JPH0977729A - Acetamide derivative and heat-sensitive recording material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an acetamide derivative, excellent in acceleration of coupling reaction of a diazonium salt compound and promotion of decoloring of a colored material using an electron donative colorless dye and useful as an intermediate for medicines and agrochemicals or an additive to heat-sensitive recording materials. SOLUTION: This acetamide derivative is represented by formula I [X is H, a halogen, hydroxyl group, etc.; Y is H, an alkyl, etc.; (n) is an integer of 2-9; R is a group represented by formula II or III; R<1> and R<2> are each an alkyl; R<3> and R<4> are each independently an alkyl or an aryl]. The acetamide derivative is obtained by converting a phenol derivative into an acetamide. For example, this derivative in which R is a substituted amino group is prepared by providing an acid chloride having hydroxyl group protected with benzyl group or acetyl group, etc., esterifying the protected acid chloride with an alcoholic derivative such as the corresponding substituted amino-alcohol or monohydroxyalkylguanidines, removing the protecting group of the hydroxyl group and etherifying the prepared phenolic derivative with an α-halogeno-fatty acid amide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel acetic acid amide derivative which is useful as an intermediate for medicines and agricultural chemicals or as an additive for heat-sensitive recording materials, and a recording material utilizing the photosensitivity of diazonium salt compounds.

[0002]

2. Description of the Related Art Various basic substances have been studied as coupling reaction accelerators for diazo heat-sensitive recording materials. Representative examples thereof include imidazole derivatives (Japanese Patent Publication No. 52-46806, Japanese Patent Laid-Open No. 62806/1987). -70082),
N-substituted fatty acid amide derivative (JP-A-57-16974)
5, JP-A-60-94381), guanidine derivatives (JP-A-57-123086, JP-A-58-1347).
90, JP-A-60-49991, JP-B-2-249
16, JP-B-2-28479), amidine derivatives (JP-A-60-165288), urea derivatives (JP-A-57-185430), and the like.

In recent years, an attempt has been made to prepare a recording material having high storage stability and recording sensitivity before recording, such as a thermal recording material using a diazonium salt compound and a thermal recording material using a color former of an electron-donating colorless dye. However, the present situation is that the level has not reached to a sufficiently satisfactory level, and in particular, from the viewpoint of increasing the sensitivity of the recording material, the coupling reaction of the diazonium salt compound is promoted and the coloring matter of the electron-donating colorless dye is erased. Improved color reactivity is needed. As a result of intensive studies made by the present inventors for the purpose of solving this problem, they have found that a basic compound having a specific acetic acid amide group exhibits excellent performance, and arrived at the present invention.

[0004]

An object of the present invention is to promote a coupling reaction of a diazonium salt compound, or a compound effective as an erasing accelerator of a color developing material using an electron donating colorless dye, and a compound containing the same. Therefore, it is to provide a heat-sensitive recording material having high storage stability before recording and high recording sensitivity.

[0005]

The object of the present invention has been achieved by finding an acetic acid amide derivative represented by the general formula (1). General formula (1)

[0006]

[Chemical 7]

In the formula, X is a hydrogen atom, a halogen atom, a hydroxyl group, a lower alkyl group or a lower alkoxy group, Y is a hydrogen atom or a lower alkyl group, and n is an integer of 2 to 9,
R represents a group represented by the following general formula (2) or the following general formula (3). General formula (2)

[0008]

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In the general formula (2), R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group, or a 5- or 6-membered ring group in which R ¹ and R ² are bonded to each other. General formula (3)

[0010]

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In the general formula (3), R ³ and R ⁴ each independently represent an alkyl group or an aryl group.

In the general formula (1), the group represented by X is hydrogen atom, chlorine atom, fluorine atom, hydroxyl group, methyl group, ethyl group, propyl group, butyl group, methoxy group,
Examples thereof include an ethoxy group and a propoxy group, preferably a hydrogen atom, a chlorine atom, a hydroxyl group, a methyl group and a methoxy group.

In the general formula (1), examples of the group represented by Y include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group, and a hydrogen atom and a methyl group are preferable.

Examples of the linking group represented by —C _n H _2n — in the general formula (1) include the structures shown below.

[0015]

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The following structures are preferred.

[0017]

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In the general formula (2), the alkyl groups represented by R ¹ and R ² are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group,
t-butyl group, pentyl group, hexyl group, octyl group,
Examples include 2-ethylhexyl group and cyclohexyl group.

