JPH0672021A - Recording material - Google Patents

Abstract

PURPOSE:To improve shelf life, color developing properties by using special compound as dye precursor, aromatic carboxylic acid derivative or its polyvalent metal salt as a coloring agent and together using special phenol series compound, phenol resin. CONSTITUTION:One or more types of compound represented by a formula I is used as dye precursor. As a coloring agent aromatic carboxylic acid or polyvalent metal salt of zinc, etc., such as benzoic acid is used. Further, one or more types of phenolic compounds represented by formulae II-IV, phenolic resin having a partial structure represented by a formula V are used. In the formulae, R1 is alkyl group, alkoxyalkyl group, aryl group, R2, R3 are alkyl group, aryl group, R4 is arylkyl group, aryl group, amino group, R5, R6 are alkoxy group, alkyl group, a halogen atom, p is 0.1-5, q is 0.1-4. R7-R12 are hydrogen atom, halogen atom, hydroxyl group, amino group, alkyl group, aryl group, alkoxy group, carbamoyl group, etc., X is hydrogen atom or eliminable group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material, which is particularly excellent in raw storability, recorded image storability and color development.
Moreover, the present invention relates to a recording material capable of obtaining a blue or dark blue color image.

[0002]

2. Description of the Related Art A recording material utilizing a color reaction between a colorless or light-colored dye precursor and an organic or inorganic coloring agent is typified by a pressure-sensitive recording material, a heat-sensitive recording material, an electric heat-sensitive recording material and the like. Various things are known. These recording materials should have sufficient recording density and recording sensitivity,
It is required to have excellent storability of recorded images under external environmental conditions such as high temperature, high humidity, light exposure, chemical contact, etc., and performance such as background color development is not required, but currently these are completely satisfied. Things have not been obtained.

For example, the thermal recording material has been diversified in its fields of application and forms in association with the recent remarkable progress of the thermal recording system, and not only as a recording medium for a thermal facsimile or a thermal printer, but also as a POS (Point of Sales). ) The use for new applications such as labels, ATMs, and handy terminals is rapidly increasing. However, conventional thermal recording media are subject to discoloration of the printed area and background areas when stored under high temperature and high humidity conditions, in contact with plasticizers, solvents, oils and fats, and used under sunlight exposure conditions. It has a drawback that it causes a fog.

For the purpose of improving the above-mentioned drawbacks, a method of providing a protective layer of various polymer compounds on the heat-sensitive recording layer has been proposed and put into practical use. However, heat resistance, moisture resistance,
The effects of plasticizer, light resistance, and chemical resistance are not sufficiently satisfactory. Since the thermal recording medium has such drawbacks, its use is currently subject to certain restrictions, and its improvement is strongly demanded.

As an approach from the side of the color-developing system for the purpose of improving the storability of the recorded image of the thermosensitive recording medium, recording using irreversible color-developing reactions such as chelate system, redox system and diazo coupling system has been conducted so far. Various materials have been studied. However, in the chelate method, the image fastness is sufficient but the sensitivity is low, and the background is colored by the metal compound. In the redox method, ground color is gradually generated by air oxidation. In the diazo coupling method, the system is unstable and the raw storability is poor, and fixing is required, so that the apparatus is complicated. Also,
The raw storability is improved by separating it from other materials by microencapsulation, but there are problems such as color density and paper cost. Due to such a drawback, none of the methods has been widely spread.

As one of recording materials utilizing such irreversible color development reaction, there is a recording material using a pyrazolone derivative leuco compound as a color former described in US Pat. No. 3,409,457. However, as a recording material using such a leuco compound, only one using the present compound alone has been proposed so far, and such a recording material has been put to practical use because of its insufficient coloring property. Not not.

[0007]

DISCLOSURE OF THE INVENTION The present inventors
By using a specific pyrazolone derivative leuco compound as a color former and an acidic substance as the color former, a recording material excellent in color developability and storability, particularly storability of recorded images has been proposed. However, although such a recording material is excellent in storability, its coloring color tone is generally limited to reddish purple to purple, so that its use is subject to certain restrictions. Further, it has been found that the storability of a recorded image is not always sufficient when it comes into contact with a plasticizer under high temperature conditions. The present invention has not only ordinary recorded image storability but also excellent plasticizer resistance in a high temperature environment, and excellent raw storability and color developability,
Moreover, it is intended to provide a recording material having a blue or deep blue color tone.

[0008]

The present invention relates to a recording material utilizing a reaction between a colorless or light-colored dye precursor and a color-forming agent capable of developing a color by contacting with the dye precursor. The compound represented by the following general formula [Chemical formula 1] is used as the colorant, and at least one kind of the aromatic carboxylic acid derivative or its polyvalent metal salt is used as the colorant. A recording material characterized by using at least one selected from the group consisting of a phenolic compound represented by 4] and a phenolic resin having a partial structure represented by the following general formula [Chemical formula 5].

[0009]

[Chemical 1]

[Wherein R ₁ represents an alkyl group, an alkoxyalkyl group or an aryl group which may have a substituent, R 1
₂ , R ₃ is an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ₄ may have an alkyl group which may have a substituent or a substituent. A good aryl group or an optionally substituted amino group is represented by R ₅ ,
R ₆ represents an alkyl group, an alkoxyl group or a halogen atom, p is 0 or an integer of 1 to 5, and q is 0.
Or the integer of 1-4 is shown. ]

[0011]

[Chemical 2]

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[In the formula, R _{7 to} R ₁₂ are each a hydrogen atom,
Halogen atom, hydroxyl group, amino group, optionally substituted alkyl group, optionally substituted alkoxyl group, optionally substituted aryl group, optionally substituted Carbamoyl group, sulfamoyl group which may have a substituent, alkylcarbonylamino group which may have a substituent, arylcarbonylamino group which may have a substituent, and ureido group which may have a substituent. , An aryloxycarbonyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an alkylsulfonylamino group which may have a substituent, an arylsulfonylamino which may have a substituent Group, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an aryloxy group which may have a substituent, X
Represents a hydrogen atom or a removable group. ]

By adopting such a constitution, the storability, particularly the plasticizer resistance of the recorded image, is remarkably improved, and the coloring property can be further improved, and the coloring color tone is blue or dark blue. It was possible to obtain the recording material of.

[0017]

The pyrazolone derivative leuco compound of the present invention is capable of activating the pyrazolone ring 4
It is known that a decomposition reaction occurs in which an acylamino group substituted at the position is eliminated together with a hydrogen atom of an adjacent amino group to form an azomethine dye.

The present invention has an important feature in that an aromatic carboxylic acid derivative or a polyvalent metal salt thereof is used as a color-developing colorant, and that a specific phenol compound or phenol resin is used in combination. . The phenolic compound and the phenolic resin used in the present invention are compounds similar to the coupler in the diazo coupling system or the cyan coupler in the silver salt color photograph, and an active methine group which may have a leaving group in the molecule. It is necessary that the compound has

In the dye precursor represented by the general formula [Chemical Formula 1], R ₁ represents an alkyl group, an alkoxyalkyl group or an aryl group which may have a substituent. Here, the aryl group means a phenyl group. , A naphthyl group or a heteroaromatic ring residue, and examples of the substituent thereof include an alkyl group, an alkoxyl group, and a halogen atom. Of these, R ₁ is preferably a C ₁ -C ₄ alkyl group or a phenyl group.

