JPS63128984A - Multicolor thermosensitive recording material - Google Patents

Abstract

PURPOSE:To obtain a high-quality multicolor developed image with a low temperature color deleloping layer which has a significantly improved color development and discharging properties by using compounds such as bis(3-chloro-4- hydroxyphenyl)ethylacetate as developers. CONSTITUTION:In multicolor thermosensitive recording materials consisting of at least one kind of decoloring agent and at least two kinds of dye and developer, for instance, a compound such as bis(3-chloro-4-hydroxyphenyl) ethylacetate shown by the formula I is incorporated as the developer. A leuco dye is used alone or in a mixture of two or more kinds of other chemical, for instance 3,3-bis(p-dimethylaminophenyl)-phthalide may be mentioned. The color development of a low temperature color-developing layer needs to be prevented when a color is developed at high temperatures. A such decoloring agent, for instance, N-methyl-N'-phenylacetylpiperazine is named. In order to obtain a bicolor thermosensitive recording material, a solution containing dispersed or dissolved color developing dye, developing agent, decoloring agent and bider is applied to the surface of a support such as paper, synthetic paper and plastic and dried. The process is repeated to obtain the bicolor thermosensitive recording material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a multicolor heat-sensitive recording material, and more particularly to a two-color heat-sensitive recording material formed by laminating a plurality of heat-sensitive coloring layers having different color tones.

[Prior art]

A thermosensitive recording material is a material in which a thermosensitive coloring layer capable of forming a colored image by heating is provided on a support such as paper, and a thermal printer equipped with a thermal head is widely used for heating.

These conventional heat-sensitive recording materials include a colorless or light-colored leuco dye (color-forming main agent) having a lactone ring, lactam ring, spiropyran ring, etc. in the heat-sensitive coloring layer, and a color developer that reacts with this leuco dye when heated to form a color. Agent (coloring aid)
Those containing these are often used because they have clear color tones and less fogging.

By the way, heat-sensitive recording materials can easily produce colored images just by heating them, so they are not only used for copying books, documents, etc., but are also used in various fields such as computer, facsimile, telex, and other fields for recording various types of information and measuring equipment. However, depending on the purpose of recording, in order to display particularly necessary data and numbers more clearly, the coloring of that part (
It goes without saying that it is desirable to be able to record with the display color (displayed color) different from the developed color of other parts.

Recently, attempts have been made to obtain multicolor recording by utilizing differences in heating temperature or thermal energy, and various multicolor thermosensitive recording papers have been proposed accordingly. Multi-color thermosensitive recording paper is generally formed by stacking two types of high-temperature and low-temperature coloring layers that develop different tones with different coloring heat energies on a support, and can be broadly classified into the following two types: Divided into types. One is to mix the color with the color tone of the low temperature coloring layer when coloring the high temperature coloring layer to obtain a color tone different from the coloring tone of the low temperature coloring layer, and the other is to color the high temperature coloring layer. In this case, by using a decoloring agent that decolorizes the low-temperature color-forming layer, only the color tone of the high-temperature color-forming layer is obtained without color mixture of the color tone of the low-temperature color-forming layer. As specific examples of these, the former is disclosed in Japanese Patent Publication No. 49-69 and Japanese Patent Publication No. 49-4342.

Special Publication No. 49-27708, Japanese Patent Publication No. 48-86543
No. 49-65239, JP-A No. 49-65239, etc.
The latter ones are published in Japanese Patent Publication No. 50-17865, Japanese Patent Publication No. 17866, Japanese Patent Publication No. 51-29024.
Publication No. 1987-87542, Japanese Patent Publication No. 1987-87542
These are disclosed in Japanese Patent Publication No. 18048, Japanese Patent Publication No. 55-36519, etc., respectively.

However, in the case of the former multicolor thermosensitive recording paper,
When coloring at a high temperature, the color tones that can be concretely achieved in order to mix the color with the color tone of the low temperature coloring layer are limited to black threads where the high temperature coloring tone is strong, such as red-black, blue-black, etc. There is. On the other hand, in the case of the latter multicolor thermosensitive recording paper, the decoloring speed of the low temperature coloring layer is an important point in obtaining multiple colors. The decoloring speed is influenced not only by the decoloring agent, but also by the dye and color developer.

Texture and color development are also greatly affected by decolorizers, dyes, and color developers. Therefore, in terms of quality, it is required that the coloring property is stable under temperature and humidity, and that the coloring speed is fast.

aPA 'bp, which has been well known as a color developer
-Benzyl hydroxybenzoate and the like had drawbacks such as low concentration and slow decoloring speed.

〔the purpose〕

An object of the present invention is to overcome the above-mentioned problems of the prior art and provide a multicolor thermosensitive recording material that has a low-temperature coloring layer that has excellent coloring properties and excellent color erasing properties.

〔composition〕

According to the present invention, in a multicolor thermosensitive recording material comprising at least one decolorizing agent, two or more dyes, and a color developer, a compound having a structure represented by the following general formula (1) is used as the color developer. Provided is a multicolor heat-sensitive recording material characterized by containing the following.

(In the formula, X: halogen or hydrogen; R: represents an alkyl group, an aralkyl group, an aryl group, or a cycloalkyl group.) Examples of the color developer of the general formula used in the present invention include the compounds shown below. It will be done.

