxy) salicylic acid, 5-
(6-p-methoxybenzoyloxyhexyloxy) salicylic acid, 4-(3-p-ethoxybenzoyloxypropyloxy) salicylic acid, 5-(3-p-ethoxybenzoyloxypropyloxy) salicylic acid, 4-
(3-p-isopropyloxybenzoyloxypropyloxy) salicylic acid, 5-(3-p-isopropyloxybenzoyloxypropyloxy) salicylic acid,
4-(3-o-octyloxybenzoyloxypropyloxy)salicylic acid, 5-(3-.

-octyloxybenzoyloxypropyloxy)salicylic acid, 4-(3-p-tetradecyloxybenzoyloxypropyloxy)salicylic acid, 5-(3-p-tetradecyloxybenzoyloxypropyloxy)salicylic acid,
-tetradecyloxybenzoyloxypropyloxy) salicylic acid, 4-(3p-octadecyloxybenzoyloxypropyloxy) salicylic acid, 5-(3-p
-octadecyloxybenzoyloxypropyloxy) salicylic acid, 4-[3-p-(2-hydroxyethoxy)benzoyloxypropyloxyfusalicylic acid, 5
-(3-p-(2-hydroxyethoxy)benzoyloxypropyloxyfusalicylic acid, 4-(3-p-(2-hydroxyethoxy)benzoyloxypropyloxyfusalicylic acid,
-methoxyethoxy)benzoyloxyprobyloxysalicylic acid, 5(3-p-(2-methoxyethoxy)
Benzoyloxypropyloxyfusalicylic acid, 4-[
3-p-(2-ethoxyethoxy)benzoyloxypropyloxyfusalicylic acid, 5-(3-p-(2-ethoxyethoxy)benzoyloxypropyloxyfusalicylic acid, 4-(3-p-allyloxybenzoyloxyprobyl) Oxusalicylic acid, 5-(3-p-allyloxybenzoyloxyprobyloxysalicylic acid, 4
-(3-p-(2-vinyloxyethoxy)benzoyloxypropyloxyfusalicylic acid, 5-(3-p(2-vinyloxyethoxy)benzoyloxypropyloxyfusalicylic acid,
-vinyloxyethoxy)benzoyloxyprobyloxysalicylic acid, 4-(3-p-phenoxybenzoyloxypropyloxy)salicylic acid, 5-(3
-p-phenoxybenzoyloxypropyloxy)salicylic acid, 4-(3-p-(p-chlorophenoxy)benzoyloxypropyloxysalicylic acid, 5-(3
-p-(p-chlorophenoxy)benzoyloxypropyloxyfusalicylic acid, 4-(3-p-(2-phenoxyethoxy)benzoyloxypropyloxyfusalicylic acid, 5-(3-p-(2-phenoxyethoxy)benzoyl) Oxypropyloxyfusalicylic acid, 4-[3
-p-(2-p-methoxyphenoxyethoxy)benzoyloxypropyloxyfusalicylic acid, 5-(3
-p-(2-p-methoxyphenoxyethoxy)benzoyloxypropyloxyfusalicylic acid, 4-(3
-p-(2-P-isopropyloxyphenoxyethoxy)benzoyloxypropyloxyfusalicylic acid, 5
- (3-p-di(2-P-isopropyloxyphenoxyethoxy)benzoyloxypropyloxyfusalicylic acid, 4-(3-p-benzyloxybenzoyloxypropyloxy)salicylic acid, 5-(3-p-benzyloxybenzoyloxy) propyloxy) salicylic acid,
4-(3-p-(p-methylbenzyloxy)benzoyloxyprobyloxysalicylic acid, 5-(3-p-
(p-Methylbenzyloxy)benzoyloxypropyloxyfusalicylic acid, 4-(3-p-methoxycarbonylbezoyloxyprobyloxy)salicyl 15-(
3-p-methoxylponylbezoyloxypropyloxy) salicylic acid, 4-(2-p-acetoxybenzoyloxyethoxy) salicylic acid, 5-(2-p-acetoxybenzoyloxyethoxy) salicylic acid, 4-(3-p-acetoxybenzoyloxyethoxy) salicylic acid,
-p-acetoxybenzoyloxypropyloxy) salicylic acid, 5-(3-p-acetoxybenzoyloxypropyloxy) salicylic acid, 4-(3-0-acetoxybenzoyloxypropyloxy) salicylic acid, 5-