In the general formula (2), the substituted alkyl group for R ¹ and R ² is an allyl group, an alkoxyalkyl group,
Examples thereof include an aralkyl group and an aryloxyalkyl group. Among them, the alkoxyalkyl group includes 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group and the like, and the aralkyl group includes benzyl group, p-methylbenzyl group, p-methoxybenzyl group, p-chlorobenzyl group,
β-phenethyl group, 2- (4-methylphenyl) ethyl group, 2- (4-methoxyphenyl) ethyl group, 2- (4
-Chlorophenyl) ethyl group and the like, and as the aryloxyalkyl group, a 2-phenoxyethyl group, 2-
(4-methylphenoxy) ethyl group, 2- (4-methoxyphenoxy) ethyl group, 2- (4-chlorophenoxy) ethyl group, 2-phenoxy-1-methylethyl group,
2- (4-methylphenoxy) -1-methylethyl group,
2- (4-methoxyphenoxy) -1-methylethyl group, 2- (4-chlorophenoxy) -1-methylethyl group, 2-phenoxypropyl group, 2- (4-methylphenoxy) propyl group, 2- ( 4-methoxyphenoxy)
Propyl group, 2- (4-chlorophenoxy) propyl group, 3-phenoxypropyl group, 3- (4-methylphenoxy) propyl group, 3- (4-methoxyphenoxy)
Examples thereof include a propyl group and a 3- (4-chlorophenoxy) propyl group.

In formula (2), the 5- to 6-membered ring group in which R ¹ and R ² are bonded to each other is a pyrrolidinino group, a piperidino group, a morpholino group, a thiomorpholino group,
Examples thereof include a piperazino group and the like, which may have a substituent on the ring, and examples thereof include a lower alkyl group, an aryl group, an aralkyl group and an aryloxyalkyl group.

The following are preferred examples of the substituted amino group represented by the general formula (2). N, N-
Dimethylamino group, N, N-diethylamino group, N, N
-Dipropylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N, N-diisobutylamino group, N, N-dicyclohexylamino group, N,
N-dibenzylamino group, N, N-di-β-phenethylamino group, N, N-di (2-phenoxyethyl) amino group, N-methyl-N-ethylamino group, N-methyl-N
-(2-Methoxyethyl) amino group, N-methyl-N-
(2-ethoxyethyl) amino group, N-methyl-N-propylamino group, N-methyl-N-octylamino group,
N-methyl-N-benzylamino group, N-methyl-N-
β-phenethylamino group, N-methyl-N- (2-phenoxyethyl) amino group, N-methyl-N- [2- (4
-Methylphenoxy) ethyl] amino group, N-methyl-
N- [2- (4-methylphenoxy) ethyl] amino group, N-methyl-N- [2- (4-methoxyphenoxy) ethyl] amino group, N-methyl-N- [2- (4-
Chlorophenoxy) ethyl] amino group, N-methyl-N
-(2-phenoxy-1-methylethyl) amino group, N
-Ethyl-N- (2-methoxyethyl) amino group, N-
Ethyl-N- (2-ethoxyethyl) amino group, N-ethyl-N-propylamino group, N-ethyl-N-octylamino group, N-ethyl-N-benzylamino group, N-
Ethyl-N-β-phenethylamino group, N-ethyl-N
-(2-phenoxyethyl) amino group, N-ethyl-N
-[2- (4-methylphenoxy) ethyl] amino group,
N-ethyl-N- [2- (4-methylphenoxy) ethyl] amino group, N-ethyl-N- [2- (4-methoxyphenoxy) ethyl] amino group, N-ethyl-N- [2
-(4-Chlorophenoxy) ethyl] amino group, N-ethyl-N- (2-phenoxy-1-methylethyl) amino group, pyrrolidinino group, piperidino group, 2,2,6,6
-Tetramethylpiperidino group, 2-methylpiperidino group, morpholino group, N-methylpiperazino group, N-phenylpiperazino group, N-benzylpiperazino group, N-
Examples thereof include (2-phenoxyethyl) piperazino group, N- (2-phenoxyethyl) piperazino group and N- (2-phenoxy-1-methylethyl) piperazino group.

In the general formula (3), the alkyl groups represented by R ³ and R ⁴ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl. Group, hexyl group, octyl group, 2-ethylhexyl group, cyclohexyl group and the like. In the general formula (3), the aryl group of R ³ and R ⁴ is a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 4-methoxyphenyl group, a 3-methoxyphenyl group, 2-methoxyphenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group and the like can be mentioned.

Preferred examples of the guanidino group represented by the general formula (3) include the following.

[0024]

[Chemical 12]

Typical examples of the acetic acid amide derivative of the present invention are shown below, but the compounds used in the present invention are not limited thereto.

