JPS61220888A - Two color forming thermal recording material - Google Patents

Abstract

PURPOSE:To provide the titled material having a sufficient decolorizing effect, favorable separation property of two colors and free of mixing of colors in high-temperature developed color images, by a method wherein at least the second thermal color forming layer constituting an upper layer of two thermal color forming layers is provided by using a color forming system comprising a basic leuco dye and a color developer, and the amount on a dry weight basis of the dye used is specified. CONSTITUTION:A color forming system comprising a basic leuco and a color developer is used to provide at least the second thermal color forming layer constituting the upper layer of two thermal color forming layers, in a two color forming thermal recording material comprising on a base the first and second thermal color forming layers differing in color forming thermal energy and in tone of the color formed, wherein the thermal color forming layer requiring less energy for color forming is provided as the upper layer, and the second thermal color forming layer comprises a decolorizing agent at a position suitable for showing a decolorizing effect, the dye being used in an amount of 0.2-0.5g/m<2> on a dry weight basis. The dye may be a leuco compound of a dye based on triphenylmethane, fluoran, spiropyran or the like.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a two-color heat-sensitive recording material, and more specifically, the present invention relates to a two-color heat-sensitive recording material, and more specifically, heat-sensitive color-forming layers having different color-forming heat energy and different color tones are sequentially stacked on a support. The present invention relates to a two-color thermosensitive recording material formed by the method.・ [Prior art] A thermosensitive recording material is a material in which a thermosensitive coloring layer that can form a colored image by heating is provided on a support such as paper, and thermal printers equipped with a thermal head are widely used for heating. It is used.

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 develops color by reacting with this leuco dye when heated. Agent (color development aid)
Those containing these are widely 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 records using differences in heating temperature or thermal energy.

Accordingly, various multicolor thermosensitive recording papers have been proposed. 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 of them is that when coloring the high temperature coloring layer, the color is mixed with the color tone of the low temperature coloring layer to obtain a color tone different from that of the low temperature coloring layer.

The other method is to use a decoloring agent that decolorizes the low-temperature color-forming layer when coloring the high-temperature color-forming layer to obtain only the color tone of the high-temperature color-forming layer without color mixing of the color tone of the low-temperature color-forming layer. As a specific example of these, the former is
Publication No. 49-4342.

Special Publication No. 49-27708, Japanese Patent Publication No. 48-86543
Publication No.

It is described in Japanese Patent Publication No. 49-65239, etc., and the latter is described in Japanese Patent Publication No. 50-17865, Japanese Patent Publication No. 50-17866, Japanese Patent Publication No. 51-29024,
Japanese Patent Publication No. 51-87542, Japanese Patent Publication No. 50-1804
8, Japanese Patent Publication No. 55-36519, etc., respectively.

However, in the case of the former multicolor thermosensitive recording paper,
During high-temperature color development, the color tone that can be specifically achieved is red-black because the color is mixed with the color tone of the low-temperature color development layer.

There is a drawback that high-temperature color tones such as blue-black are limited to black threads that have hiding power. On the other hand, in the case of the latter multicolor thermosensitive recording paper, the combination of color tones can be freely selected;
A higher aliphatic alcohol and polyether that decolorizes the low-temperature coloring layer during high-temperature coloring.

Polyethylene glycol derivatives, acetamide, stearamide, phthalonitrile as nitrogen-containing organic compounds,
Decoloring agents such as guanidine derivatives and morpholine derivatives as amine derivatives have low decoloring effects and cannot completely decolorize the color tone of the low-temperature coloring layer during high-temperature coloring, resulting in color mixing or blurring of the low-temperature coloring layer. It has the disadvantage that it can cause To deal with this, it is necessary to apply multiple layers of a high-temperature color forming layer, a decoloring agent layer, and a low-temperature coloring layer, and to make the decolorizing agent layer sufficiently thick. When coloring a high-temperature coloring layer in a printer, facsimile, etc., the thermal head requires high energy.
In the case of a recorder, when performing high-speed recording, heat conduction in the depth direction of the thermosensitive coloring layer becomes low, resulting in a problem that the lowermost high-temperature coloring layer does not develop sufficient color.

〔the purpose〕

An object of the present invention is to provide a two-color thermosensitive recording material that has a sufficient decolorizing effect, has good color separation between the two colors, and does not cause color mixing in high-temperature color images.