R ₂ and R ₃ each represent an alkyl group which may have a substituent or an aryl group which may have a substituent. The substituent of the alkyl group is an aryl group, an alkoxyl group or a hydroxyl group. , An alkylsulfonylamino group, etc., as the substituent of the aryl group, an alkyl group,
Examples thereof include an alkoxyl group and a halogen atom. Incidentally, R
₂ and R ₃ include, among these, a C _{1 to} C ₄ alkoxyl group, a hydroxyl group or C as a substituent.
₁ -C ₄ alkylsulfonyl group for the amino group which may have a C ₁ -C ₄ are preferred.

R ₄ is an alkyl group which may have a substituent,
An aryl group which may have a substituent or an amino group which may have a substituent is shown. As the substituent of the alkyl group, an aryl group, an alkoxyl group, an aryloxy group,
Examples thereof include an acylamino group, an N-substituted carbamoyl group, and an N-substituted sulfamoyl group, and examples of the substituent of the aryl group include an alkyl group, an alkoxyl group, an aryloxy group, a halogen atom, an arylalkyl group, an arylalkoxy group, and aryloxy. Examples thereof include an alkoxy group, an arylsulfonylalkoxy group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an N-substituted carbamoyl group and an N-substituted sulfamoyl group.

Further, examples of the substituent of the amino group include an alkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, and the like. It may have a substituent, and examples of the substituent of the alkyl group include an aryl group, an alkoxyl group, an aryloxy group, an acylamino group, an N-substituted carbamoyl group and an N-substituted sulfamoyl group. Is an alkyl group, an alkoxyl group, an aryloxy group, a halogen atom, an arylalkyl group, an arylalkoxy group, an aryloxyalkoxy group, an arylsulfonylalkoxy group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, N-
Examples thereof include a substituted carbamoyl group and an N-substituted sulfamoyl group.

Of these, R ₄ has light resistance,
In terms of chemical resistance, an arylcarbonylamino group represented by the following general formula [Chemical formula 6], [Chemical formula 7] or [Chemical formula 8] or a compound represented by the following general formula [Chemical formula 9], [Chemical formula 10] or [Chemical formula 11] The alkylcarbonylamino group represented by the formula is particularly preferable, the arylcarbonylamino group represented by the formula [Chemical formula 6] or [Chemical formula 7] is particularly preferable, and the arylcarbonylamino group represented by the general formula [Chemical formula 6] is particularly preferable.

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[Wherein R ₁₃ is a C ₁ -C ₄ alkyl group,
The C ₁ -C ₄ alkoxyl group or halogen atom is replaced by R
₁₄ is a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₄ alkoxyl group or a halogen atom, R ₁₅ is a C _{1 to} C ₂₅ alkyl group, Q is an ether bond or a sulfonyl bond, and A is A branched or straight chain C ₂ -C ₆ alkylene group,
A'represents a branched or linear C ₁ -C ₆ alkylene group,
r represents 0 or an integer of 1 to 5. ]

In the dye precursor represented by the general formula [Chemical Formula 1], R ₅ and R ₆ represent an alkyl group, an alkoxyl group or a halogen atom, and R ₅ is C ₁ -C
₄ alkyl groups, C ₁ -C ₄ alkoxyl groups or halogen atoms are preferred, and R ₆ is preferably C ₁ -C ₄ alkyl groups or C ₁ -C ₄ alkoxyl groups.
Further, p represents 0 or an integer of 1 to 5, but 0 or 1
An integer of 3 is preferred. Further, q represents 0 or an integer of 1 to 4, but 0 or 1 is preferable.

Specific examples of the compound represented by the general formula [Chemical Formula 1] include the following. 1-phenyl-3-
Methyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-methyl-4- (4-N, N-dimethylaminophenylamino) -4- Acetylamino-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3-
Methyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-methyl-4- (4-N, N-dimethylaminophenylamino) -4- Benzoylamino-5-pyrazolone, 1-phenyl-3-benzoylamino-4-
(4-N, N-diethylaminophenylamino) -4-
Benzoylamino-5-pyrazolone, 1-phenyl-3
-Phenyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1
-(2,4,6-Trichlorophenyl) -3-phenyl-4- (4-N, N-diethylaminophenylamino)
-4-Acetylamino-5-pyrazolone, 1-phenyl-3-benzoylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1- (2,4,6 -Trichlorophenyl)-
3-benzoylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-benzoylamino-4-
(4-N, N-diethylamino-2-methylphenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-benzoylamino-4- (4-N, N-diethylamino-2-methoxyphenylamino ) -4-Acetylamino-5-pyrazolone, 1-phenyl-3-acetylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone,
1-phenyl-3-stearoylamino-4- (4-
N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-phenylacetylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone , 1-phenyl-3- (3,4,5-trichlorophenylacetylamino) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- ( 3,4,5-Trimethylphenylacetylamino) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-
Pyrazolone, 1-phenyl-3-phenoxyacetylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (3,4,5-trichlorophenoxy Acetylamino) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1
-Phenyl-3- (3,4,5-trimethylphenoxyacetylamino) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-benzoylamino- 4- [4-
N-ethyl-N- (2-hydroxyethyl) amino-2
-Methylphenylamino] -4-acetylamino-5-
Pyrazolone, 1-phenyl-3-benzoylamino-4
-[4-N-Ethyl-N- (2-methylsulfonylaminoethyl) amino-2-methylphenylamino] -4-
Acetylamino-5-pyrazolone, 1-phenyl-3-
Benzoylamino-4- (4-N, N-dimethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-benzoylamino-4- [4-
N-ethyl-N- (2-hydroxyethyl) aminophenylamino] -4-acetylamino-5-pyrazolone,
1-phenyl-3-benzoylamino-4- [4-N-
Ethyl-N- (2-methoxyethyl) aminophenylamino] -4-acetylamino-5-pyrazolone, 1-
(4-chlorophenyl) -3-benzoylamino-4-
(4-N, N-diethylamino-2-methylphenylamino) -4-acetylamino-5-pyrazolone, 1-
(4-chlorophenyl) -3-benzoylamino-4-
(4-N, N-diethylaminophenylamino) -4-
Acetylamino-5-pyrazolone, 1- (2-chlorophenyl) -3-benzoylamino-4- (4-N, N-
Diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1- (2,4-dichlorophenyl)
-3-Benzoylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1- (4-methoxyphenyl) -3-benzoylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1
-P-tolyl-3-benzoylamino-4- (4-N,
N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (2-chlorobenzoylamino) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5 -Pyrazolone, 1-phenyl-3- (4-chlorobenzoylamino) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (3,4 , 5-Trichlorobenzoylamino) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (3,4,5-trimethylbenzoylamino) -4 -(4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (4-me Carboxymethyl benzoylamino) -4-
(4-N, N-diethylaminophenylamino) -4-
Acetylamino-5-pyrazolone, 1-phenyl-3-
(4-Methylbenzoylamino) -4- (4-N, N-
Diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- [3- (2,4
-Di-tert-pentylphenoxyacetylamino) benzoylamino] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1- (2,4,6-trichlorophenyl)- 3-
[3- (2,4-Di-tert-pentylphenoxyacetylamino) benzoylamino] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-
5-pyrazolone, 1-phenyl-3- [3- (phenoxyacetylamino) benzoylamino] -4- (4-
N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- [3-
(Phenylsulfonylamino) benzoylamino] -4
-(4-N, N-diethylaminophenylamino) -4
-Acetylamino-5-pyrazolone, 1-phenyl-3
-[3- (N-Phenylsulfamoyl) benzoylamino] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- [3- (N -Phenylcarbamoyl) benzoylamino] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- [4- (3-p-tolylsulfonylpropoxy) benzoyl Amino] -4- (4-N,
N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- [3- (3
-P-Tolylsulfonylpropoxy) benzoylamino] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- [4- (3-p-tolylsulfonyl) Propoxy) benzoylamino] -4- [4-N-ethyl-N-
(2-Hydroxyethyl) aminophenylamino] -4
-Acetylamino-5-pyrazolone, 1-phenyl-3
-[4- (3-p-Methoxyphenylsulfonylpropoxy) benzoylamino] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-
Pyrazolone, 1-phenyl-3- [4- (3-phenylsulfonylpropoxy) benzoylamino] -4- (4
-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- [4
-(3-p-Chlorophenylsulfonylpropoxy) benzoylamino] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- [4- (4-p -Tolylsulfonylbutoxy) benzoylamino] -4- (4-N, N
-Diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- [4- (2-
p-tolylsulfonylbutoxy) benzoylamino]-
4- (4-N, N-diethylaminophenylamino)-
4-acetylamino-5-pyrazolone, 1-phenyl-
3- {4- [3- (3,4,5-trimethylphenylsulfonyl) propoxy] benzoylamino} -4- (4
-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- {4
-[3- (3,4,5-Trichlorophenylsulfonyl) propoxy] benzoylamino} -4- (4-N,
N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- [4- (3
-Phenoxypropoxy) benzoylamino] -4-
(4-N, N-diethylaminophenylamino) -4-
Acetylamino-5-pyrazolone, 1-phenyl-3-
[4- (2-p-methoxyphenoxyethoxy) benzoylamino] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone,
1-phenyl-3- [4- (2-phenoxyethoxy)
Benzoylamino] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-anilino-4- (4-N, N
-Diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (2-chloroanilino) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1
-Phenyl-3- (4-methoxyanilino) -4- (4
-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-p-
Toluidino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1
-(2,4,6-Trichlorophenyl) -3-anilino-4- (4-N, N-diethylaminophenylamino)
-4-Acetylamino-5-pyrazolone, 1-phenyl-3- (2-chloroanilino) -4- (4-N, N-diethylamino-2-methylphenylamino) -4-acetylamino-5-pyrazolone and the like. Of course, the compounds are not limited to these compounds, and two or more compounds can be used in combination as required.