Ethyl bis(3-chloro-4-hydroxyphenyl)acetate, Isopropyl bis(3-chloro-4-hydroxyphenyl)acetate, Butyl bis(3-chloro-4-hydroxyphenyl)acetate.

Bis(3-chloro-4-hydroxyphenyl)phenyl acetate.

Cyclohexyl bis(3-chloro-4-hydroxyphenyl)acetate, Benzyl bis(3-chloro-4-hydroxyphenyl)acetate, Methyl bis(3-chloro-4-hydroxyphenyl)acetate, Bis(3-chloro-4- hydroxyphenyl) phenethyl acetate, bis(3-chloro-4-hydroxyphenyl) naphthyl acetate, bis(3-chloro-4-hydroxyphenyl) isoamyl acetate.

Bis(3-chloro-4-hydroxyphenyl)acetic acid-n
-nonyl, bis(3-chloro-4-hydroxyphenyl)ethyl acetate, bis(3-bromo-4-hydroxyphenyl)isopropyl acetate, bis(3-bromo-4-hydroxyphenyl)butyl acetate, bis(3- Bromo-4-hydroxyphenyl)phenyl acetate, bis(3-bromo-4-hydroxyphenyl)cyclohexyl acetate, bis(3-bromo-4-hydroxyphenyl)phenethyl acetate, bis(3-bromo-4-hydroxyphenyl) Naphthyl acetate, bis(3-bromo-4-hydroxyphenyl)isoamyl acetate, bis(3-bromo-4-hydroxyphenyl)acetic acid-n
-nonyl.

Bis(3-bromo-4-hydroxyphenyl)benzyl acetate, Bis(3-bromo-4-hydroxyphenyl)methyl acetate, Bis(4-hydroxyphenyl)ethyl acetate, Bis(4-hydroxyphenyl)ethyl acetate
-hydroxyphenyl)isopropyl acetate.

Bis(4-hydroxyphenyl)butyl acetate, bis(4-hydroxyphenyl)butyl acetate
-hydroxyphenyl)phenyl acetate, bis(4-hydroxyphenyl)cyclohexyl acetate, bis(4-hydroxyphenyl)benzyl acetate, bis(
4-hydroxyphenyl)methyl acetate, bis(4-hydroxyphenyl)phenethyl acetate, bis(4-hydroxyphenyl)naphthyl acetate, bis(4-hydroxyphenyl)isoamyl acetate, bis(4-hydroxyphenyl)acetate-n-nonyl .

These compounds are added in an amount of 0.5 to 10 parts by weight of the dye.
It is preferable to use within the range of parts by weight. Furthermore, in the present invention, it is also possible to add conventionally known color developers such as tetrabromophenol A and bis(4-hydroxyphenylsulfone), if necessary.

The leuco dyes used in the present invention can be applied singly or in combination of two or more types, but such leuco dyes include:
Those applied to this type of heat-sensitive material can be arbitrarily applied. For example, leuco compounds of dyes such as triphenylmethane-based, fluoran-based, phenothiazine-based, auramine-based, spiropyran-based, and indolinophthalide-based dyes are preferably used. . Specific examples of such leuco dyes include those shown below.

3.3-bis(ρ-dimethylaminophenyl)-phthalide, 3.3-bis(ρ-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet lactone), 3.3-bis(p- dimethylaminophenyl)-6-dibutylaminophenyl, 3.3-bis(ρ-dimethylaminophenyl)-6-chlorophthalide.

3.3-bis(p-dibutylaminophenyl)phthalide, 3-cyclohexylamino-6-chlorofluorane, 3-dimethylamino-5,7-dimethylfluorane.

3-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7,8-benzfluorane, 3-diethylamino-
6-Methyl-7-chlorofluorane, 3-(N-p-tolyl-N-ethylamino)-6-methyl-7-anilinofluorane.

3-pyrrolidino-6-methyl-7-anilinofluorane.

2- (N-(3'-trifluoromethylphenyl)
amino)-6-dinithylaminofluorane, 2-(3,
6-bis(diethylamino)-9-(o-chloroanilino)xantylbenzoic acid lactam), 3-diethylamino-6-methyl-7-(m-trichloromethylanilino)fluoran, 3-diethylamino-7-(0-chloroanilino) ) fluoran, 3-dibutylamino-7-(o-chloroanilino)fluoran, 3-N-methyl-N-amylamino-6-methyl-7-
7-anilinofluorane, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino) -5-methyl-7-(
N.

N-dibenzylamino)fluoran, benzoylleucomethylene blue, 6'-chloro-815-methoxy-benzoindolino-
Pyrylospiran, 6'-bromo-3'-methoxy-benzoindolino-pyrylospiran, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-chlorophenyl) phthalide, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-nitrophenyl)phthalide, 3-(2'-hydroxy-4'-diethylaminophenyl)-3- (2'-methoxy-5'-methylphenyl)phthalide, 3-(2'-methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chloro-5'-
methylphenyl)phthalide, 3-morpholino-7-(N-propyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7-(N -benzyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-(di-P-chlorophenyl)methylaminofluorane, 3-diethylamino-5-chloro-7-(α-phenylethylamino)fluorane, 3- (N-ethyl-p-toluidino)-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-(o-methoxycarbonylphenylamino)fluoran.