(3-o-acetoxybenzoyloxypropyloxy) salicylic acid, 4-(3-p-hydroxybenzoyloxypropyloxy) salicylic acid, 5-(3-p-hydroxybenzoyloxypropyloxy) salicylic acid,
4(3-o-hydroxybenzoyloxypropyloxy) salicylic acid, 5-(3-o-hydroxybenzoyloxypropyloxy) salicylic acid, 4-(2-p-chlorobenzoyloxyethoxy) salicylic acid, 5-(2
-p-chlorobenzoyloxyethoxy) salicylic acid,
4-(2-o-chlorobenzoyloxyethoxy)salicylic acid, 5-(2-o-chlorobenzoyloxyethoxy)salicylic acid, 4-(3-p-chlorobenzoyloxypropyloxy)salicylic acid, 5-(3-p- Chlorobenzoyloxypropyloxy) salicylic acid, 4
- [2-(2-naphthoyloxy)ethoxy]salicylic acid, 5-(2-(2-naphthoyloxy)ethoxy)salicylic acid, 4-(3-(2-naphthoyloxy)propyloxyfusalicylic acid, 5 - (3-(2-naphthoyloxy)propyloxyfusalicylic acid, 4- (6
-(2-naphthoyloxy)hexyloxy]salicylic acid, 5-(6-(2-naphthoyloxy)hexyloxy)salicylic acid, 4-(3-(1-naphthoyloxy)propyloxytasalicylic acid, 5-[ 3-(1naphthoyloxy)propyloxytasalicylic acid, 4-(
3-(6-methyl-2-naphthoyloxy)propyloxytasalicylic acid, 5-(3-(6methyl-2-naphthoyloxy)propyloxytasalicylic acid, 4-(
3-(4-methoxy-1-naphthoyloxy)propyloxytasalicylic acid, 5-(3-(4-methoxy-1)
-naphthoyloxy)propyloxytasalicylic acid, 4
-(2-cyclopentanecarbonyloxyethoxy)salicylic acid, 5-(2-cyclopencunecarfokinyloxyethoxy)salicylic acid, 4-(3-cyclohexylcarfokinyloxyprobyloxy)salicylic acid, 5-(
3-cyclohexylcarphokinyloxypropyloxy) salicylic acid, 4-(3-(4-methylcyclohexanecarbonyloxy)propyloxytasalicylic acid, 5-
[3-(4-Methoxycyclohexanecarbonyloxy)propyloxytasalicylic acid, 4-(3-(4-methoxycyclohexanecarbonyloxy)propyloxytasalicylic acid, 5-(3-(4-methoxycyclohexanecarbonyloxy)propyloxyta) Salicylic acid, 4-(3-(2-chlorocyclohexanecarbonyloxy)propyloxytasalicylic acid, 5-[3-(
2-chlorocyclohexanecarbonyloxy)propyloxy]salicylic acid, 4- (3-(2,4-dimethylbenzoyloxy)propyloxytasalicylic acid, 5-
(3-(2゜4-dimethylbenzoyloxy)propyloxytasalicylic acid, 3-methyl-4-(3-benzoyloxypropyloxy)salicylic acid, 3-methyl-
5-(3-benzoyloxypropyloxy)salicylic acid, 3,5-dimethyl-4-(3-benzoyloxypropyloxy)salicylic acid, 3-cyclohexyl-4-
(3-benzoyloxypropyloxy) salicylic acid,
3-allyl-4-(3-benzoyloxypropyloxy)salicylic acid, 3-α,α-dimethylbenzyl-4-
(3-benzoyloxypropyloxy) salicylic acid, 3-α-methylbenzyl-4-(3-benzoyloxypropyloxy) salicylic acid, 3-phenyl-4-(
3-benzoyloxypropyloxy) salicylic acid, 3
-phenoxy-4-(3-benzoyloxypropyloxy)salicylic acid, 4-chloro-5-(3-benzoyloxypropyloxy)salicylic acid, 5-chloro-4-
(3-benzoyloxypropyloxy) salicylic acid,
3.5-dichloro-4-(3-benzoyloxypropyloxy)salicylic acid, 3-methoxy-5-(3benzoyloxypropyloxy)salicylic acid, 5-nitro-
4-(3-benzoyloxypropyloxy) salicylic acid, 4-(3-acetoxypropyloxy) salicylic acid, 5-(3-acetoxypropyloxy) salicylic acid,
4-(3-propionyloxypropyloxy) salicylic acid, 5-(3-propionyloxypropyloxy)