In the present invention, examples of the aromatic carboxylic acid derivative or its polyvalent metal salt used as a color former for the above-mentioned specific dye precursor include the following compounds. Benzoic acid, 4-tert-butylbenzoic acid, 4-
Trifluoromethylbenzoic acid, 4-chlorobenzoic acid, 4-
Nitrobenzoic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, α-
Naphthoic acid, β-naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, monomethyl terephthalate, gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid,
3,5-di-tert-butylsalicylic acid, 3-methyl-5
-Benzylsalicylic acid, 4-pentyloxysalicylic acid, 3-phenyl-5- (α, α-dimethylbenzyl)
Salicylic acid, 3,5-di- (α-methylbenzyl) salicylic acid, 2-hydroxy-1-benzyl-3-naphthoic acid, 3-dodecylsalicylic acid, 3-nonylsalicylic acid,
3-benzyl salicylic acid, 3- (α-methylbenzyl)
Salicylic acid, 3-chloro-5- (α-methylbenzyl)
Salicylic acid, 3,5-di- (α, α-dimethylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl)-
5-Methylsalicylic acid, 4- (3-phenylsulfonylpropoxy) salicylic acid, 5- (3-phenylsulfonylpropoxy) salicylic acid, 4- (4-phenylsulfonylbutoxy) salicylic acid, 4- (5-phenylsulfonyl-3-oxa- Pentyloxy) salicylic acid, 4-
(3-p-tolylsulfonylpropoxy) salicylic acid,
5- (3-p-tolylsulfonylpropoxy) salicylic acid, 4- (6-p-tolylsulfonylhexyloxy)
Salicylic acid, 4- (5-p-tolylsulfonyl-3-oxa-pentyloxy) salicylic acid, 4- (3-p-methoxyphenylsulfonylpropoxy) salicylic acid, 4
-(3-p-Chlorophenylsulfonylpropoxy) salicylic acid, 4- (2-phenoxyethoxy) salicylic acid, 4- (2-p-methoxyphenoxyethoxy) salicylic acid, 5- (2-p-methoxyphenoxy) salicylic acid, 4- ( 5-p-methoxyphenoxy-3-oxa-
Pentyloxy) salicylic acid, 4- (5-phenoxy-)
3-oxa-pentyloxy) salicylic acid, 4- (3-
p-methoxypropoxy) salicylic acid, 4- [p- (2
-Phenoxyethoxy) cumyl] salicylic acid, 5- [p
-(2-phenoxyethoxy) cumyl] salicylic acid, 5
-[P- (5-phenoxy-3-oxa-pentyloxy) cumyl] salicylic acid, 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] salicylic acid, 5- [p
Such as-(4-p-tolylsulfonylpropoxy) cumyl] salicylic acid, 5- [p- (3-phenylsulfonylpropoxy) cumyl] salicylic acid, 5- [p- (3-p-methoxyphenylsulfonylpropoxy) cumyl] salicylic acid. Aromatic carboxylic acid. Of course, it is not limited to these compounds, and it is also possible to use two or more kinds in combination.

As the polyvalent metal forming a salt with such an aromatic carboxylic acid, a divalent, trivalent or tetravalent metal is preferable, and zinc, calcium, aluminum, magnesium, tin and iron are particularly preferable.

In the present invention, the ratio of the specific dye precursor to the color former used is not particularly limited, but is generally 5 per 100 parts by weight of the dye precursor.
It is preferable to use the color former in the range of 0 to 700 parts by weight, preferably 100 to 500 parts by weight.

In the present invention, the phenol compound and the phenol resin used together with the specific dye precursor and the aromatic carboxylic acid derivative or the polyvalent metal salt thereof as the coloring agent are represented by the following general formula: , [Chemical Formula 3] and [Chemical Formula 4], and at least one selected from resins having a partial structure represented by the following general formula [Chemical Formula 5].

[0037]

[Chemical 2]

[0038]

[Chemical 3]

[0039]

[Chemical 4]

[0040]

[Chemical 5]

[In the formula, R _{7 to} R ₁₂ are each a hydrogen atom,
Halogen atom, hydroxyl group, amino group, optionally substituted alkyl group, optionally substituted alkoxyl group, optionally substituted aryl group, optionally substituted Carbamoyl group, sulfamoyl group which may have a substituent, alkylcarbonylamino group which may have a substituent, arylcarbonylamino group which may have a substituent, and ureido group which may have a substituent. , An aryloxycarbonyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an alkylsulfonylamino group which may have a substituent, an arylsulfonylamino which may have a substituent Group, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an aryloxy group which may have a substituent, X
Represents a hydrogen atom or a removable group. ]

The general formulas [Chemical formula 2], [Chemical formula 3], [Chemical formula 4]
In [Chemical Formula 5] and [Chemical Formula 5], some of the same symbols are used to represent the substituents, but this is merely to avoid redundant description of the substituents.