〔composition〕

According to the present invention, first and second heat-sensitive coloring layers each having different coloring heat energy and producing different color tones are stacked on a support such that the one with lower coloring heat energy is the upper layer. 2, which has a two-color thermosensitive coloring layer, and a decoloring agent is present in a position where it can decolorize the second thermosensitive coloring layer.
In the color-forming thermosensitive recording material, the second thermosensitive coloring layer forming at least the upper layer of the two thermosensitive coloring layers is constructed using a coloring system consisting of a basic leuco dye and a color developer; A two-color thermosensitive recording material is provided, characterized in that the amount of dye used is 0.2 to 0.5 g/m2 on a dry weight basis.

In the present invention, the amount of basic leuco dye used in the second thermosensitive coloring layer is 0.2 to 0.5 g/dry weight basis.
rrl' range. In this case, this usage amount is 0
．． If it is less than 2g/rrr, the density of the recorded image will be low although it is easy to erase the color.
If it is larger than f, the density of the recorded image will be high, but it will be difficult to erase the color. According to the research of the present inventors, by specifying the amount of basic leuco dye used within the above range,
It has been found that it is possible to obtain a high-quality two-color thermosensitive recording material that has excellent quality of recorded images and also has good color separation between the two colors.

As the color erasing agent used in the present invention, various conventionally known color erasing agents such as those shown in the explanation of the prior art can be used, and as a color erasing agent with a higher color erasing effect, the following general formula (1), (II), (I[I
), (IV) and (V), compounds having three or more amide groups in the molecule, or having two or more amide groups and one or more tertiary amino group, N ,
Preference is given to using N'-dithiocicaprolactam and the like.

General formula (I) General formula (II) General formula (m) General formula (IV) General formula (V) In the general formulas (1), (II) and (III), R1 and R2 have a substituent. is optionally alkyl, cycloalkyl, aryl or aralkyl, and X is carbonyl or sulfonyl. The alkyl represented by R1 and R2 is usually a straight chain or branched chain having 1 to 18 carbon atoms, the cycloalkyl is cyclohexyl, and the aryl is phenyl, tolyl, xylyl, etc. Examples of aralkyl 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. In addition, the piperazine ring in general formulas (I) to (m) also includes alkyl, aryl, halogen, alkoxy, aryloxy,
One or more substituents such as acyl, acyloxy, alkoxycarbonyl, carbamoyl, and acylamino may be bonded.

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'
-p-methylbenzoylpiperazine, N-phenyl-NJ 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'benzoyl piperazine.

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, N-lauryl-N'-benzenesulfonylpiperazine, N-stearyl-N'-benzenesulfonylpiperazine, 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-Nl-P-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, etc.

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

N,N'-bis(benzenesulfonyl)piperazine.

N,N'-bisCP-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(P-laurylbenzenesulfonyl)
piperazine.

N,N'-bis(cyclohexylsulfonyl)piperazine, N-butylsulfonyl-N'-benzenesulfonylbiperazine.

N-octylsulfonyl-N'-benzenesulfonylpiperazine, N-(o-chlorobenzenesulfonyl)-N'-benzenesulfonylpiperazine, N-lauroyl-N'-benzenesulfonylpiperazine, N-lauroyl-N'-(p-methyl benzenesulfonyl)piperazine.

N-benzoyl-N'-benzenesulfonylpiperazine.

N-(o-chlorobenzoyl)-N'-benzenesulfonylpiperazine, N-(o-methylbenzoyl)-N'-benzenesulfonylpiperazine, and the like.

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

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(stearoyl)piperazine.

N,N'-bis(pivaloyl)piperazine, N,N'
-bis(cyclohexyloyl)piperazine, N, N'
-bis(p-methylcyclohexyloyl)piperazine, N,N'-bis(p-methylphenylacetyl)piperazine, N,N'-bis(phenylacetyl)piperazine, N
, N'-bis(phenylpropionyl)piperazine, N,N'-bis(benzoyl)biperandin, N,N'
-Bis(phenoxyacetyl)piperazine.

N,N'-bis(p-chlorobenzoyl)piperazine, N,N'-bis(2-phenoxypropionyl)piperazine, N,N'-bis(-monochlorobenzoyl)piperazine.

N,N'-bis(0-chlorobenzoyl)piperazine,
N,N'-bis(p-methylbenzoyl)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 (p-phenylbenzoyl)piperazine.

N,N'-bis(p-methoxycarbonylbenzoyl)piperazine, N,N'-bis(P-isopropoxycarbonylbenzoyl)piperazine, N,N'-bis(p-octadecylcarbamoylbenzoyl)piperazine, and the like.