[0026]

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[0027]

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[0028]

[Chemical 15]

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

[Chemical 21]

The acetic acid amide derivative of the present invention is a known method (Japanese Patent Laid-Open No. 58-92659 and Japanese Patent Laid-Open No. 4-41472).
No.) or a similar method thereto can be synthesized by acetic acid amidation. For example, in the general formula (1), R is a substituted amino group or an acetic acid amide derivative represented by a guanidino group, and a 4-substituted benzoic acid in which a 4-position hydroxyl group is protected with a benzyl group, an acetyl group or the like is used as an acid chloride. It can be synthesized by esterifying with a corresponding substituted amino alcohol, or an alcohol derivative such as monohydroxyalkylguanidines, and then etherifying a phenol derivative with a hydroxyl-protecting group deprotected with α-halogeno fatty acid amide. . The first reaction, acid chloride formation of benzoic acids, is performed using an acid chloride agent such as thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, oxalic acid dichloride, etc., in an amount of 1 to 10 times equivalent to the corresponding benzoic acid.
The reaction is carried out using a solvent such as acetonitrile, benzene, toluene or the like or without a solvent. Reaction temperature is -10
It is carried out at -150 ° C, preferably 0-120 ° C. At this time, pyridine, dimethylformamide or the like may be added as a reaction promoter in a catalytic amount. The esterification is carried out using triethylamine, pyridine, etc. as a base in an amount of 1 to 5 times equivalent to that of the acid chloride. The alcohol derivative is used in 1 to 3 equivalents relative to the acid chloride. As a reaction solvent, acetonitrile, benzene, toluene, methylene chloride,
Chloroform, tetrahydrofuran, ethyl acetate and the like can be mentioned, and they are used at 1 to 100 times equivalent to the acid chloride. For deprotection, when the protecting group is a benzyl group, catalytic hydrogen reduction using palladium carbon or the like, and when the protecting group is an acetyl group, sodium acetate, potassium carbonate, sodium carbonate in the presence of methanol or ethanol is used. And the like at 0-60 ° C.

The etherification in the final step is carried out in the presence of a solvent such as methanol, ethanol, propanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfolane, etc. as a base, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, water. It is carried out at a reaction temperature of 0 to 150 ° C. using potassium oxide, sodium hydroxide and the like. The acetic acid amidation can also be carried out by etherifying a phenol derivative with an α-halogeno fatty acid ester in the same manner as above, and then allowing ammonia water to act at 20 to 40 ° C. in the presence of methanol, ethanol or the like. it can. The phenol derivative which is the precursor of the target compound can also be obtained by dehydration condensation or transesterification of hydroxybenzoic acid or its lower alkyl ester and the corresponding alcohol derivative in the presence of a suitable condensing agent. . The alcohol derivative is used in 1 to 3 equivalents relative to hydroxybenzoic acid or its lower alkyl ester. Examples of the condensing agent or catalyst at this time include a dehydrating agent such as sulfuric acid, polyphosphoric acid, paratoluenesulfonic acid, and amberlyst, or a transesterification catalyst. These dehydrating agents are used in an amount of 1.01 to 10 times equivalent to the alcohol derivative. As the solvent, benzene, toluene, xylene, mesitylene or an alcohol derivative of the reaction reagent is used. Next, a recording material containing the compound of the present invention will be described below. The acetic acid amide derivative of the present invention is used in the heat-sensitive recording layer in an amount of 0.02 to 5 g / m ² , preferably 0.1 to 3 g / m ² . The acetic acid amide derivative of the present invention may be used alone or in combination of two or more kinds. Hereinafter, other components used in the recording material of the present invention will be described.

The present diazonium salt compound used in the invention is represented by the following general formula Ar-N ₂ ⁺ X ^- [wherein Ar represents an aromatic moiety, X ^- represents an acid anion] is a compound represented by, It is a compound that can undergo a coupling reaction with a coupling component to develop a color and can be decomposed by light. These have various maximum absorption wavelengths depending on the position and type of the substituent in the Ar portion.