Of the phenolic compounds represented by the general formulas [Chemical Formula 2], [Chemical Formula 3] and [Chemical Formula 4] and the phenolic resin having the partial structure represented by the general formula [Chemical Formula 5], the general formula A phenolic compound represented by [Chemical Formula 2] or [Chemical Formula 3] and a phenol resin having a partial structure represented by the general formula [Chemical Formula 5] are preferable. In addition,
In the general formulas [Chemical Formula 2], [Chemical Formula 3], [Chemical Formula 4] and [Chemical Formula 5], the removable group represented by X is a halogen atom, an alkoxyl group which may have a substituent or a substituent. And an arylthio group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, and the like.

Among the phenolic compounds represented by the general formula [Chemical Formula 2], 1 to 2 of the substituents represented by R _{7 to} R ₁₀ are ureido groups and N'-alkylureido groups,
A N′-phenylalkylureido group which may have a nuclear substituent, an N′-phenoxyalkylureido group which may have a nuclear substituent, an N′-phenylureido group which may have a nuclear substituent, An alkylcarbonylamino group, a phenylalkylcarbonylamino group which may have a nuclear substituent, a phenoxyalkylcarbonylamino group which may have a nuclear substituent, or a phenylcarbonylamino group which may have a nuclear substituent. And a compound in which other substituents including X are hydrogen atoms is preferable. Here, preferably an alkyl group of C ₁ -C ₂₀ as an alkyl group constituting N'- alkylureido group and alkylcarbonylamino group. In addition, an N'-phenylalkylureido group,
The alkyl constituting the N'-phenoxyalkylureido group, the phenylalkylcarbonylamino group, and the phenoxyalkylcarbonylamino group is C ₁ -C ₆
Branched or straight chain alkylene is preferred. Further, as the nuclear substituent, a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₄ alkoxyl group and a halogen atom are preferable, and each phenyl group may have 1 to 5 of these nuclear substituents. Good.

In the phenolic compounds represented by the general formulas [Chemical Formula 3] and [Chemical Formula 4], 1 to 2 of the substituents represented by R _{7 to} R ₁₂ are carbamoyl groups or alkylcarbamoyl groups. A phenylalkylcarbamoyl group which may have a nuclear substituent, a phenoxyalkylcarbamoyl group which may have a nuclear substituent, or a phenylcarbamoyl group which may have a nuclear substituent, and includes X A compound in which the other substituent is a hydrogen atom is preferable.
Here, the alkyl group forming the alkylcarbamoyl group is preferably a C _{1 to} C ₂₀ alkyl group. The alkyl group constituting the phenylalkylcarbamoyl group and the phenoxyalkylcarbamoyl group is C _1-
C ₆ branched or straight chain alkylene is preferred. Furthermore,
As the nuclear substituent, a C _{1 to} C ₅ alkyl group, C _{1 to} C
The alkoxyl group of ₄ and a halogen atom are preferable, and each phenyl group may have 1 to 5 of these nuclear substituents.

Examples of such phenol compounds include the following. Phenol, p-methoxyphenol, m-methoxyphenol, guaiacol, p-
Chlorophenol, o-chlorophenol, m-aminophenol, o-aminophenol, m-acetylaminophenol, m-benzoylaminophenol, resorcinol, catechol, pyrogallol, p- (methylthio) phenol, m- (methylthio) phenol,
2,5-Dimethylphenol, (4-hydroxyphenylthio) acetic acid-2- (4-hydroxyphenylthio) ethyl ester, n-octyl gallate, n-propyl gallate, 4,4'-thiodiphenol, 4 -(Benzylthio) phenol, 4- (phenylthio) phenol,
2-methylresorcinol, 4-chlororesorcinol, 4- (dodecylthio) catechol, 2,6-dimethoxyphenol, m-cresol, 4-methylthio-m.
-Cresol, 2-acetylaminophenol, 2-propionylaminophenol, 2,4-dichloro-6-
Acetylaminophenol, 2,4-dichloro-3-methyl-6-acetylaminophenol, 2-phenoxyacetylamino-5-methylphenol, 2-phenoxyacetylaminophenol, 2-benzoylaminophenol, 2-phenylacetylaminophenol Two
-Benzoylamino-1-naphthol, 8-benzoylamino-1-naphthol, 3-hydroxyphenylurea, 2-hydroxyphenylurea, 1,3-bis (3
-Hydroxyphenyl) urea, 2- (3-N-octylureido) phenol, 1,3-bis (2-hydroxyphenyl) urea, 2- (3-N-phenylureido) phenol, 2,5-diacetylaminophenol , 2,4-dichloro-3-methyl-6-phenoxyacetylaminophenol, 2- [2- (2,4-di-te
rt-Pentylphenoxy) butyrylamino] phenol, 2-acetylamino-5- (2-phenoxybutyrylamino) phenol, 2-acetylamino-5- [2
-(2,4-Di-tert-pentylphenoxy) butyrylamino] phenol, 2-acetylamino-5-phenoxyacetylaminophenol, 2,4-dichloro-3
-Methyl-6- [2- (2,4-di-tert-pentylphenoxy) butyrylamino] phenol, 2- (3-N
-Phenylureido) -5- [2- (2,4-di-tert
-Pentylphenoxy) butyrylamino] phenol,
2-benzoylamino-5-phenoxyacetylaminophenol, 2-acetylamino-4-methoxyphenol, α-naphthol, β-naphthol, 1-hydroxy-2-naphthanilide, 1-hydroxy-2-phenyl naphthoate, 4- Methoxy-1-naphthol, 4-chloro-1-naphthol, 2-hydroxy-3-naphthanilide, 4-phenylthio-1-naphthol, 4- (p
-Chlorophenylthio) -1-naphthol, 6-benzylthio-2-naphthol, 4-methylthio-1-naphthol, 4-benzylthio-1-naphthol, 4-n-octylthio-1-naphthol, 6- (p-chlorophenylthio) ) -2-Naphthol, 6-bromo-2-naphthol, 2,3-dihydroxynaphthol, 6-dodecylthio-2-naphthol, 2-N-methylcarbamoyl-1
-Naphthol, 2-N-benzylcarbamoyl-1-naphthol, 2-N- [4- (2,4-di-tert-pentylphenoxy) butyl] carbamoyl-1-naphthol, 2-N- [4- (2 , 4-Di-tert-pentylphenoxy) butyl] carbamoyl-4-chloro-1-naphthol, 2-N- [3- (2,4-di-tert-pentylphenoxy) propyl] carbamoyl-1-naphthol, 2 -N- (3-phenoxypropyl) carbamoyl-1-naphthol, 2-N-dodecylcarbamoyl-1
-Naphthol, 1-hydroxy-4-phenylthio-2
-Naphthoanilide, 4- (2-carboxymethylthioethoxy) -2-N-phenylcarbamoyl-1-naphthol, 2-N- {3-N- [4- (2,4-di-tert-
Pentylphenoxy) butyl] sulfamoylphenyl} carbamoyl-1-naphthol, 2-N- (4-phenoxybutyl) carbamoyl-4-methoxy-1-naphthol, 3-N- (3-phenoxypropyl) carbamoyl-2- Naphthol, 3-N-phenylcarbamoyl-6-benzylthio-2-naphthol, 2-N-phenylcarbamoyl-4-benzylthio-1-naphthol and the like.

Further, in the present invention, a phenol resin having a partial structure represented by the general formula [Chemical Formula 5] may be used in place of the above-mentioned phenol compound. In such a phenol resin, R ₇ and R ₈ are each a hydrogen atom, a C ₁ -C ₄ alkyl group or C ₁
An alkoxyl group -C _4, and X is a hydrogen atom, number of nuclei of the phenol nucleus preferably has 2 to 20. Further, a phenol resin in which 50 to 100% of the total phenol nucleus has a partial structure represented by the general formula [Chemical Formula 5] is preferable. Specific examples of such a phenol resin include, for example, 2,2′-dihydroxydiphenylmethane,
2,6-bis (2'-hydroxybenzyl) phenol, compounds represented by the following general formula [Chemical formula 12], and linear oligomers such as high ortho novolac resin, calix [4] arene, calix [6] arene and calix [8] Examples include cyclic oligomers such as arenes.