3-diethylamino-5-methyl-7-(α-phenylethylamino)fluorane, 3-diethylamino-7-piperidinofluorane, 2-
Chloro-3-(N-methyltoluidino)-7-(p-n
-butylanilino)fluoran, 3-(N-benzyl-N-cyclohexylamino)-5
, 6-penzo 7-α-naphthylamino-4'-bromofluorane, 3-diethylamino-6-methyl-7-mesitidino 4
',5'-benzofluorane etc.

In the present invention, the combination of color tones can be freely selected, but it is necessary to prevent the low-temperature coloring layer from coloring during high-temperature coloring. Material properties required for such a color erasing agent include showing basicity, being poorly soluble in water, having a melting point of at least 80°C, and being stable in air or against heat. , low toxicity, etc. Examples of such decolorizing agents include the following.

(a) A piperazine derivative represented by the following general formula (1), (II) or (TV); (b) a disubstituted amide compound of a dihydric carboxylic acid represented by the following general formula (m); ) and (c) have 3 or more amide groups in the molecule, or 2 or more amide groups and 1
Compounds having 3 or more tertiary amine groups.

General formula (I) 2 General formula (■) 2 General formula (■) 2 General formula (■) 2 General formula (V) General formula (1), (Ul), (m), (IV) and (
V) Inside, R1, R2, R1, R4, R,, R6, R,,
R,, R9, R10% R11 and R13 are alkyl, cycloalkyl, aryl or aralkyl which may have a substituent, and the terminals of R5 and R6 and R7 and R8 are bonded to each other to form a cyclic structure. Very good. R1□ represents a lower alkylene group, A represents a divalent aliphatic group or an aromatic group, X, X and X are carbonyl or sulfonyl, and Y and Y represent alkylene. The alkyl represented by R~Rxx, R13 is usually a straight chain or branched chain having 1 to 18 carbon atoms, the cycloalkyl is cyclohexyl, and the aryl is phenyl, Examples of aralkyl include tolyl and xylyl.
Examples include benzyl and phenethyl. These substituents may further have other substituents, such as alkyl, aryl, halogen, alkoxy, aryloxy, acyl, acyloxy, alkoxycarbonyl, carbamoyl, Examples include acylamino. Also, general formula (1)
The piperazine ring in (II) and (rV) is also bonded with one or more C substituents such as alkyl, aryl, halogen, alkoxy, aryloxy, acyl, acyloxy, alkoxycarbonyl, carbamoyl, acylamino, etc. You can leave it there.

Specific examples of the compound represented by the general formula (1) include the following.

N-Methyl-N'-phenylacetylpiperazine N-propyl-N'-phenylacetylpiperazine, N-propyl-N'-benzoylpiperazine, N-butyl-N'-benzoylpiperazine, N-cyclohexyl-N'- Benzoylpiperazine, N-hexyl-N'-benzoylpiperazine, N-lauryl-N'-benzoylpiperazine.

N-stearyl-N'-benzoylpiperazine, N-phenyl-N'-benzoylpiperazine, N-benzyl-
N'-benzoylpiperazine, N-phenyl-N'-cyclohexyloylpiperazine, N-phenyl-N'-acetylpiperazine, N-phenyl-N'-lauroylpiperazine, N-phenyl-N'
-ρ-methylbenzoylpiperazine, N-phenyl-N/-p-chlorobenzoylpiperazine, N-benzoylaminoethyl-N'-benzoylpiperazine.

N-benzoylaminopropyl-N'-benzoylpiperazine, N-benzoylaminobutyl-N'-benzoylpiperazine, N-benzoylaminopropyl-N'-cyclohexylpiperazine, N-cyclohexylaminopropyl-N' - Cyclohexyloylpiperazine.

N-benzoylaminoamyl-N'benzoylpiperazine, N (p-chlorobenzoylaminoamyl)-N'-
(Chlorobenzoyl)piperazine, N-phenyl-N'-benzenesulfonylpiperazine, N-benzyl-N'-benzenesulfonylpiperazine, N-methyl-N'-benzenesulfonylpiperazine.

N-propyl-N'-benzenesulfonylpiperazine, N-butyl-N'-benzenesulfonylpiperazine, N-hexyl-N'-benzenesulfonylpiperazine, N-cyclohexyl-N'-benzenesulfonylpiperazine, piperazine, N -Lauryl-N'-benzenesulfonylpiperazine, N-stearyl-N'-benzenesulfonylpipebutane, N-phenyl-N'-butylsulfonylpiperazine, N-phenyl-N'-laurylsulfonylpiperazine, N-phenyl-N' -stearylsulfonylpiperazine.

N-phenyl-N'-cyclohexylsulfonylpiperazine, N-phenyl-N'-benzylsulfonylpiperazine, N-phenyl-N'-(p-methylbenzenesulfonyl)piperazine, N-butyl-N'-(p- methylbenzenesulfonyl)piperazine, N-benzoylaminopropyl-N'-benzenesulfonylpiperazine, N-benzoylaminopropyl-N'-ρ-methylbenzenesulfonylpiperazine, N-benzoylaminoethyl-N'-benzenesulfonylpiperazine, N- Benzoylaminobutyl-N'-benzenesulfonylpiperazine, N-benzoylaminopropyl-N'-butanesulfonylpiperazine.