Specific examples of the diazonium which forms a salt include 4- (p-tolylthio) -2,5-dibutoxybenzenediazonium and 4- (4-chlorophenylthio)-.
2,5-dibutoxybenzenediazonium, 4- (N,
N-dimethylamino) benzenediazonium, 4-
(N, N-diethylamino) benzenediazonium, 4
-(N, N-dipropylamino) benzenediazonium, 4- (N-methyl-N-benzylamino) benzenediazonium, 4- (N, N-dibenzylamino) benzenediazonium, 4- (N-ethyl-N) -Hydroxyethylamino) benzenediazonium, 4- (N, N-
Diethylamino) -3-methoxybenzenediazonium, 4- (N, N-dimethylamino) -2-methoxybenzenediazonium, 4- (N-benzoylamino)-
2,5-diethoxybenzenediazonium, 4-morpholino-2,5-dibutoxybenzenediazonium, 4-
Anilinobenzenediazonium, 4- [N- (4-methoxybenzoyl) amino] -2,5-diethoxybenzenediazonium, 4-pyrrolidino-3-ethylbenzenediazonium, 4- [N- (1-methyl-2- ( 4-Methoxyphenoxy) ethyl) -N-hexylamino]-
2-hexyloxybenzenediazonium, 4- [N-
(2- (4-methoxyphenoxy) ethyl) -N-hexylamino] -2-hexyloxybenzenediazonium and the like can be mentioned.

Specific examples of the acid anion include C_nF_{2n + 1}
COO^-(N is an integer of 3 to 9), C _mF_{2m + 1}SO
_Three ^-(M is an integer of 2 to 8), BF_Four ^-, PF₆ ^-Etc.
BF because of its low water solubility and solubility in organic solvents_Four
^-, PF₆ ^-Is preferred. These diazonium salt compounds
For details, see Japanese Patent Application No. 5-278608 and Japanese Patent Application No.
No. 5-297024, Japanese Patent Application No. 6-118964, Japanese Patent Application
No. 7-121208.

In the present invention, the diazonium salt compound is
0.02 to 3 g / m in the thermal recording layer ²Used in the range of
And preferably 0.1 to 2 g / m²Used in the range of
You. In the present invention, the diazonium salt compound is a microca
Encapsulation in a capsule is preferable from the viewpoint of storability.
The method of microencapsulation is not particularly limited.
Instead of gelatin, polyurea, polyurethane,
Liimide, polyester, polycarbonate, melamine
Encapsulation by a conventionally known method using wall materials such as
Can be done. For more information on microencapsulation methods
It is described in JP-A-2-141279. Ma
In addition, at the time of encapsulation, a dispersion solvent for the diazonium salt compound and
Then, a high boiling point organic solvent may be used. In this organic solvent
There is no particular limitation regarding the alkyl phthalate.
, Phosphoric acid ester, citric acid ester, benzoic acid ester
Tell, alkylamide, aliphatic ester, trimesic acid
Conventionally known ones such as ester can be used. Details
The details are described in JP-A-7-17145.
I have.

The coupler used in the present invention causes a coupling reaction with the above-mentioned diazo compound in a basic atmosphere to develop a color, and can be selected according to the desired hue. Specific examples of these include resorcin, phloroglysin, and 2,3-hydroxynaphthalene-
Sodium 6-sulfonate, sodium 2-hydroxy-3-naphthalenesulfonate, 2-hydroxy-3-naphthalenesulfonic acid anilide, 2-hydroxy-3-naphthalenesulfonic acid morpholinoamide, 2-hydroxy-3-naphthalenesulfonic acid morpholino Pyropyramide, 2-hydroxy-3-naphthalenesulfonic acid-2-
Ethyl-hexyloxypropylamide, 2-hydroxy-3-naphthalenesulfonic acid-2-ethyl-hexylamide, 1-hydroxy-8-acetylaminonaphthalene-3,6-disulfonic acid sodium salt, 1-hydroxy-8-acetylamino Naphthalene-3,6-disulfonic acid dianilide, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxy-6-naphthalenesulfonic acid amide, 2 -Hydroxy-3-naphthoic acid morpholinopropylamide, 2-
Hydroxy-3-naphthoic acid anilide, 2-hydroxy-3-naphthoic acid-2'-methylanilide, 2-hydroxy-3-naphthoic acid ethanolamide, 2-hydroxy-3-naphthoic acid octylamide, 2-hydroxy-
3-naphthoic acid octylamide, 2-hydroxy-3-
Naphthoic acid morpholinoethylamide, 2-hydroxy-
3-naphthoic acid piperidinoethylamide, 2-hydroxy-3-naphthoic acid piperidinopropylamide, 2-hydroxy-3-naphthoic acid-N-dodecyloxy-propylamide, 2-hydroxy-3-naphthoic acid tetra Decylamide, 6-methoxy-2-hydroxy-3-naphthoic acid anilide, 6-ethoxy-2-hydroxy-3-
Naphthoic acid anilide, 6-methoxy-2-hydroxy-
3-naphthoic acid morpholinopropylamide, 6-methoxy-2-hydroxy-3-naphthoic acid-2-hydroxyethylamide