Salicylic acid, 4-(・3-butyryloxypropyloxy) salicylic acid, 5-(3-butyryloxypropyloxy) salicylic acid, 4-(3-3so -butyryloxypropyloxy) salicylic acid, 5-(3-iso −
Butyryloxypropyloxy)salicylic acid, 4-(3
-valeryloxypropyloxy)salicylic acid, 5-(
3-valeryloxypropyloxy)salicylic acid, 4-
(3-hexanoyloxypropyloxy) salicylic acid, 5-(3-hexanoyloxypropyloxy) salicylic acid, 4-(3-octanoyloxypropyloxy) salicylic acid, 5-(3-octanoyloxypropyloxy) salicylic acid, 4-(2-lauroyloxyethoxy) salicylic acid, 5-(2-lauroyloxyethoxy) salicylic acid, 4-(2-palmitoyloxyethoxy) salicylic acid, 5-(2-palmitoyloxyethoxy) salicylic acid, 4-(2-steroilic acid) 5-(2-steroyloxyethoxy)salicylic acid, 4-(3-oleoyloxypropyloxy)salicylic acid, 5-(3-oleoyloxypropyloxy)salicylic acid, 4-(6-acryloyl oxyhexyloxy) salicylic acid, 5-(6-acryloyloxyhexyloxy) salicylic acid, 4-(3-methacryloyloxypropyloxy) salicylic acid, 5-(
3-methacryloyloxypropyloxy) salicylic acid, 4-(3-r-methylhexanoyloxypropyloxy) salicylic acid, 5-(3-r-methylhexanoyloxypropyloxy) salicylic acid, 4-(2-r-
methoxysteroyloxyethoxy) salicylic acid, 5-
(2-r-methoxysteroyloxyethoxy) salicylic acid, 4-[3-β-(2-methoxyethoxy)butyryloxypropyloxy] salicylic acid, 5-[3-β-
(2-methoxyethoxy)butyryloxypropyloxy]salicylic acid, 4-(3-r-allyloxyvaleryloxypropyloxy)salicylic acid, 5-(3-γ-allyloxyvaleryloxypropyloxy)salicylic acid, 4- (3-phenylacetoxypropyloxy) salicylic acid, 5-(3-phenylacetoxypropyloxy) salicylic acid, 4- (3-(5-phenylvaleryloxy) propyloxyfusalicylic acid, 5- (3-(5
-phenylvaleryloxy)propyloxyfusalicylic acid, 4-(3-diphenylacetoxypropyloxy)
Salicylic acid, 5-(3-diphenylacetoxypropyloxy)salicylic acid, 4-(2-(2-naphthylacetoxy)ethoxy)salicylic acid, 5-(2-(2-naphthylacetoxy)ethoxy)salicylic acid, 4-(3-
Phenoxyacetoxypropyloxy) salicylic acid, 5
-(3-phenoxyacetoxypropyloxy) salicylic acid, 4-(3-(5-phenoxyvaleryloxy)propyloxyfusalicylic acid, 5-(3-(5-phenoxyvaleryloxy)propyloxyfusalicylic acid, 4-
(3-(2-phenoxyethoxy)acetoxypropyloxysalicylic acid, 5-[3(2-phenoxyethoxy)acetoxypropyloxysalicylic acid, 4-
[3-(6-(2-furyl)hexanoyloxyfupropyloxy)salicylic acid, 5-(3-(6-(2-furyl)hexanoyloxy]propyloxy)salicylic acid, 4-(3-(3- (2-tetrahydrofuryl)prohionyloxy]propyloxy)salicylic acid, 5-
(3-(3-(2-tetrahydrofuryl)prohionyloxy]propyloxy)salicylic acid, 4-(3-p
-1lylacetoxypropyloxy)salicylic acid, 5-
(3-p-)lylacetoxypropyloxy)salicylic acid, 4-(3-p-ethoxyphenylacetoxypropyloxy)salicylic acid, 5-(3-p-ethoxyphenylacetoxypropyloxy)salicylic acid, 4-(
3-(4-p-chlorophenylbutyloxy)propyloxyfusalicylic acid, 5-(3-(4-p-chlorophenylbutyloxy)propyloxyfusalicylic acid, 4-
(3-cinnamoyloxypropyloxy) salicylic acid, 5-(3-cinnamoyloxypropyloxy) salicylic acid, and the like.