N-naphthoylaminopropyl-N'-benzenesulfonylpiperazine, N-benzenesulfonylaminopropyl-N'-benzenesulfonylpiperazine, N-butyroylaminopropyl-N'-benzoylpiperazine, N-hexyloylaminopropyl-N '-benzoylpiperazine, N-lauroylaminopropyl-N'-benzoylpiperazine.

N-stearoylaminopropyl-N'-benzoylpiperazine.

N-stearoylaminopropyl-N'-benzenesulfonylpiperazine and the like.

Specific examples of the compound represented by the general formula (■) include the following.

N,N'-bis(benzenesulfonyl)piperazine,
N,N'-bis(P-methylbenzenesulfonyl)piperazine, N,N'-bis(P-isopropylbenzenesulfonyl)piperazine, N,N'-bis(p-chlorobenzenesulfonyl)piperazine, N,N'-bis (0-chlorobenzenesulfonyl)piperazine, N,N'-bis(m-chlorobenzenesulfonyl)piperazine, N,N'-bis(p-bromobenzenesulfonyl)piperazine, N,N'-bis(butylsulfonyl)piperazine.

N,N'-bis(octylsulfonyl)piperazine.

N,N'-bis(laurylsulfonyl)piperazine.

N,N'-bis(stearylsulfonyl)piperazine, N,N'-bis(cyclohexylsulfonyl)piperazine.

N,N'-bis(ρ-laurylbenzenesulfonyl)
piperazine.

N,N'-bis(cyclohexylsulfonyl)piperazine, N-butylsulfonyl-N'-benzenesulfonylpiperazine, N-octylsulfonyl-N'-benzenesulfonylpiperazine, N-(o-chlorobenzenesulfonyl)-N' -Benzenesulfonylpiperazine.

N-lauroyl-N'-benzenesulfonylpiperazine, N-lauroyl-N'-(p-methylbenzenesulfonyl)piperazine.

N-benzoyl-N'-benzenesulfonylpiperazine, N-(0-chlorobenzoyl)-N'-benzenesulfonylpiperazine.

N-(o-methylbenzoyl)-N'-benzenesulfonylpiperazine.

N,N'-bis(butyroyl)piperazine, N,N'
-bis(hexyloyl)piperazine, N,N'-bis(n-ofthyroyl)piperazine, N,N'-bis(tertiary-ofthyroyl)piperazine, N,N'-bis(lauriloyl)piperazine, N,N
' -bis(steacoil)piperazine, NIN' -
Bis(pivaloyl)piperazine, N,N'-bis(cyclohexyloyl)piperazine, N,N'-bis(ρ
-methylcyclohexyloyl)piperazine, N,N'-bis(P-methylphenylacetyl)piperazine, N,N'-bis(phenylacetyl)piperazine, N
, N'-bis(phenylpropionyl)piperazine, N,N'-bis(benzoyl)piperazinone, N,N
'-bis(phenoxyacetyl)piperazine, N,N
'-bis(P-chlorobenzoyl)piperazine, N,
N'-bis(2-phenoxypropionyl)piperazine, N,N'-bis(m-chlorobenzoyl)piperazine, N,N'-bis(0-chlorobenzoyl)piperazine, N,N'-bis(ρ-methyl benzoyl)piperazine, N,N'-bis(m-methylbenzoyl)piperazine, N,N'-bis(0-methylbenzoyl)piperazine, N,N'-bis(0-acetyloxybenzoyl)piperazine, N,N '-bis(0-butyryloxybenzoyl)piperazine, N,N'-bis(ρ-phenylbenzoyl)piperazine, N,N'-bis(ρ-methoxycarbonylbenzoyl)piperazine, N,N'-bis(P- isopropoxycarbonylbenzoyl)piperazine, N,N'-bis(ρ-octadecylcarbamoylbenzoyl)piperazine, and the like.

In the general formula (m), R, R, R, R, etc. represent substituted or unsubstituted alkyl, cycloalkyl, aryl, or aralkyl, and R and R or R and R, etc. are bonded at their terminal ends, respectively. It is also possible to form a ring. Examples of the alkyl include straight or branched chains having 4 to 18 carbon atoms; examples of the cycloalkyl include cyclohexyl; examples of the aryl include phenyl, tolyl, xylyl, etc.; Examples of alkyl include benzyl and phenethyl. These substituents are
It may further have other substituents, such as alkyl, aryl, alkoxy, acyl, halogen, acylamino such as benzoylamino, acetylamino, alkoxycarbonyl, carbamoyl, aryloxy, etc. , aralkyloxy, and the like. A is an aliphatic group or an aromatic group, and in the case of an aliphatic group, it is usually substituted or unsubstituted and has 1 to 1 carbon atoms.
8, and in the case of an aromatic group, it is a substituted or unsubstituted arylene such as phinidine, tolylene, xylylene, etc. In this case, the substituent is the above-mentioned halogen, acylamino, alkoxycarbonyl, Examples include carbamoyl, aryloxy, aralkyloxy, and the like.