[0048]

[Chemical 12]

Specific examples of the phenolic compound and the phenol resin are not limited to these, and two or more kinds can be used in combination. The proportion of the phenolic compound or phenolic resin used is not particularly limited, but is generally 1 to 500 parts by weight, preferably 10 to 30 parts by weight with respect to 100 parts by weight of the dye precursor.
It is preferably used in the range of about 0 parts by weight.

In the present invention, when a metal compound is contained in the recording material together with the color former, the characteristics as a recording material can be further improved. The metal compound referred to here is an oxide of a divalent, trivalent or tetravalent metal, for example, a metal selected from zinc, magnesium, barium, calcium, aluminum, tin, titanium, nickel, cobalt, manganese, iron and the like. Examples thereof include hydroxides, sulfides, halides, carbonates, phosphates, silicates, sulfates, nitrates, and halogen complex salts, and of these, zinc compounds are particularly preferable. Specific examples of the metal compound include zinc oxide, zinc hydroxide, zinc aluminate, zinc sulfide,
Examples include zinc carbonate, zinc phosphate, zinc silicate, aluminum oxide, magnesium oxide, titanium oxide, aluminum hydroxide, aluminum silicate, aluminum phosphate, magnesium aluminate, magnesium hydroxide, magnesium carbonate, magnesium phosphate and the like. be able to.

The use ratio of these metal compounds is not necessarily limited, but usually, the coloring agent 100 is used.
1 to 500 parts by weight, preferably 5 to 30 parts by weight
It is preferably used in the range of about 0 parts by weight.

The present invention uses the above-mentioned specific pyrazolone derivative leuco compound as a dye precursor, but if necessary, known basic dyes may be used as long as they do not impair the desired effects of the present invention. Can also be used together. Specific examples of such known basic dyes 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,
Triarylmethane dyes such as 3-p-dimethylaminophenyl-3- (1-methylpyrrol-3-yl) -6-dimethylaminophthalide, 4,4'-bis-dimethylaminobenzhydrylbenzyl ether, Diphenylmethane dyes such as N-halophenyl-leuco auramine and N-2,4,5-trichlorophenyl leuco auramine, 3,3-bis [1,1-bis (4-pyrrolidinophenyl) ethylene-2-yl ] -4,5,6,7-Tetrabromophthalide, 3,3-bis [1- (4-methoxyphenyl) -1- (4-dimethylaminophenyl) ethylene-2-yl] -4,5, 6,7-Tetrachlorophthalide, 3,3-bis [1- (4-methoxyphenyl) -1
-(4-Pyrrolidinophenyl) ethylene-2-yl]-
Divinylphthalide dyes such as 4,5,6,7-tetrachlorophthalide, benzoyl leuco methylene blue, p-
Thiazine dyes such as nitrobenzoyl leuco methylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-
Spiro dyes such as dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho (6'-methoxybenzo) spiropyran, 3-propyl-spiro-dibenzopyran, rhodamine-B-anilinolactam, rhodamine (p- Lactam dyes such as nitroanilino) lactam and rhodamine (o-chloroanilino) lactam,
3-Dimethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7 -Chlorofluorane, 3-diethylamino-
6,7-Dimethylfluorane, 3- (N-ethyl-p-
Toluidino) -7-methylfluorane, 3-diethylamino-7- (N-acetyl-N-methylamino) fluorane, 3-diethylamino-7-N-methylaminofluorane, 3-diethylamino-7-dibenzylaminofluor Oran, 3-diethylamino-7- (N-methyl-N
-Benzylamino) fluorane, 3-diethylamino-
7- (N-chloroethyl-N-methylamino) fluorane, 3-diethylamino-7-N-diethylaminofluorane, 4-benzylamino-8-diethylamino-benzo [a] fluorane, 3- [4- (4-dimethyl) Aminoanilino) anilino] -7-chloro-6-methylfluorane, 8- [4- (4-dimethylaminoanilino) anilino] -benzo [a] fluorane, 3- (N-ethyl-p-toluidino) -6-Methyl-7-phenylaminofluorane, 3- (N-ethyl-p-toluidino) -6
-Methyl-7- (p-toluidino) fluorane, 3-diethylamino-6-methyl-7-phenylaminofluorane, 3-dimethylamino-6-methyl-7-phenylaminofluorane, 3-di-n-butyl Amino-6-methyl-7-phenylaminofluorane, 3-di-n-pentylamino-6-methyl7-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) fluorane, 3-di-n
-Butylamino-7- (o-chlorophenylamino) fluorane, 3- (N-ethyl-Nn-hexylamino) -7- (o-chlorophenylamino) fluorane,
3- (N-ethyl-N-isoamylamino) -7- (o
-Chlorophenylamino) fluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-phenylaminofluorane, 3- (N-methyl-
N-n-propylamino) -6-methyl-7-phenylaminofluorane, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-phenylaminofluorane, 3- (N-methyl-) Nn-hexylamino) -6
-Methyl-7-phenylaminofluorane, 3- [N-
(3-Ethoxypropyl) -N-methylamino] -6-
Methyl-7-phenylaminofluorane, 3- [N-ethyl-N- (3-ethoxypropyl) amino] -6-methyl-7-phenylaminofluorane, 3-diethylamino-7- [m- (trifluoro Methyl) phenylamino] fluorane, 3-diethylamino-7- (o-fluorophenylamino) fluorane, 3-dibutylamino-7- (o-fluorophenylamino) fluorane, 3
-Diethylamino-6-chloro-7-phenylaminofluorane, 3- (N-ethyl-Nn-hexylamino) -6-methyl-7-phenylaminofluorane, 3
-(N-ethyl-N-cyclopentylamino) -6-methyl-7-phenylaminofluorane, 2,2-bis {4- [6 '-(N-cyclohexyl-N-methylamino) -3'-methylspiro Fluorane dyes such as [phthalide-3,9′-xanthene] -2′-ylamino] phenyl} propane, 3,6-bis (dimethylamino) fluorene-9-spiro-3 ′-(6′-dimethylamino) Phthalide, 3-diethylamino-6- (N-allyl-N-methylaminofluorene-9-spiro-3'-
(6'-Dimethylamino) phthalide, 3,6-bis (dimethylamino) -spiro [fluorene-9,6'-6 '
H-chromeno (4,3-b) indole], 3,6-bis (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 dyes may be used in combination.

When these basic dyes are used in combination with the dye precursor of the present invention, about 0.2 to 20 parts by weight of the above general basic dye is added to 10 parts by weight of the dye precursor. It is desirable to mix in a ratio. Further, in the present invention, if necessary, a known color developing agent may be further used in combination within a range that does not impair the desired effects of the present invention.