Two or more kinds of these salicylic acid derivatives and/or their polyvalent metal salts can be used in combination, if necessary.

In the present invention, by using a salicylic acid derivative represented by the general formula [I] and/or its polyvalent metal salt as a coloring agent, the recording material has excellent color development properties and raw storage stability, especially storage stability of recorded images. 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,
Oxides, hydroxides, sulfides, halides, carbonates, phosphates, silicates, sulfates, nitrates or halogen complexes of metals selected from aluminum, tin, titanium, nickel, cobalt, manganese, iron, etc. Among these, zinc compounds are particularly preferred.

Specific examples of metal compounds include zinc oxide, zinc hydroxide, zinc amate, zinc sulfide, zinc carbonate, zinc phosphate, zinc silicate, aluminum oxide, magnesium oxide,
Examples include titanium oxide, aluminum hydroxide, aluminum silicate, aluminum phosphate, magnesium aluminate, magnesium hydroxide, magnesium carbonate, and magnesium phosphate. 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 general formula [I] 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, salicylic acid derivatives other than the salicylic acid of the present invention may be used, as long as the desired effects are not inhibited.
Various known coloring agents such as phenol derivatives, phenol resins, and acid clay can be used in combination. Specific examples of such known coloring agents include the following.

Acid clay, activated clay, attapal guide, bentonite,
Inorganic coloring agents such as colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, calcined kaolin, talc; oxalic acid, maleic acid, tartaric acid, citric acid,
Aliphatic carboxylic acids such as 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-di-tert-butylsalicylic acid, 3-methyl-5benzylsalicylic acid, 3-phenyl-5-(α.

α-dimethylbenzyl)salicylic acid, 3,5-bis-(
α-Methylbenzyl)salicylic acid, 2-hydroxy-1
- Aromatic carboxylic acids such as benzyl-3-naphthoic acid, 4-(2-p-methoxyphenoxyethoxy)salicyl M, 4-(3-p-tolylsulfonylpropyloxy)salicylic acid; 4,4'-isopropylidene di Phenol (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(2-tert-butylphenol), 41 4'-
5ec-butyldendiphenol, 2,2'-bis(4
-hydroxyphenyl)-4-methylpentane, 4.4
'-cyclohexylidene bisphenol, 4.4'-cyclohexylidene bis(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-ter
t-octylcatechol, 2,2'-methylenebis(4
-chlorophenol), 2,2'-methylenebis(4-
methyl-6-tert-butylphenol), 2.2'
-dihydroxybiphenyl, methyl-bis(4-hydroxyphenyl) acetate, ethyl-bis(4-hydroxyphenyl) acetate, benzyl-bis(4-hydroxyphenyl) acetate, 4゜4'-(p-phenylenediisopropylidene) Diphenol, 4.4'-
(m-phenylene diisopropylidene) diphenonyl,
4-hydroxydiphenylsulfone, 4.41-dihydroxydiphenylsulfone, 4-hydroxy-41-methyldiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-3'
, 4'-tetramethylene diphenyl sulfone, 3,3'
-diallyl-4,4'-dihydroxydiphenylsulfone, butyl-bis(4-hydroxyphenyl) acetate, bis(4-hydroxyphenyl)acetic acid-2-phenoxyethyl ester, p-hydroxy-N-(2-phenoxyethyl) Benzenesulfonamide, dimethyl 4-hydroxyphthalate, 1.5-bis(4-hydroxyphenylthio)-3-oxa-pentane, 1゜7-bis(
4-hydroxyphenylthio)-3゜5-dioxa-hebutane, 1,8-bis(4-hydroxyphenylthio)
-3,6-thioxaoctane, (4-hydroxyphenylthio)acetic acid-2-(4-hydroxyphenylthio)ethyl ester and other phenolic compounds 1'l: p-
Organic coloring agents such as phenolic resins such as phenylphenol-formalin resin and p-butylphenol-acetylene resin; These organic coloring agents and polyvalent compounds such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, and nickel. Salts with metals; metal complex compounds such as antipyrine complex 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 derivatives or metal salts thereof, and examples thereof include the following.