Specific examples of the disubstituted amide compounds of aliphatic and aromatic dihydric carboxylic acids include the following.

N,N,N',N'-tetrabutylsuccinic diamide, N,N,N',N'-tetraoctylsuccinic diamide.

N, N, N', N'-tetralaurylsuccinic acid diamide, N, N, N', N'-tetrastearylsuccinic acid diamide, N, N, N', N'-tetraphenyladipic acid diamide, N, N,N',N'-tetra-p-butylphenyladipate diamide, N,N,N',N'-tetrabutyladipate diamide, N,N,N',N'-tetraoctyladipate diamide, N,N,N',N'-tetralauryladipic acid diamide.

N,N,N',N'-tetrastearyladipate diamide, N,N'-dicyclohexyl-N,N'-dimethylsuccinic acid diamide, N,N'-dicyclohexyl-N,N'-dimethyl Glutaric acid diamide.

N,N'-dicyclohexyl-N,N'-dimethyladipate diamide, N,N,N',N'-tetracyclohexyladipate diamide, N,N'-dimethyl-N,N'-dicyclo xylsperate diamide 1, N,N'-dimethyl-N,N'-dicyclohexylsebacic acid diamide, N,N'-dimethyl-N,N'-dicyclohexylmalonic acid diamide, N,N,N',N'- Tetrabenzyladipic acid diamide, Adiboyldipiperidine, Adiboyldipipecoline, Adipoyl-di-ε-caprolactam, Adipoyldi-
Pyrrolidone, Adiboyldipiperidone, Sebacoyl di-mi-caprolactam, Sebacoyl di-piperidone, Adipoyl-di-3-chloro-E-caprolactam.

succinyl-di-3-chloro-ε-caprolactam, etc.

N, N'-terephthaloyl bispiperidine.

N,N'-Isophthaloyl bispiperidine, N,N'
-phthaloylbispiperidine, N,N'-terephthaloylbismorpholine, N,N'-isophthaloylbismorpholine, N,N'-phthaloylbismorpholine, N,N'-terephthaloylbis-4- Methylpiperazine, N,N'-isophthaloylbis-4-methylpiperazine, N,N'-phthaloylbis-4-methylpiperazine,
N,N'-terephthaloylbis-4-phenylpiperazine.

N,N'-Isophthaloylbis-4-phenylpiperazine, □N,N'-phthaloylbis-4-phenylpiperazine, N,N'-terephthaloylbis-4-propylpiperazine, N,N'-Isophthaloylpiperazine Roylbis-4-propylpiperazine.

N, N'-phthaloyl-4-propylpiperazine, N
, N'-terephthaloyl biscaprolactam, N, N'
-Isophthaloyl biscaprolactam, N, N' -
Phthaloyl biscaprolactam, N,N'-terephthaloyl bis-3-chlorocaprolactam.

N,N'-isophthaloylbis-3-chlorocaprolactam, N,N'-phthaloylbis-3-chlorocaprolactam, N,N'-terephthalolbisvalerolactam, N,N'
-Isophthaloyl bisvaleractam, N, N'-
Phthaloyl biscaprolactam.

N,N'-terephthaloyl bispyrrolidine, N,N'
-Isophthaloylbispirolidine, N,N'-phthaloylbispirolidine, N,N'-terephthaloylbis-diethylamine.

N, N'-isophthaloylbis-diethylamine, N
, N'-phthaloylbis-diethylamine, size, N'
-Terephthaloylbis-dipropylamine, N,N'-isophthaloylbis-dipropylamine, N,N'-terephthaloylbis-dibutylamine, N
, N'-isophthaloylbis-dibutylamine, N,
N'-terephthaloylbis-cyclohexyl-methylamine.

N,N'-isophthaloylbiscyclohexyl-methylamine, N,N'-terephthaloylbis-dicyclohexylamine N,N'-isophthaloylbis-dicyclohexyl-
Amine, N,N'-Terephthaloylbis-dibenzylamine, N,N'-Isophthaloylbis-dibenzylamine, N,N'-Terephthaloylbis-dioctylamine, N,N'-Isophthaloyl Loylbis-dioctylamine, N,N'-terephthaloylbis-jethoxypropylamine.

N,N'-terephthaloylbis-4-chlorobutylamine, N,N'-terephthaloylbis-dibenzoylaminoethylamine, N,N'-isophthaloylbis-dibenzoylaminoethylamine, N,N'- Terephthaloylbis-benzoylaminoprobylamine, N,N'-isophthaloylbis-benzoylaminoprobylamine, N,N'-terephthaloylbis-diacetylaminoethylamine.

N,N'-isophthaloylbis-diacetylaminoethylamine, N,N'-terephthaloylbis(4-methylpiperidine), N,N'-terephthaloylbis(3-methylpiperidine), N,N' -terephthaloyl bis(3,5-dimethylpiperidine), N,N'-terephthaloyl bis(2-methylpiperidine), N,N'-terephthaloyl bis(2,6-dimethylpiperidine), N, N'-isophthaloyl bis(4-methylpiperidine), N,N'-phthaloyl bis(4-methylpiperidine)
, N,N'-isophthaloylbis(3-methylpiperidine), N,N'-phthaloylbis(3-methylpiperidine)
, N,N'-isophthaloylbis(3,5-dimethylpiperidine).