Further, for example, in a thermosensitive recording medium, various heat fusible substances can be used as a recording sensitivity improving agent in order to obtain high speed recording property. Examples of such a heat-fusible substance include the following. Caproic acid amide, capric acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, erucic acid amide, linoleic acid amide, linolenic acid amide, N-methylstearic acid amide, stearic acid anilide, N-methyloleic acid amide, Benzanilide, linoleic acid anilide,
N-ethylcapric acid amide, N-butyllauric acid amide, N-octadecylacetamide, N-oleinacetamide, N-oleylbenzamide, N-stearylcyclohexylamide, polyethylene glycol, 1
-Benzyloxynaphthalene, 2-benzyloxynaphthalene, 1-hydroxynaphthoic acid phenyl ester,
1,2-diphenoxyethane, 1,4-diphenoxybutane, 1,2-bis (3-methylphenoxy) ethane,
1,2-bis (4-methoxyphenoxy) ethane, 1-
Phenoxy-2- (4-chlorophenoxy) ethane, 1
-Phenoxy-2- (4-methoxyphenoxy) ethane, 1- (2-methylphenoxy) -2- (4-methoxyphenoxy) ethane, terephthalic acid dibenzyl ester, oxalic acid dibenzyl ester, oxalic acid di (4- Methylbenzyl) ester, p-benzyloxybenzoic acid benzyl ester, p-benzylbiphenyl, 1,5-
Bis (p-methoxyphenoxy) -3-oxa-pentane, 1,4-bis (2-vinyloxyethoxy) benzene, p-biphenyl-p-tolyl ether, benzyl-
p-methylthiophenyl ether, 2,2'-methylenebis (4-methyl-6-tert-butylphenol),
2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert
-Butyl-3-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (5-cyclohexyl-4-hydroxy-) 2-methylphenyl) butane,
Benzotriazole, 1-N-hydroxy-benzotriazole, 1-N-benzoyl-benzotriazole,
1-N-acetyl-benzotriazole, 2- (2'-
Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ',-5'-di-tert
-Butylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-
5'-methylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert
-Amylphenyl) benzotriazole, 2- (2'-
Hydroxy-3 ', 5'-di-tert-butylphenyl)
Benzotriazole, 2- (2'-hydroxy-5'-
tert-butylphenyl) benzotriazole, 2-
(2'-hydroxy-5'-tert-octylphenyl)
-Benzotriazole, 2- [2'-hydroxy-
3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] benzotriazole and the like.

The amount of the heat-fusible substance used is not particularly limited, but generally 50 to 700 parts by weight, preferably 100 to 500 parts by weight, relative to 100 parts by weight of the dye precursor.
It is desirable to adjust in the range of parts by weight.

In the following, as a dye precursor, a compound represented by the general formula:
In addition to using the compound represented by the formula (1) and using an aromatic carboxylic acid or a polyvalent metal salt thereof as the colorant, a phenolic compound represented by the general formula (2) to (4) or the general formula (5) ] Various typical recording materials in combination with a phenol resin having a partial structure represented by the above will be specifically described. In addition, below, a phenolic compound and a phenol resin are generically described as a phenolic compound.

A pressure-sensitive recording medium is disclosed in, for example, US Pat. No. 2,505,47.
0, 2,505,471, 2,505,489, 2,548,366
No., No. 2,712,507, No. 2,730,456, No. 2,730, 457
No. 3,418,250, No. 3,924,027, No. 4,010,038, etc., there are various forms, and the present invention can be applied to pressure-sensitive recording materials of these various forms.

Generally, a coloring agent coating solution prepared by dispersing the coloring agent and the phenol compound of the present invention together with a pigment in various binders such as styrene / butadiene copolymer latex and polyvinyl alcohol is used for paper and plastic. A color-developing agent sheet (so-called lower sheet) is manufactured by applying it on a suitable support such as a sheet or resin coated paper.

On the other hand, a color former sheet (so-called upper sheet) used in combination with the above color former sheet is prepared by adding the dye precursor of the present invention to alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl. Synthetic oils such as; vegetable oils such as cottonseed oil and castor oil; animal oils; mineral oils, or a dispersion obtained by dissolving them in a suitable solvent consisting of a mixture thereof, etc. in a binder, or the above solution by a coacervation method. , Interfacial polymerization method, in-s
It is produced by coating a suitable support such as paper, plastic sheet or resin coated paper with a dispersion liquid which is contained in microcapsules and dispersed in a binder by various encapsulation methods such as in situ method.

Of course, a so-called intermediate sheet in which the above-mentioned coloring agent coating liquid is applied to one side of the support and the dye dispersion or dye capsule dispersion is applied to the other side, and further, a dye capsule is applied to the same side of the support. A so-called unity feeling in which a dye capsule and a colorant coexist on the same surface by applying a colorant-mixing coating liquid or a dye capsule dispersion liquid and then applying a colorant coating liquid. A form such as a pressure copy sheet is also possible.

The proportions of the dye precursor, the coloring agent and the phenolic compound used are the desired coating amount, the form of the pressure-sensitive recording material, the encapsulation method, the composition of the coating solution including various other auxiliaries, and the coating method. Since it depends on various conditions such as the above, it may be appropriately selected according to the conditions.

The heat-sensitive recording material is, for example, Japanese Patent Publication No. 44-3680,
44-27880, 45-14039, 48-43830, 49
There are various forms as described in No. 69, No. 49-70, No. 52-20142, etc., and the color forming system of the present invention can be applied to these various forms of heat-sensitive recording materials.

Generally, a coating solution obtained by dispersing the dye precursor of the present invention, a color former, and a phenolic compound in a medium in which a binder is dissolved or dispersed is used as a paper, a plastic film, a synthetic paper or a nonwoven fabric. The thermosensitive recording medium of the present invention is produced by coating it on a suitable support such as a sheet or a molded product.

The use ratio of the dye precursor and the coloring agent in the recording layer is not particularly limited, but is generally 50 to 700 parts by weight, preferably 100 to 5 parts by weight per 100 parts by weight of the dye.
About 100 parts by weight of a coloring agent is used. The use ratio of the dye precursor and the phenolic compound in the recording layer is not particularly limited, but is generally 1 to 500 parts by weight, preferably 10 to 300 parts by weight per 100 parts by weight of the dye precursor. Phenolic compounds are used.

Further, for the purpose of improving the color-forming ability, matting the surface of the recording layer, and improving the writability, an inorganic pigment is generally used in an amount of 0.1 to 10 parts by weight, preferably 0.1 part by weight. 5
Can be used in combination of about 3 to 3 parts by weight, and further, for example, a dispersant, an ultraviolet absorber, a heat-fusible substance, an antifoaming agent, a fluorescent dye,
Various auxiliary agents such as coloring dyes can be appropriately used in combination as necessary.
As described above, the thermal recording material of the present invention is generally a dye precursor,
It is produced by coating a support with a coating liquid in which fine particles of a colorant and a phenolic compound are dispersed, and three kinds in which a dye precursor, a colorant and a phenolic compound are separately dispersed. Of course, the coating liquid may be applied over the support, and it is of course also possible to produce it by impregnation and papermaking.

There are no particular restrictions on the method for preparing the coating liquid, the coating method, etc., and the coating amount is generally about ² to 12 g / m ² in terms of dry weight. Further, for the purpose of protecting the recording layer on the recording layer, improving the writability, etc., a dry weight of 0.2 to 10 g / m ² , preferably 0.
It is of course possible to provide an overcoat layer of 5 to 5 g / m ² or to provide an undercoat layer on the support, and various known techniques in the field of producing a thermal recording medium can be appropriately added.

Examples of the binder include starches, celluloses, proteins, gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer salts,
A styrene-butadiene copolymer emulsion, vinyl acetate-maleic anhydride copolymer salt, polyacrylic acid salt, etc. are appropriately selected and used. The binder is blended in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, based on the total solid content of the coating liquid.