Acetanilide, acetoacetanilide,
2 ', 5'-di-n-heptyloxy-2-acetoacetanilide, benzoylacetanilide, 1-phenyl-3-methyl-5-pyrazolone, 1- (2', 4 ',
6'-trichlorophenyl) -3-benzamide-5-
Pyrazolone, 1- (2 ', 4', 6'-trichlorophenyl) -3-anilino-5-pyrazolone, 1-phenyl-3-phenylacetamido-5-pyrazolone, 1-methyl-3-phenyl-2,4 , 6,-(1H, 3H, 5
H) -pyrimidinetrione, 1-octadecyloxypropyl-3-phenyl-2,4,6,-(1H, 3H,
5H) -pyrimidinetrione, 1-phenyl-3-
(2,5-Dioctyloxyphenyl) -2,4,6
-(1H, 3H, 5H) -Pyrimidinetrione, 1,3
-Bis (2,5-dioctyloxyphenyl) -2,
4,6,-(1H, 3H, 5H) -pyrimidinetrione, 1,3-bis (n-octadecyloxycarbonylmethyl) -2,4,6,-(1H, 3H, 5H) -pyrimidinetrione, 5, 5-dimethyl-cyclohexane-
1,3-dione, 5- (2-tetradecyloxyphenyl) -cyclohexane-1,3-dione, N- (2-ethyl-hexyloxypropyl) -3-cyano-4-ethyl-6-hydroxy-2 -Pyridone, N- (dodecyloxypropyl) -3-acetyl-4-methyl-6-hydroxy-2-pyridone and the like can be mentioned. Details of the coupler are described in JP-A-4-201283, Japanese Patent Application No. 5-278608, Japanese Patent Application No. 5-297024.
It is described in Japanese Patent Application Nos. 6-18669 and 6-18670. These couplers may be used alone or in combination of two or more.

In the present invention, in addition to the acetic acid amide derivative represented by the general formula (1) of the present invention, a tertiary amine, a piperidine or a piperazine is used for the purpose of making the system basic during heat development to accelerate the coupling reaction. , Organic bases such as amidines, formamidines, pyridines, guanidines and morpholines may be used in combination.

Specific examples of these organic bases include N, N
^' -Bis (3-phenoxy-2-hydroxypropyl)
Piperazine, N, N ^'- bis [3- (p-methylphenoxy) -2-hydroxypropyl] piperazine, N, N
^'- bis [3- (p-methoxyphenoxy) -2-hydroxypropyl] piperazine, N, ^N' - bis (3-phenylthio-2-hydroxypropyl) piperazine,
N, N ^'- bis [3- (beta-naphthoxy) -2-hydroxypropyl] piperazine, N-3- (beta-naphthoxy) -2-hydroxypropyl ^-N' - methylpiperazine, 1,4-bis {[ 3- (N-methylpiperazino)-
2-Hydroxy] propyloxy} benzene and other piperazines, N- [3- (β-naphthoxy) -2-hydroxy] propylmorpholine, 1,4-bis [(3-morpholino-2-hydroxy) propyloxy] benzene ,
Morpholines such as 1,3-bis [(3-morpholino-2-hydroxy) propyloxy] benzene, N- (3
-Phenoxy-2-hydroxypropyl) piperidine,
Examples thereof include piperidines such as N-dodecylpiperidine, triphenylguanidine, tricyclohexylguanidine, dicyclohexylphenylguanidine and the like. These organic bases may be used alone or in combination of two or more.

In the present invention, the amount of the coupler and the organic base used is not particularly limited, but both the coupler and the organic base may be used in the range of 1 to 30 mol based on 1 mol of the diazonium salt compound. preferable.
The coupler used in the present invention can be used by adding a water-soluble polymer together with other components and solid-dispersing it with a sand mill or the like, or it can be used as an emulsion together with a suitable emulsification aid. The solid dispersion method and the emulsification method are not particularly limited, and conventionally known methods can be used. Details of these methods are described in JP-A-59-190886 and JP-A-2-14.
No. 1279 and JP-A No. 7-17145.

In the present invention, in addition to the acetic acid amide derivative represented by the general formula (1), a color forming auxiliary can be added for the purpose of promoting the color forming reaction. Examples of these coloring aids include phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, hydroxy compounds, carboxylic acid amide compounds, sulfonamide compounds and the like. These compounds are
Reduce the melting point of the coupler or basic substance,
Alternatively, improve the heat permeability of the microcapsule wall,
As a result, it is considered that high color density can be obtained.