N,N'-phthaloylbis(3,5-dimethylpiperidine), N,N'-isophthaloylbis(2-methylpiperidine), N,N'-phthaloylbis(2-methylpiperidine)
, N,N'-isophthaloyl bis(2,6-dimethylpiperidine), N,N'-phthaloyl bis(2,6-dimethylpiperidine).

N,N'-terephthaloyl bis(4-benzylpiperidine).

N,N'-isophthaloylbis(4-benzylpiperidine), N,N'-phthaloylbis(4-benzylpiperidine), -N,N'-terephthaloylbis(4-methoxycarbonylpiperidine), N,N '-isophthaloyl bis(4-methoxycarbonylpiperidine), N,N'-terephthaloyl bis(2-methoxycarbonylpiperidine), N,N'-isophthaloyl bis(2-methoxycarbonylpiperidine).

N,N'-phthaloylbis(2-methoxycarbonylpiperidine).

N, N'-terephthaloyl bis(4-ethylpiperidine), N, N'-terephthaloyl bis(4-propylpiperidine), N, N'-terephthaloyl bis(4-butylpiperidine), N, N'-Isophthaloylbis(4-ethylpiperidine).

N,N'-Isophthaloylbis(4-n-n-propylpiperidine).

N,N'-isophthaloylbis(4-butylpiperidine), N,N'-isophthaloylbis(4-butylpiperidine), N,N'-phthaloylbis(4-ethylpiperidine)
, N,N'-phthaloylbis(4-propylpiperidine), NIN'-phthaloylbis(4-butylpiperidine)
, N,N'-terephthaloyl bis(3-hydroxymethylpiperidine), N,N'-isophthaloyl bis(3-hydroxymethylpiperidine), N,N'-phthaloyl bis(3-hydroxymethylpiperidine).

N g N' -terephthaloyl bis(5-ethyl-2
-methylpiperidine), N,N'-isophthaloylbis(5-ethyl-2-methylpiperidine), N,N'-phthaloylbis(5-ethyl-2-methylpiperidine), N,N'-terephthaloylbis Rubis (N-ethyl-N'
-cyclohexylamine), N,N'-isophthaloylbis(N-ethyl-N'
-cyclohexylamine).

N,N'-phthaloylbis(N-ethyl-N'-cyclohexylamine).

N,N'-terephthaloyl bis(N-propyl-N'
-cyclohexylamine), N,N'-isophthaloylbis(N-propyl-N'
-cyclohexylamine).

N,N'-phthaloylbis(N-propyl-N'-cyclohexylamine) N,N'-terephthaloylbis(N-butyl-N'
-cyclohexylamine).

N,N'-isophthaloylbis(N-butyl-N'
-cyclohexylamine), N,N'-phthaloylbis(N-butyl-N'-cyclohexylamine).

N,N'-terephthaloyl bis(4-ethyloxymethylpiperidine), N,N'-isophthaloyl bis(4-ethyloxymethylpiperidine), N,N'-terephthaloyl bis(4-ethyloxy ethylbiperidine), N,N'-isophthaloylbis(4-ethyloxyethylpiperidine), N,N'-terephthaloylbis(2-methoxyethylpiperidine), N,N'-isophthaloylbis (2-methoxyethylpiperidine), N,N'-terephthaloylbis(4-methoxyethylpiperidine), N,N'-(isophthaloylbis(4-methoxyethylpiperidine)).

N,N'-terephthaloylbis(4-phenylpiperidine), N,N'-isophthaloylbis(4-phenylpiperidine), N,N'-phthaloylbis(4-phenylpiperidine), N,N'- Terephthaloyl bis(4-phenylpropylpiperidine), N,N'-isophthaloylbis(4-phenylpropylpiperidine), N,N'-phthaloylbis(4-phenylpropylpiperidine), and the like.

In the general formula (TV), R9 and R1° represent alkyl, cycloalkyl, aryl, or aralkyl which may have a substituent. The alkyl is usually
Examples include straight or branched chains having 1 to 18 carbon atoms, and examples of cycloalkyl include cyclohexyl;
Examples of aryl include phenyl, tolyl, xylyl, etc., and examples of aralkyl include benzyl, phenethyl, etc. These substituents can further have other substituents, such as alkyl, aryl, halogen, alkoxy, aryloxy, aralkyloxy, acyl, acyloxy, alkoxycarbonylacyl amino, etc. The following substituents are mentioned. Y and Y are linear or branched alkylene groups having 1 to 18 carbon atoms.

Specific examples of the compound represented by the general formula (TV) include the following.

N,N'-bis(benzoylaminoethyl)piperazine, N,N'-bis(benzoylaminopropyl)piperazine, N,N'-bis(benzoylaminobutyl)piperazine, N,N'-bis(cyclohexylamino N,N'-bis(hexyloylaminopropyl)piperazine.