3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(4-dimethylaminophenyl)-3-(4-diethylamino- 2-methylphenyl)-6-(dimethylamino)phthalide, 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-dimethylaminophthalide, 3.3-bis(9-ethylcarbazol-3-yl)-6-dimethylaminophthalide, 3゜3-bis(2-phenylindol-3-yl)6-dimethylaminophthalide , 3-P-dimethylaminophenyl-3-(1-methylpyrrol-3-yl)-
Triallylmethane dyes such as 6-dimethylaminophthalide, 4,4'-bis(dimethylamino)benzhydrylbenzyl ether, N-halophenyl-leucoauramine, N-2,4°5-trichlorophenylleucoauramine Diphenylmethane dyes such as amine, 3,3-bis(1,
l-Bis(4-pyrrolidinophenyl)ethylene-2yl)-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-(
Divinylphthalide dyes such as 4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7-titrachlorophthalide, benzoylleucomethylene blue, p-nitrobenzoylleuco Thiazine dyes such as methylene blue, 3-methyl-spiro-
Dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho(6'
- Spiro dyes such as methoxybenzo)spiropyran and 3-propyl-spirodibenzopyran, lactam dyes such as rhodamine B-anilinolactam, rhodamine (p-nitroanilino) lactam, and rhodamine (0-chloroanilino) lactam, 3-dimethyl Amino-7-methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-7-methoxyfluoran,
3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-
Diethylamino-6,7-dimethylfluorane, 3-(
N-ethyl-p-)luidino)-7methylfluorane,
3-diethylamino-7-(N-acetyl-N-methylamino)fluorane, 3-diethylamino-7-N-methylaminofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-(
N-methyl-N-benzylamino)fluorane, 3-diethylamino-7-(N-chloroethyl-N-methylamino)fluorane, 3-diethylamino-7-diethylaminofluorane, 4-benzylamino-8-diethylamino-benzo(a) Fluoran, 3-(4-(,4-dimethylaminoanilino)anilino]-7-chloro-6-methylfluoran, 8-(4-(4-dimethylaminoanilino)anilino)-benzo(a)fluoran , 3-(
N-Ethyl-p-)luidino)-6-methyl 7-phenylaminofluorane, 3-(N-ethyl-P-toluidino)-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) -6methyl-7-phenylaminofluorane, 3-pyrrolidino-6-methyl-
7-phenylaminofluorane, 3-piperidino-6-
Methyl-7-phenylaminofluorane, 3-diethylamino-6-methyl-7-xylidinofluorane, 3-
Diethylamino-7-(0-chlorophenylamino)fluoran, 3-dibutylamino-7-(0-chlorophenylamino)fluoran, 3-(N-ethyl-N-tetrahydrofurfurylamino)-6methyl-7-phenylaminofluoran Oran, 3-(N-methyl-N-n-propylamino)-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-N-isobutylamino)-6-
Methyl-77phenylaminofluorane, 3-(N-methyl-Nn-hexylamino)-6-methyl-7-phenylaminofluorane, 3-dipentylamino-6-methyl-7-phenylaminofluorane, 3- [N-(
3-ethoxypropyl)N-methylamino-6-methyl-phenylaminofluorane, 3-[N-ethyl-N-(3-ethoxypropyl)amino-6-methyl-phenylaminofluorane, 3-diethylamino-7- Cm-()lifluoromethyl)phenylaminocofluorane, 3-diethylamino-7-(0-fluorophenylamino)fluorane, 3-cyptylamino-7
-(0-fluorophenylamino)fluoran, 3-diethylamino-6-chloro-7-phenylaminofluoran, 3-(N-ethyl-N-n-hexylamino)-
6-Methyl-7-phenylaminofluorane, 3-(N
-ethyl-N-cyclopentylamino)-6-methyl-
Fluoran dyes such as 7-phenylaminofluorane,
3,6-bis(dimethylamino)fluorene-9-spiro-3'-(6'-dimethylamino)phthalide, 3-
Diethylamino-6-(N-allyl-N-methylamino)fluorene-9spiro-3'-(6'-dimethylamino)phthalide, 3,6-bis(dimethylamino)-spiro[fluorene-9,6'- 6' H-chromeno (
4゜3-b) indole), 3,6-bis(dimethylamino)-3'-methyl-spiro[fluorene-9,6'
-6'H-chromeno(4,3-b)indole),
3.6-bis(diethylamino)-3'-methylsubiro[fluorene-9,6'-6'H-chromeno(4,
3-b) Fluorene dyes such as indole]. Of course,
The dyes are not limited to these dyes, and two or more types of dyes can be used in combination.