In the recording material of the present invention, a free radical generator (a compound that generates a free radical upon irradiation with light) used in a photopolymerizable composition or the like for the purpose of reducing yellowing of the background after recording.
Alternatively, a polymerizable compound having an ethylenically unsaturated bond can be used. For details of these, Japanese Patent Application No. 6-
18670 and the like. In addition to these, various organic or inorganic pigments, various stabilizers, if necessary,
It is also possible to add an antioxidant, a compound having an ultraviolet transmittance adjusting function, and the like.

The binder that can be used in the present invention is not particularly limited, and conventionally known binders such as polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, styrene and acrylic acid copolymer can be used. You can For details, see JP-A-2-141.
No. 279.

The recording material of the present invention is prepared by preparing a coating solution containing a diazonium salt compound, an acetic acid amide derivative represented by the general formula (1), a coupler, and other additives, and supporting a paper or a synthetic resin film. Body coating by bar coating, blade coating, air knife coating, gravure coating, roll coating, spray coating, dip coating, curtain coating, etc.
Providing ² heat sensitive layers.

In the recording material of the present invention, the diazonium salt compound, the coupler, the acetic acid amide derivative represented by the general formula (1) and the like may be contained in the same layer as described in the above method, or may be contained in another layer. It is also possible to adopt a laminated structure such as that included in. On the support, Japanese Patent Application No. 59-
After providing the intermediate layer described in the specification such as 177669,
A thermal recording layer can also be applied.

As the support used in the present invention, a conventionally known support can be used. Specifically, neutral paper, acidic paper, recycled paper, polyolefin resin laminated paper, synthetic paper, polyester film, cellulose derivative film such as cellulose triacetate film, polystyrene film, polyolefin film such as polypropylene film and polyethylene film, etc. These can be used alone or in combination. The thickness of the support used is 20 to 200 μm.

When an image is formed on the recording material of the present invention,
The following method can be used. One is a method of exposing a document to form a latent image, and then irradiating light to a portion other than the image forming portion to fix the latent image.
In this method, a color image is obtained by heat from a hot pen, a thermal head, etc., and then the area other than the image area is irradiated with light to fix the color image. Either method can be preferably used. As the light source for exposure, various fluorescent lamps, xenon lamps, mercury lamps, etc. are used, and the fact that the emission spectrum is almost the same as the absorption spectrum of the diazo compound used in the recording material makes it possible to efficiently use other than the image forming portion. It is preferable because it can be fixed by light. In the step of heating and developing the material, a heating pen, a thermal head, an infrared ray, a high frequency, a heat block, a heat roller, or the like can be used as the heating means.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" in an Example shows all weight parts.

[0054]

【Example】

Example 1 Synthesis of compound (1-5) 9 g of 4-benzyloxybenzoic acid and 5 g of thionyl chloride,
Toluene (150 ml) was added, dimethylformamide (a few drops) was added, and the mixture was stirred at 80 ° C. for 3 hr, and the solvent was evaporated under reduced pressure to give 9.7 g of 4-benzyloxybenzoic acid chloride as a solid. Di-n-butylaminoethanol 7.6
g, triethylamine 20 ml toluene solution 50 ml
To 100 ml of a toluene solution of 9.7 g of 4-benzyloxybenzoic acid chloride was added under stirring, the mixture was stirred at room temperature for 30 minutes, water was added, the organic layer was washed with water, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 3/1) and 4-benzyloxybenzoic acid 2-di-n-butylaminoethyl ester 1
1 g was obtained as a colorless oil. To this oil, 1 g of 10% palladium carbon and 50 ml of ethanol were added as a catalyst, and the mixture was stirred under a hydrogen atmosphere at room temperature and atmospheric pressure for 3 hours. After the catalyst was separated by furnace, the solvent was distilled off and recrystallized from hexane to obtain 8.6 g of 4-hydroxybenzoic acid 2-di-n-butylaminoethyl ester. To this compound, 6.4 g of α-chloroacetic acid amide, 12 g of potassium carbonate, and 30 ml of dimethylacetamide were added, and the mixture was stirred at 110 ° C. for 2 hours. The reaction solution was poured into water, and the precipitated crystals were collected by filtration and recrystallized from hexane to obtain 6.8 g of the target compound (1-5). Melting point 92-93 ° C ¹ H-NMR (CDCl ₃ ): δ 0.90 (t, 6H), 1.25-
1.37 (m, 4H), 1.40 ~ 1.51 (m, 4H), 2.60 (t, 4H), 2.82 (t, 2
H), 4.35 (t, 2H), 4.56 (s, 2H), 5.88 ~ 5.96 (brs, 1H), 6.
48 ~ 6.56 (brs, 1H), 6.95 (d, 2H), 8.03 (d, 2H)