N-benzoylaminopropyl-N'-cyclohexylaminoethylpiperazine, N-benzoylaminopropyl-N'-benzoylaminobutylpiperazine, N-(P-chlorobenzoylaminoamyl)-N'-benzoylaminopropylpiperazine, N -Cyclohexyloylaminopropyl-N'-cyclohexyloylaminobutylpiperazine.

N-naphthoylaminopropyl-N'-benzoylaminopropylpiperazine.

N-butyroylaminopropyl-N'-benzoylaminopropylpiperazine, N-lauroylaminopropyl-N'-benzoylaminopropylpiperazine, N-stearoylaminopropyl-N'-benzoylaminopropylpiperazine, N-butyroylaminopropyl- N'-cyclohexylaminobutylpiperazine, N-naphthoylaminopropyl-N'-lauroylaminopropylpiperazine, N-naphthoylaminopropyl-N'-stearoylaminopropylpiperazine, and the like.

Further, specific examples of the compound having three or more amino groups in the molecule, or having two or more amide groups and one or more tertiary amino groups include, for example, the following.

N,N',N'-hribenzoyl-diethylenetriamine, N,N',N'-tribenzoyl-dipropylenetriamine, N,N',N',N"-tetrabenzoyl-triethylenetetramine, 7 -dibencyyl-4-methyl-diethylenetriamine, 1.9-dibenzoyl-5-methyl-dipropylenetriamine, 1.7-diα-naphthoyl-4-methyl-diethyltriamine, 1.7-diα-naphthoyl-4-cyclohexyl -diethylenetriamine, N,N'+N'hlipivaloyl-diethylenetriamine,N,N',N',N"'-tetraacetyltriethylenetetramine,NIN'IN'IN'IN"-tetracyclohexyloyl-triethylene Tetramine.

Ethylenediaminetetraacetic acid tetraanilide, ethylenediaminetetraacetic acid tetracyclohexylamide, ethylenediaminetetraacetic acid tetra-2-ethylhexylamide, ethylenediaminetetraacetic acid tetralaurylamide, ethylenediaminetetraacetic acid tetrastearylamide, ethylenediaminetetraacetic acid tetrapiperidide, ethylenediaminetetraacetic acid tetra-C- Cabrolactamide etc.

In the general formula (V), R1 and R13 represent alkyl, cycloalkyl, aryl, or alkyl which may have a substituent group. The alkyl usually includes a straight chain or branched chain having 1 to 18 carbon atoms, the cycloalkyl includes cyclohexyl, and the aryl includes phenyl.

Examples of aralkyl include tolyl and xylyl, and examples of aralkyl include benzyl and phenethyl.

These ]4 substituents can further have other substituents, such as alkyl,
In addition to aryl and halogen, examples include alkoxy, aryloxy, acyl, acyloxy, alkoxycarbonyl, carbamoylno, and the like. R1 represents a lower alkyl group.

Specific examples of the compound represented by the general formula (V) include the following.

1,3-bis(N-cyclohexylbenzoylbiperidyl)propane, 1,3-bis(N-benzoylpiperidyl)propane,
1,3-bis(N-p-trioylpiperidyl)propane.

1,3-bis(N-pivaloylpiperidyl)propane,
1,3-bis(N-lauroylpiperidyl)propane,
Other examples include polyethers, polyethylene glycol derivatives, solid alcohols, guanidine derivatives, morpholine derivatives, thiurado compounds, and the like.

The decolorizing agent used in the present invention may be used alone or in the form of a mixture of two or more, and these are usually white solids that are stable in the air. Those having a melting point in the range of 120 to 250°C are preferably used.

In the present invention, various conventional binders can be used as appropriate to bind and support the leuco dye, color developer, and decolorizer on the support, such as polyvinyl alcohol, starch and its derivatives, methoxycellulose,
Cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide/acrylic acid ester copolymer, acrylamide/acrylic acid ester/methacrylic acid ternary copolymer, styrene / maleic anhydride copolymer alkali salt, imbutylene / maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein, and other water-soluble polymers, as well as polyvinyl acetate, polyurethane, styrene/butadiene, etc. Latexes such as polymers, polyacrylic acid, polyacrylic esters, vinyl chloride/vinyl acetate copolymers, polybutyl methacrylate, ethylene/vinyl acetate copolymers, styrene/butadiene/acrylic copolymers can be used. .

In addition, in the present invention, in addition to the leuco dye and color developer, if necessary, auxiliary additive components commonly used in this type of heat-sensitive recording material, such as fillers, surfactants, thermofusible substances ( or lubricant) etc. can be used in combination. In this case, fillers include, for example, calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, and surface-treated inorganic fine powders such as calcium and silica. , urea-polymarine resin, styrene/methacrylic acid copolymer, polystyrene resin, and other organic fine powders. Examples of thermofusible substances include higher fatty acids or their esters, amides, or metal salts. In addition, various waxes, condensates of aromatic carboxylic acids and amines, phenyl benzoate, higher linear glycols, dialkyl 3,4-epoxy-hexahydrophthalates, higher ketones, and other thermofusible organic Examples include compounds having a melting point of about 50 to 200°C.