An electrically-conductive heat-sensitive recording material is disclosed, for example, in JP-A-49-11344.
No. 50-48930 and the like. In general, a conductive material, a dye precursor of the present invention, a colorant and a phenolic compound are dispersed together with a binder to apply a coating solution to a suitable support such as paper, or a conductive material is applied to the support. Forming a conductive layer on which the dye precursor,
It is manufactured by applying a coating liquid in which a color former and a phenolic compound are dispersed together with a binder. When neither the dye precursor nor the color former melts in a preferable temperature range of 70 to 120 ° C., the sensitivity to Joule heat can be adjusted by using an appropriate heat-fusible substance together.

The recording material of the present invention thus obtained is excellent in color developability, and even when exposed to a high temperature or high humidity environment or in contact with chemicals, the white paper part may develop color or the recorded image may be discolored. In addition, the recording material is excellent in plasticity resistance in a high temperature environment, and is capable of obtaining a blue or deep blue color image, and is extremely excellent in quality.

[0070]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% in an example show a weight part and weight%, respectively.

Example 1 [Preparation of Coloring Agent Sheet for Pressure Sensitive Recording Material] 6 parts of 1,3-diphenyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone was added to isopropyl. It was dissolved in 100 parts of modified naphthalene and added to 350 parts of warm water (50 ° C.) in which 25 parts of pigskin gelatin having an isoelectric point of 8 and 25 parts of gum arabic were dissolved and emulsified and dispersed. To this emulsion, add 1000 parts of warm water and adjust the pH to 4 with acetic acid.
After adjusting to 10 ° C., the mixture was cooled to 10 ° C., and 10 parts of a 25% aqueous solution of glutaraldehyde was added to cure the capsule. This capsule-containing coating liquid was applied onto one side of a base paper of 45 g / m ^{2 so} that the dry weight was 5 g / m ² , to obtain a color former sheet.

[Preparation of Coloring Agent Sheet for Pressure Sensitive Recording Material] Meanwhile, 200 parts of water, 20 parts of zinc salt of 3,5-di (α-methylbenzyl) salicylic acid, 3 parts of 2-benzoylaminophenol and 80 parts of kaolin Part, 30 parts of a styrene-butadiene copolymer emulsion (50% solid content) are dispersed in a coloring agent coating liquid, and a dry weight of 5 g / m is applied to 45 g / m ² of base paper.
Coating was performed so that the colorant sheet became ² . (Evaluation) The pressure-sensitive recording material obtained by stacking the color-developing agent sheet and the color-developing agent sheet thus prepared so that the capsule-coated surface and the color-developing agent-coated surface face each other, was written and pressed,
A blue image was obtained. Further, this image had high density and was excellent in solvent resistance and light resistance.

Examples 2 to 3 Two kinds of colorants were prepared in the same manner as in Example 1 except that the following phenolic compound was used in place of 3 parts of 2-benzoylaminophenol in the preparation of the color developing agent sheet of Example 1. A color developing agent sheet was obtained. Example 2: 2-acetylamino-5- [2- (2,4-
Di-tert-pentylphenoxy) butyrylamino] phenol 3 parts Example 3: 2-N- [3- (2,4-di-tert-pentylphenoxy) propyl] carbamoyl-1-naphthol 3 parts These colorant sheets The pressure-sensitive recording material using
When a color was developed in the same manner as above, a blue image was obtained in each case. Further, all of these images had high density and were excellent in solvent resistance and light resistance.

Example 4 Instead of 1,3-diphenyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone in the preparation of the color former sheet of Example 1, 1 -Phenyl-3-stearoylamino-4- (4
A color former sheet was obtained in the same manner as in Example 1 except that -N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone was used. When a pressure-sensitive recording material using this color-forming agent sheet was colored in the same manner as in Example 1, a blue image was obtained. This image had high density and was excellent in solvent resistance and light resistance.

Example 5 [Preparation of thermosensitive recording medium] Preparation of liquid A 1-phenyl-3-benzoylamino-4- (4-
N, N-Diethylaminophenylamino) -4-acetylamino-5-pyrazolone 10 parts Methylcellulose 5% aqueous solution 10 parts Water 20 parts This composition was ground with a sand mill until the average particle size was 1.5 μm. Preparation of solution B: 1,2-bis (3-methylphenoxy) ethane 3
0 part-Methylcellulose 5% aqueous solution 30 parts-Water 60 parts This composition was ground with a sand mill until the average particle size became 1.5 µm. Preparation of liquid C-Zinc salt of α-naphthoic acid 30 parts-Methylcellulose 5% aqueous solution 30 parts-Water 90 parts This composition was ground with a sand mill until the average particle size became 1.5 µm. Preparation of D liquid 2-Acetylaminophenol 5 parts Methylcellulose 5% aqueous solution 5 parts Water 10 parts This composition was ground with a sand mill until the average particle size became 1.5 μm. Formation of Recording Layer Liquid A 40 parts, liquid B 120 parts, liquid C 150 parts, liquid D 20
Parts, silicon oxide pigment (oil absorption: 180 ml / 100 g) 1
Mix 0 part, 75% 20% aqueous solution of oxidized starch, and 85 parts water.
The solution was stirred to obtain a coating liquid. The resulting coating liquid was applied to a base paper of 50 g / m ^{2 so} that the dry weight was 6.0 g / m ² , dried and supercalendered to obtain a heat-sensitive recording paper.

Examples 6 to 17 and Comparative Examples 1 to 2 Example 5 except that the following compound was used in place of 2-acetylaminophenol in the preparation of solution D of Example 5.
In the same manner as above, 14 kinds of thermal recording papers were obtained. -Example 6: 1-hydroxy-2-naphthanilide-Example 7: 2- (3-N-phenylureido) phenol-Example 8: 2-N- (3-phenoxypropyl) carbamoyl-1-naphthol-Implementation Example 9: 2-phenoxyacetylaminophenol Example 10: Phenolic resin represented by the following formula

[0077]

[Chemical 12]

Example 11: Calix [6] arene (phenolic resin represented by the following formula [Chemical Formula 13])

[0079]

[Chemical 13]

Example 12: 4- (2-Carboxymethylthioethoxy) -2-N-phenylcarbamoyl-1-
Naphthol Example 13: 2-benzoylamino-1-naphthol Example 14: 8-Benzoylamino-1-naphthol Example 15: 2-N-methylcarbamoyl-1-naphthol Example 16: 2-N -Benzylcarbamoyl-1-naphthol-Example 17: 2- (phenylacetylamino) phenol-Comparative Example 1: 4,4'-isopropylidibisphenol-Comparative Example 2: 4-hydroxy-4'-isopropoxydiphenylsulfone

Comparative Example 3 Except that the D liquid was removed in the formation of the recording layer of Example 5,
A thermal recording paper was obtained in the same manner as in Example 5.

Examples 18 to 23 In place of 1-phenyl-3-benzoylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone in the preparation of solution A of Example 5 In addition, 6 types of thermal recording papers were obtained in the same manner as in Example 5 except that the following compounds were used.