Further, for example, in the case of a heat-sensitive recording medium, various thermofusible substances can be used as a recording sensitivity improving agent in order to obtain high-speed recording performance. Such thermofusible substances include:
For example, 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-methyl stearic acid amide, stearic acid anilide, N-methyl oleic acid amide, 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, l,2-diphenoxyethane, 1
．． 4-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-(4methoxyphenoxy)ethane, terephthalic acid dibenzyl ester, oxalic acid dibenzyl ester, ShuH p-methylbenzyl ester, p-benzyloxybenzoic acid benzyl ester, p-pendylbiphenyl, 1, 5-bis(p-methoxyphenoxy)-3-
Examples include oxapencune, 1,4-bis(2-vinyloxyethoxy)benzene, p-biphenyl-P-tolyl ether, and benzyl-p-methylthiophenyl ether.

Below, various representative recording materials using the salicylic acid derivative represented by the general formula [I] or its metal salt and the above-mentioned basic dyes will be specifically explained.

For example, the pressure-sensitive recording medium is disclosed in U.S. Pat. No. 2.505.470,
No. 2,505,471, No. 2,505,489, No. 2.548.366, No. 2,712.507, No. 2
, 730.456, 2,730゜457, 3,
No. 418,250, No. 3,924.027, No. 4゜0
As described in No. 10.038, there are various types of pressure-sensitive recording bodies, and the present invention can be applied to these various types of pressure-sensitive recording bodies.

Generally, at least one of the salicylic acid derivatives or metal salts thereof of the present invention is dispersed in various binders such as styrene-butadiene copolymer latex and polyvinyl alcohol, along with other coloring agents and pigments as necessary. A color former sheet (so-called bottom sheet) is produced by applying a color former 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 basic dye, alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl; A dispersion obtained by dissolving this in a suitable solvent such as oil, vegetable oil such as castor oil; animal oil; mineral oil or a mixture thereof, or the like, and dispersing it in a binder, or the above solution can be processed by coacervation method, interfacial polymerization method, It is produced by containing it in microcapsules by various encapsulation methods such as the 1n-situ method, and coating the dispersion liquid dispersed 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. Various types of so-called stand-alone copying sheets, etc., in which dye capsules and coloring agent coexist on the same surface, are produced by applying a coating liquid containing a mixture of dye capsules and coloring agent, or by applying a coloring agent coating liquid on top of a dye capsule dispersion. As mentioned above, this includes the following forms.

In addition, the usage ratio of basic dye and coloring agent depends on the desired coating amount,
Since it varies depending on various conditions such as the form of the pressure-sensitive recording medium, the encapsulation method, the composition of the coating liquid including various auxiliary agents, and the coating method, it may be selected appropriately according to 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. 4B-4383
No. 0, No. 49-69, No. 49-70, No. 52-20
142, etc., and the salicylic acid derivative or its metal salt of the present invention can be applied to these various types of heat-sensitive recording materials.

- For boat fishing, a coating liquid obtained by dispersing the salicylic acid derivative of the present invention or its metal salt and fine particles of a basic dye in a medium in which a binder is melted 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 generally the basic dye is 100%
50 to 700 parts by weight, preferably 100 parts by weight
A color former in the range of 500 parts by weight is used.

In addition, for the purpose of improving coloring ability, matting the surface of the recording layer, improving writing properties, etc., inorganic pigments are 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 the coloring agent. It can be used in combination with about parts by weight, and further includes, for example, a dispersant, an ultraviolet absorber, a thermofusible substance (recording sensitivity improver as described above),
Various auxiliary agents such as antifoaming agents, fluorescent dyes, and colored dyes can be used in combination as necessary.