For example, in order to obtain a two-color heat-sensitive recording material according to the present invention, a liquid in which a color-forming dye, a color developer, a decolorizing agent, a binder, etc. are dispersed or dissolved on a support such as paper, synthetic paper, or plastic film is used. It can be obtained by applying, drying, and repeating the process. When further laminating on top of the coated layer, it is necessary to pay close attention to the solubility and releasability of the layer so that the lower layer does not mix with the upper layer. Further, after coating and drying, the upper layer may be applied after calendering. The amount of dye attached to the high-temperature coloring layer is 0.3 g/resistance -1.0 g/i, and the amount of dye attached to the decoloring agent layer is 1.0 g/rrr to 10 g/r.
rf, and the amount of the low-temperature coloring layer deposited is 0.2 g/rr when the leuco dye is deposited as a dry product, as described above.
i-0.6g/proof. The amount of adhesion when providing a protective layer is 0.5g/rr? ~5. Og/m is preferred. When providing an intermediate layer between the decoloring agent layer and the low-temperature coloring layer or between the decoloring layer and the high-temperature coloring layer, the former has a content of 0.5g/% to 5.0g/%.
rri' is preferred, and the latter is preferably Ig/-10 g/n.

Furthermore, by further increasing the number of thermosensitive coloring layers in the same manner as described above, it is also possible to obtain a multicolor thermosensitive recording material having three or more colors.

〔effect〕

The multicolor thermosensitive recording material of the present invention has the above structure.

By using the compound of the general formula ([) as a color developer, the color development and decolorization properties of the low-temperature color formation layer are significantly improved, and an excellent multicolor color image can be obtained.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples. Note that all parts and percentages shown below are based on weight.

Example 1 The following components were each pulverized and dispersed for 24 hours using a ball mill to obtain dispersions A-D.

[Dispersion A]

3-(N-ethyl-N-amylamino)-6-methyl-7-anilite fluorane (black) 20 parts 10% polyvinyl alcohol aqueous solution 20 parts water
60 parts [Dispersion B] Calcium carbonate 10 parts Polyvinyl alcohol 10% aqueous solution 20 parts Water
60
Part [Dispersion C] 10% polyvinyl alcohol aqueous solution 20 parts water
60 parts [Dispersion D] 3.3-Dichlorophenylthiourea 10 parts Calcium carbonate 10 parts Polyvinyl alcohol 10% aqueous solution 20 parts Water
60 parts or more of Dispersion A and Dispersion B obtained in the above manner were mixed and stirred to obtain a thermosensitive coloring layer forming liquid for low temperature coloring.

On the other hand, the dispersion liquid C1 was mixed and stirred to obtain a thermosensitive coloring layer forming liquid for high temperature coloring. Furthermore, a decolorizing agent layer forming liquid for forming a decolorizing agent layer was prepared at the following ratio.

[Decolorant forming liquid]

Polyvinyl alcohol aqueous solution 20 parts water

60 parts Next, on high-quality paper with a basis weight of approximately 52 g/rf, the high temperature thermosensitive color forming layer forming liquid (dry coating amount 6 g/B) and decoloring agent layer forming liquid (dry coating @4 g/B) A multicolor heat-sensitive recording material was obtained by sequentially coating and drying.

Example 2 Same as Example 1 except that benzyl bis(3-chloro-4-hydroxyphenyl)acetate was used instead of ethyl bis(3-bromo-4-hydroxyphenyl)acetate in Solution B. A thermosensitive recording material was obtained in the same manner.

Example 3 Heat-sensitive recording was carried out in the same manner as in Example 1 except that methyl bis(4-hydroxyphenyl)acetate was used instead of ethyl bis(3-bromo-4-hydroxyphenyl)acetate in Solution B. I got the material.

Comparative Example 1 In Example 1, a heat-sensitive recording material was obtained by using bis(4-hydroxyphenyl)sulfone instead of ethyl bis(3-bromo-4-hydroxyphenyl)acetate in the B solution.

Comparative Example 2 In Example 1, a heat-sensitive recording material was obtained using benzyl p-hydroxybenzoate instead of ethyl bis(3-bromo-4-hydroxyphenyl)acetate in Solution B.

The multicolor heat-sensitive recording materials of Examples and Comparative Examples obtained as described above were tested as follows.

■Image density: Head power 0.611/dot using a printing tester with a thin film head manufactured by Matsushita Electronic Components Co., Ltd.■Line recording time Ion's/Q, scanning line density 8X7.7 dots/mm
Under these conditions, the low-temperature coloring layer was printed for 1.0ms during the pulse, and the high-temperature coloring layer was 2.2Ils during the pulse, and the print density was measured using a Macbeth densitometer RD-514 (filter Wratten-106).
It was measured with

■Survival rate The residual rate of low-temperature coloring during high-temperature coloring, It is expressed by the formula.

The results are shown in the table.

Table 1 As shown above, it can be seen that the multicolor heat-sensitive recording material of the present invention has excellent coloring properties of the low-temperature coloring layer and significantly improved color erasing properties.

Claims (1)

[Claims] (1) A multicolor thermosensitive recording material comprising at least one decolorizing agent, two or more dyes, and a color developer, which contains a compound having a structure represented by the following general formula as the color developer. A multicolor heat-sensitive recording material characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X: halogen or hydrogen, R: represents an alkyl group, aralkyl group, aryl group, or cycloalkyl group.)