Example 18: 1-Phenyl-3- [4-
(3-p-Tolylsulfonylpropoxy) benzoylamino] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone Example 19: 1-phenyl-3- [4- ( 2-phenoxyethoxy) benzoylamino] -4- (4-N, N-
Diethylaminophenylamino) -4-acetylamino-5-pyrazolone Example 20: 1-phenyl-3-benzoylamino-4
-[4-N-Ethyl-N- (2-hydroxyethyl) aminophenylamino] -4-acetylamino-5-pyrazolone Example 21: 1-phenyl-3- [4- (3-p-tolylsulfonyl) Propoxy) benzoylamino] -4-
[4-N-ethyl-N- (2-hydroxyethyl) aminophenylamino] -4-acetylamino-5-pyrazolone Example 22: 1-phenyl-3-phenylacetylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone Example 23: 1-phenyl-3- (chloroanilino)-
4- (4-N, N-diethylaminophenylamino)-
4-acetylamino-5-pyrazolone

Examples 24 to 31 Eight kinds of thermal recording papers were prepared in the same manner as in Example 5 except that the following compounds were used in place of the zinc salt of α-naphthoic acid in the preparation of the liquid C of Example 5. Obtained. Example 24: Zinc salt of 4- (3-p-tolylsulfonylpropoxy) salicylic acid Example 25: Zinc salt of 4- (2-p-methoxyphenoxyethoxy) salicylic acid Example 26: 5- [p- (2-p-Methoxyphenoxyethoxy) cumyl] salicylic acid zinc salt Example 27: 3,5-di (α, α-dimethylbenzyl)
Zinc salt of salicylic acidExample 28: Zinc salt of 4-nitrobenzoic acidExample 29: Zinc salt of 4-chlorobenzoic acidExample 30: Zinc salt of 4-trifluoromethylbenzoic acidExample 31: Phenylacetic acid zinc salt

Comparative Example 4 In the preparation of the liquid C of Example 5, 2-acetylaminophenol was used instead of the zinc salt of α-naphthoic acid, and D
A thermosensitive recording paper was obtained in the same manner as in Example 5 except that the liquid was removed.

Example 32 A thermosensitive recording paper was obtained in the same manner as in Example 5 except that the following solution E was used instead of the solution C in Example 5. Preparation of solution E-α-naphthoic acid 30 parts-zinc oxide 10 parts-methyl cellulose 5% aqueous solution 60 parts-water 50 parts This composition was ground with a sand mill until the average particle size became 1.5 µm.

Example 33 Example 32 was repeated except that 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] salicylic acid was used in place of α-naphthoic acid in the preparation of solution E of Example 32. Thermal recording paper was obtained in the same manner.

The heat-sensitive recording papers obtained in Examples 5 to 33 and Comparative Examples 1 to 4 were heat-sensitive facsimiles (manufactured by Hitachi Ltd., HI).
FAX-700) was used for recording, and the color density was measured with a Macbeth densitometer (Macbeth RD-914 type), and the results are shown in [Table 1] and [Table 2] together with the color tone. Indicated.

Further, the heat-sensitive recording paper after recording is kept at 50 ° C. 90%
R. H. After leaving it in the atmosphere for 24 hours (moisture and heat resistance), stacking vinyl chloride films and leaving it at 40 ° C for 24 hours (plasticizer resistance), then apply ethanol to the coloring surface and leave it at 20 ° C for 24 hours (resistant Ethanol), and after leaving for 24 hours under the conditions of direct sunlight exposure (light resistance), the state of fog on the white paper part and the fading state of the recorded image were evaluated,
The results are shown in [Table 1] and [Table 2].

[Evaluation Criteria] A: Excellent. ◯: Excellent. Δ: Somewhat inferior and not suitable for practical use depending on the target quality. ×: Inferior and not practical

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

As is clear from the above results, the recording material of the present invention has good color developability, excellent preservability of the recorded image and the undeveloped area, and a blue or deep blue colored image is obtained. It was a recording material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location B41M 5/30 6956-2H B41M 5/18 102 6956-2H 108 (72) Inventor Haruo Omura Hyogo Prefecture 4-3-1, Jokoji, Amagasaki City Kanzaki Paper Manufacturing Co., Ltd. Kanzaki Mill

Claims (5)

[Claims] 1. A recording material utilizing a reaction between a colorless or light-colored dye precursor and a color-forming agent capable of developing a color by contacting with the dye precursor, wherein the dye precursor is represented by the following general formula: At least one of an aromatic carboxylic acid derivative or a polyvalent metal salt thereof is used as a colorant for the compound represented by
At least one selected from the group consisting of a phenolic compound represented by the following general formulas [Chemical Formula 2] to [Chemical Formula 4] and a phenol resin having a partial structure represented by the following general formula [Chemical Formula 5]. A recording material characterized by being used together. [Chemical 1] [Wherein R ₁ is an alkyl group, an alkoxyalkyl group or an aryl group which may have a substituent, and R ₂ and R ₃ each have an alkyl group or a substituent which may have a substituent] An aryl group which may have a substituent, R ₄ represents an alkyl group which may have a substituent, an aryl group which may have a substituent or an amino group which may have a substituent, and R ₅ and R ₆ respectively represent It represents an alkyl group, an alkoxyl group or a halogen atom, p is 0 or an integer of 1 to 5, and q is 0 or 1 to 4.
Indicates an integer. ] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [In the formula, R _{7 to} R ₁₂ are each a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. Optionally aryl group, optionally substituted carbamoyl group, optionally substituted sulfamoyl group, optionally substituted alkylcarbonylamino group, optionally substituted aryl Carbonylamino group, optionally substituted ureido group, optionally substituted aryloxycarbonyl group, optionally substituted alkoxycarbonyl group, optionally substituted alkylsulfonyl Amino group, arylsulfonylamino group optionally having substituent (s), alkylthio group optionally having substituent (s), arylthio group optionally having substituent (s), aryl optionally having substituent (s) Indicates an oxy group, X is a hydrogen atom or a group capable. ] 2. The recording material according to claim 1, wherein at least one kind of an aromatic carboxylic acid derivative or a polyvalent metal salt thereof is used as a coloring agent, and at least one kind of a metal compound is used in combination. 3. In the general formula [Chemical formula 1], R ₁ is C ₁ to C.
₄ alkyl group or phenyl group, R ₂ and R
₃ is an alkoxyl group of C ₁ -C ₄ as respective substituents, a alkylsulfonylamino group for hydroxyl group or a C ₁ -C ₄ alkyl group which may C ₁ ~C _4, R ₄ is represented by the following general An arylcarbonylamino group represented by the formula [Chemical formula 6], [Chemical formula 7] or [Chemical formula 8] or an alkylcarbonylamino group represented by [Chemical formula 9], [Chemical formula 10] or [Chemical formula 11], wherein R ₅ is A C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxyl group or a halogen atom, and R ₆ represents a C ₁ -C ₄ alkyl group or C ₁ -C
The recording material according to claim 1, wherein the recording material is an alkoxyl group of ₄ , p is 0 or an integer of 1 to 5, and q is 0 or an integer of 1 to 4. [Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] [Chemical 10] [Chemical 11] [In the formula, R ₁₃ represents a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxyl group or a halogen atom, and R ₁₄ represents a C _{1 to} C 4
_{5 is} an alkyl group, a C _{1 to} C ₄ alkoxyl group or a halogen atom, and R ₁₅ is a C _{1 to} C ₂₅ alkyl group,
Q represents an ether bond or a sulfonyl bond, A represents a branched or linear C _{2 to} C ₆ alkylene group, A ′ represents a branched or linear C _{1 to} C ₆ alkylene group, and r is 0 or 1 to Indicates an integer of 5. ] 4. The recording material is a heat-sensitive recording material.
Recording material described. 5. The recording material is a pressure-sensitive recording material.
Recording material described.