As mentioned above, the heat-sensitive recording material of the present invention is generally manufactured by coating a support with a coating liquid in which fine particles of a basic dye and a coloring agent are dispersed. The support may be overcoated with two types of coating liquids dispersed in the same material, or may be produced 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/po is applied. Furthermore, for the purpose of protecting the recording layer or improving writing properties, dry weight of 0.2 to 10 g/bo, preferably 0.5 to 5 g/r is added to the recording layer.
Of course, it is also possible to provide an overcoat layer or an undercoat layer on the support, and various known techniques in the field of heat-sensitive recording material production can be added as appropriate.

Examples of the binder include starches, cellulose, proteins, gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer salt, acetic acid bee-maleic anhydride copolymer salt, polyacrylate, and styrene-butadiene copolymer. Polymer emulsions and the like are appropriately selected and used.

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 containing a conductive substance, a basic dye, and a coloring agent 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. In addition, both the dye and the coloring agent are 70%
If it does not melt in the preferred temperature range of ~120°C, the sensitivity to Joule heat can be adjusted by using a suitable thermofusible substance.

Thus, the recording material obtained by the present invention has excellent color development, and even when exposed to high temperature or high humidity environments or in contact with chemicals, the white paper area does not develop color or the recorded image does not change color. It has extremely well-balanced properties in terms of quality.

"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 6 parts of 3-(N-ethyl-N-isoamylamino)=6-methyl-7-phenylamitofluorane were dissolved in 100 parts of isopropylated naphthalene, and 25 parts of big skin gelatin having an isoelectric point of 8 were dissolved. 35 by dissolving 25 parts of gum arabic
It was added to 0 parts 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 25 parts of geltaraldehyde.
% aqueous solution was added to harden the capsules.

This capsule-containing coating liquid was coated on one side of a 45 g/rrT base paper so that the dry weight was 5 g/rrr to obtain a color former sheet.

On the other hand, a coloring agent prepared by dispersing 20 parts of zinc salt of 4-(3-benzoyloxyfurobyloxy) salicylic acid, 80 parts of kaolin, and 30 parts of styrene-butadiene copolymer emulsion (solid content: 50%) in 200 parts of water. Coating liquid, 45 g/
Coat it on rd base paper so that the dry weight is 5g/bo,
A coloring agent sheet was obtained.

When the thus prepared coloring agent sheet and coloring agent sheet were stacked and pressed so that the capsule-coated surface and the coloring agent-coated surface were in contact with each other, a black image was instantly obtained. This image had high density (and excellent light resistance).

Examples 2 to 4 Example 1 except that in the coloring agent coating liquid of Example 1, the following coloring agent was used instead of 20 parts of zinc salt of 4-(3-benzoyloxypro-ruoxy)salicylic acid. A coloring agent sheet was obtained in the same manner as above.

Example 2: 20 parts of the zinc salt of 5-(4-p-methylbenzoyloxybutyloxy)salicylic acid Example 3: 20 parts of the zinc salt of 4-(3-octanoyloxypropyloxy)salicylic acid Example 4: 3. 5 to 10 parts of zinc salt of bis(α-methylbenzyl)salicylic acid 10 parts of zinc salt of 4-(3-benzoyloxypropyloxy)salicylic acid Evaluation of these colored sheets was carried out in the same manner as in Example 1, and the printed image was A coloring agent sheet with high concentration and excellent light resistance was obtained.

Example 5 ■ Preparation of liquid A 3-dibutylamino-6-methyl-7-phenylaminofluorane 10 parts 1.2-bis(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 liquid B.

Zinc salt of 4-(3-benzoyloxypropyloxy)salicylic acid 30 parts Methylcellulose 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 1
80 m1/100 g), 150 parts of a 20% oxidized starch aqueous solution, and 210 parts of water were mixed and stirred to prepare a recording layer coating liquid. The obtained coating liquid was applied to a base paper of 50 g/rrT so that the dry weight was 6.0 g/rrf and dried to obtain a thermosensitive recording paper.

Examples 6 to 12 Seven types of heat-sensitive products were prepared in the same manner as in Example 5, except that the following compound was used instead of the zinc salt of 4-(3-benzoyloxypropyloxy) salicylic acid in the preparation of Solution B I got the recording paper.