Examples 2 to 7 The following compounds were obtained in the same manner as in Example 1 except that various substituted amino alcohols were used in place of 2-di-n-butylaminoethanol. Compound (1-17) Melting point 126-128 ° C Compound (1-30) Melting point 148-150 ° C Compound (1-45) Melting point 88-90 ° C Compound (1-46) Melting point 97-99 ° C Compound (1-51) Melting point 110-112 ° C Compound (1-52) Melting point 102-103 ° C

Example 8 [Preparation of Capsule Liquid A]: 4- (p
-Tolylthio) -2,5-dibutoxybenzenediazonium hexafluorophosphate (2.8 parts) and tricresylphosphate (10 parts) were added and uniformly mixed.
Next, Takenate D-110N as a wall agent was added to this mixed solution.
(Takeda Pharmaceutical Co., Ltd.) Add 7.6 parts and mix evenly.
A liquid was obtained. Next, an 8 wt% aqueous solution of phthalated gelatin 4
The solution I was added to a mixed solution of 6.1 parts, 17.5 parts of water, and 2 parts of a 10% aqueous solution of sodium dodecylbenzenesulfonate, and the mixture was added at 40 ° C., 10,000 r. p. m for 10 minutes. After adding 20 parts of water to the obtained emulsion and homogenizing,
Capsule liquid A was obtained by carrying out an encapsulation reaction at 40 ° C. for 3 hours while stirring. The particle size of the capsule was 0.35 μm.

[Preparation of coupler emulsion B]: 2.5 parts of the acetic acid amide derivative (1-5) of the present invention in 8 parts of ethyl acetate,
2.4 parts of 2 ', 5'-di-n-heptyloxy-2-acetoacetanilide, 3.2 parts of 4-hydroxybenzoic acid 2-ethylhexyl ester, 1,1-bis (4-hydroxyphenyl) -2- 2.5 parts of ethylhexane,
3.5 parts of 4,4 ^' -(m-phenylenediisopropylidene) diphenol, tricresyl phosphate 0.6
Liquid II was obtained by dissolving 4 parts and 0.32 part of maleic acid diethyl ester. Next, 32 parts of a 15 wt% aqueous solution of lime-processed gelatin, 10% sodium dodecylbenzenesulfonate
While uniformly mixing 5 parts of the aqueous solution and 30 parts of water at 40 ° C., I
Solution I was added and a homogenizer was used at 40 ° C, 1000
0r. p. m. For 10 minutes. The obtained emulsion was stirred at 40 ° C. for 2 hours to remove ethyl acetate, and the weight of volatilized ethyl acetate and water was supplemented with water to obtain a coupler / base emulsion B.

[Preparation of coating liquid C]: 6 parts of capsule liquid A,
Water 4.4 parts, lime-processed gelatin 15% by weight aqueous solution 1.
After uniformly mixing 9 parts at 40 ° C., coupler emulsion B
8.3 parts was added and mixed uniformly to prepare a heat-sensitive recording layer coating liquid C.
I got [Preparation of coating solution D for protective layer]: 32 parts of a 10% aqueous solution of polyvinyl alcohol (polymerization degree: 1700, saponification degree: 88%) and 36 parts of water were uniformly mixed to obtain a coating solution D for protective layer.

[Coating]: Coating on a printing paper support prepared by laminating polyethylene on high-quality paper with a wire bar in the order of thermosensitive recording layer coating liquid C and protective layer coating liquid D and at 50 ° C.
And dried to obtain the desired heat-sensitive recording material. The coating amount as a solid content is 6.4 g / m ² and 1.05 g / m ² , respectively.
^{Was 2} .

[Test of color development and fixing]: Using a thermal head (KST type) manufactured by Kyocera Corporation, the applied power and pulse width to the thermal head were determined so that the recording energy per unit area was 46 mJ / mm ^2. After heat-printing on the recording layer to obtain an image, the emission center wavelength is 42
The entire surface was irradiated with light for 15 seconds using an ultraviolet lamp of 0 nm and an output of 40 W. The density of the color-developed portion of the obtained sample was measured with a Macbeth densitometer.

[Test for Raw Preservability]: The thermosensitive recording material before recording was forcibly stored for 72 hours under the conditions of 60 ° C. and 30% RH. The density of the background portion of the heat-sensitive recording material was measured before and after forced storage.

Examples 9 to 14 Instead of the compound (1-5) used in Example 8, (1-17) [Example 9], (1-30) [Example 1]
0], (1-45) [Example 11], (1-46) [Example 12], (1-51) [Example 13], (1-5)
2) Example 8 except that an emulsion was obtained using [Example 14]
The same operation was carried out to prepare a recording material and form an image. A Macbeth densitometer was used to measure the color density of the obtained sample and the density of the background color before and after the forced storage test.

Comparative Example 1 The same operation as in Example 8 was carried out except that benzoic acid 2-di-n-butylaminoethyl ester was used in place of the compound (1-5) used in Example 8, and an image was obtained. Was formed.
A Macbeth densitometer was used to measure the color density of the obtained sample and the density of the background color before and after the forced storage test.

Table 1 shows the results of the measurement of color density and background density.

[0065]

[Table 1]

Example 15 [Preparation of capsule liquid E]: To 5 parts of ethyl acetate, 3.5 parts of 4-morpholino-2,5-dibutoxybenzenediazonium hexafluorophosphate and 24 parts of tricresylphosphate were added. Mixed evenly. Next, 12 parts of Takenate D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) as a wall agent was added to this mixed solution and uniformly mixed to obtain a solution I. Next, this liquid I was added with 5.2 parts of polyvinyl alcohol and 58 parts of water.
Part of the solution, emulsified and dispersed at 20 ° C, average particle size 2μ
To obtain an emulsion. 100 parts of water was added to the obtained emulsion,
Capsule liquid E was obtained by carrying out an encapsulation reaction at 60 ° C. for 2 hours while stirring.

[Preparation of Coupler Solid Dispersion F]: 10 parts of 2-hydroxy-3-naphthoic acid anilide and 10 parts of the acetic acid amide derivative (1-55) of the present invention were added to 100 parts of a 5% polyvinyl alcohol aqueous solution, and a sand mill was used. For about 24 hours to obtain a solid dispersion having an average particle diameter of 3μ. Further α-
20 parts of (3-methylphenoxy) acetic acid amide, 100 parts of a 4% aqueous solution of polyvinyl alcohol and 100 parts of water were added and dispersed for 2 hours with a paint shaker to obtain a solid dispersion liquid having an average particle diameter of 3 μm.

[Preparation of coating solution G]: 2.5 parts of coupler solid dispersion F was added to 5 parts of capsule solution E to obtain coating solution G.

[Coating]: Coating solution G was coated on a high-quality paper with a wire bar and dried at 25 ° C. to obtain a desired diazo heat-sensitive recording material. The coating amount as solid content is 10 g / m
^{Was 2} .

[Test for Color Development and Raw Preservation]: Example 8
Was performed in the same manner as described above.

Comparative Example 2 An image was formed in the same manner as in Example 15 except that tricyclohexylguanidine was used in place of the compound (1-55) used in Example 15. A Macbeth densitometer was used to measure the color density of the obtained sample and the density of the background color before and after the forced storage test.

Table 2 shows the results of color density and background density measurement.

[0073]

[Table 2]

From these results, the general formula (1) of the present invention was obtained.
It is understood that the acetic acid amide derivative represented by is useful as a coupling reaction accelerator of a diazonium salt compound, and a heat-sensitive recording material using the same has a high color density and is excellent in preservability before recording.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C07D 295/08 G03C 1/61 501 G03C 1/52 B41M 5/18 S 1/61 501 101S 112

Claims (3)

[Claims] 1. An acetic acid amide derivative represented by the general formula (1). General formula (1) In the formula, X is a hydrogen atom, a halogen atom, a hydroxyl group, a lower alkyl group or a lower alkoxy group, Y is a hydrogen atom or a lower alkyl group, n is an integer of 2 to 9, and R is the following general formula (2) or It represents a group represented by the following general formula (3). General formula (2) In the general formula (2), R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group, or R ¹ and R ²
And represent a 5- or 6-membered ring group bonded to each other. General formula (3) In the general formula (3), R ³ and R ⁴ each independently represent an alkyl group or an aryl group. 2. A heat-sensitive recording material comprising a support having thereon a heat-sensitive recording layer containing a diazonium salt compound and a coupler which reacts with the diazonium salt compound to form a color when heated, wherein A heat-sensitive recording material comprising an acetic acid amide derivative represented by the formula (1). General formula (1) In the formula, X is a hydrogen atom, a halogen atom, a hydroxyl group, a lower alkyl group or a lower alkoxy group, Y is a hydrogen atom or a lower alkyl group, n is an integer of 2 to 9, and R is the following general formula (2) or It represents a group represented by the following general formula (3). General formula (2) In the general formula (2), R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group, or R ¹ and R ²
And represent a 5- or 6-membered ring group bonded to each other. General formula (3) In the general formula (3), R ³ and R ⁴ each independently represent an alkyl group or an aryl group. 3. The heat-sensitive recording material according to claim 2, wherein the diazonium salt compound is encapsulated in microcapsules.