Example 6: Zinc salt of 4-(3-p-methoxybenzoyloxypropyloxy) salicylic acid Example 7: Zinc salt of 4-(2-p-chlorobenzoyloxyethoxy) salicylic acid Example 8: 4- (3- Zinc salt of p-(2-phenoxyethoxy)benzoyloxypropyloxysalicylic acid Example 9: 4-(6-(2-naphthoyloxy)
Zinc salt of hexyloxyfusalicylic acidExample 10: Zinc salt of 4-(3-octanoyloxypropyloxy)salicylic acidExample 11: Calcium salt of 5-(3-phenoxyacetitoxypropyloxy)salicylic acidExample 12:5 - Magnesium of (3-cyclohexylcarbonyloxypropyloxy) salicylic acid Example 13 In the preparation of Solution B of Example 5, 30 parts of zinc salt of 4-(3-benzoyloxypropyloxy) salicylic acid, 1 part of water
Instead of 10 parts, 30 parts of 4-(3-p-methoxybenzoyloxypropyloxy) salicylic acid, 3 parts of zinc oxide
A thermosensitive recording paper was obtained in the same manner as in Example 5 except that 0 parts and 80 parts of water were used.

Examples 14-22 Example 13(7)B:e, prepared nioty, 4-(3-p
Nine types of thermal recording paper were obtained in the same manner as in Example 13, except that the following compound was used instead of methoxybenzoyloxypropyloxy)salicylic acid.

Example 14: 4-(4-p-Methylbenzoyloxybutyloxy) salicylic acid Example 15: 4-(3-p-benzyloxybenzoyloxypropyloxy) salicylic acid Example 16: 5-(5-benzoyloxy- 3 oxa-
Pentyloxy)salicylic acid Example 17: 4-(3-p-(2-p-methoxyphenoxyethoxy)benzoyloxypropyloxysalicylic acid Example 18: 4-(3-oleoyloxypropyloxy)salicylic acid Example 19 : 4-(3-cinnamoyloxypropyloxy)salicylic acid Example 20: 4-[2-(2-naphthylacetyloxy)ethoxy]salicylic acid Example 21: 4-(3-p-isopropyloxybenzoyloxypropyloxy) ) Zinc salt of salicylic acid Example 22: Zinc salt of 4-(3-(2-phenoxyethoxy)benzoyloxypropyloxysalicylic acid Comparative Examples 1 to 3) Example 50 In the preparation of solution B, 4-(3-benzoyloxypropyl Instead of the zinc salt of oxy)salicylic acid,
3 in the same manner as in Example 5 except that the following compounds were used.
Various types of thermal recording paper were obtained.

Comparative example 1: 4.4'-isopropylidene diphenol Comparative example 2: Zinc salt of 3,5-bis(α-methylbenzyl)salicylic acid Comparative example 3: Zinc salt of 4-dodecyloxysalicylic acid 21 types thus obtained The color density was measured using a Macbeth densitometer (RD-9).
The results are shown in Table 1.

In addition, after leaving the thermal recording paper after the above recording under high temperature drying conditions of 60°C for 20 hours, and at 40°C 290% R, 11,
After being left for 20 hours under the high humidity conditions, the color density of each recorded image was measured again using a Macbeth densitometer to evaluate the heat resistance and moisture resistance of the recorded images, and the results are shown in Table 1.

Furthermore, in order to evaluate the chemical resistance, a vinyl chloride film was layered on the colored side of the recording paper and left at room temperature for 20 hours (preparation resistance), and when ethanol was applied to the colored side (ethanol resistance). ) and the case where cottonseed oil was applied to the coloring surface (oil resistance), the degree of fogging in the blank area and fading of the recorded image was evaluated, and the results are shown in Table 1.

The evaluation criteria were as follows.

◎: Very good.

○: Excellent.

Δ: Practical level.

×: Impossible for practical use.

"Effects J As is clear from the results in Table 1, the recording material according to the present invention has a high color density and is an excellent recording material with excellent storage stability of recorded images, especially without fading of colored areas and background fogging caused by chemicals. Ta.

Table 1 Procedural amendment

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 that may have a substituent, an alkenyl group that may have a substituent, or a represents a cycloalkyl group which may have a substituent, 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 have an ether bond. 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 m represents 0 or an integer of 1 to 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.