In the general formula (mV), R, R2, R3 and R4 represent substituted or unsubstituted alkyl, cycloalkyl, aryl or aralkyl, and R1 and R2 or R3 and R4 are bonded at their terminals, respectively. It is also possible to form a ring. The alkyl usually includes a straight chain or branched chain having 4 to 18 carbon atoms, the cycloalkyl includes cyclohexyl, the aryl includes phenyl, tolyl, xylyl, etc. Examples of alkyl include benzyl and phenethyl. These substituents can further have other substituents,
Examples of such substituents include alkyl, aryl, alkoxy, acyl, halogen, and acylamino such as benzoylamino and acetylamino, alkoxycarbonyl, carbamoyl, aryloxy, and aralkyloxy. A is an aliphatic group or an aromatic group, and in the case of an aliphatic group, it is usually a substituted or unsubstituted alkylene having 1 to 8 carbon atoms, and in the case of an aromatic group, ! [Substituted or unsubstituted] arylene such as dinidine, tolylene, xylylene, etc., and in this case, the substituent includes the above-mentioned halogen, acylamino, alkoxycarbonyl, carbamoyl, aryloxy, aralkyloxy, etc. It will be done.

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

N,N,N',N'-tetrabutylsuccinic acid diamide, N,N,N',N'-tetraoctylsuccinic acid 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-butylphenyladipic acid Diamide.

N, N, N', N'-tetrabutyl adipate diamide, N, N, N', N'-tetraoctyl adipate diamide, N, N, N', N'-tetralauryl adipate diamide, N, N,N',N'-tetrastearyladipate diamide, N,N'-dicyclohexyl-N,N'-dimethylsuccinic acid diamide, N,N'-dicyclohexyl-N,N'-dimethylglutaric acid diamide, N,N'-dicyclohexyl-N,N'-dimethyladipic acid diamide, N,N,N',N'-tetracyclohexyladipic acid diamide.

N,N'-dimethyl-N,N'-dicyclohexylsperic acid diamide, N,N'-dimethyl-N,N'-dicyclohexyl sebacic acid diamide.

N,N'-dimethyl-N,N'-dicyclohexylmalonic acid diamide.

N,N,N',N'-tetrabenzyladipate diamide.

Adiboyldipiperidine.

Ajiboil Jibipekorin, Adipoyl-G-E-force prolactam.

Adipoyldi-pyrrolidone.

adiboyldipiperidone, Sebacoil di- and one caprolactam.

sebacoil di-piperidone, Adipoyl-di-3-chloro-ε-caprolactam.

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

N, N'-terephthaloyl bispiperidine.

N,N'-Isophthaloyl bispiperidine, N,N'
-phthaloyl bispiperidine.

N,N'-terephthaloyl bismorpholine, N,N'
-Isophthaloyl bismorpholine.

N,N'-phthaloyl bismorpholine, 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'-terephthaloy Rubis-4-propylpiperazine, N,N'-isophthaloylbis-4-propylpiperazine, N,N'-phthaloyl-4-propylpiperazine, N
, N'-terephthaloyl biscaprolactam, N, N
'-Isophthaloyl biscaprolactam, N, N'
-phthaloylbiscaprolactam, N,N'-terephthaloylbis-3-chlorocaprolactam, N,N'-isophthaloylbis-3-chlorocaprolactam, N,N'-phthaloylbis-3-chlorocaprolactam/N, N'-terephthalorbisvalerolactam, N,N
'-Isophthaloyl bisvaleractam, N, N'
- Phthaloyl bispyrrolidine/U lactam, N, N' - Terephthaloyl bispyrrolidine, N, N' - Isophthaloyl bispyrrolidine, N, N' - Phthaloyl bispyrrolidine, N, N' - Terephthaloyl bis-diethylamine , N,N'-isophthaloylbis-diethylamine, N,N'-phthaloylbis-diethylamine, N,
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-dicyclohexyl-
Amine N,N'-isophthaloylbis-dicyclohexyl-
Amine.

N, N'-terephthaloyl bis-dibenzylamine, N, N'-isophthaloylbis-dibenzylamine, N, N'-terephthaloyl bis-dioctylamine, N,N'-isophthaloylbis-dioctylamine.

N,N'-terephthaloylbis-jethoxyprobylamine, N,N'-terephthaloylbis-4-chlorobutylamine.

N,N'-terephthaloylbis-dibenzoylaminoethylamine.

N,N'-Isophthaloylbis-dibenzoylaminoethylamine.

N,N'-terephthaloylbis-benzoylaminopropylamine, N,N'-isophthaloylbis-benzoylaminopropylamine.

N,N'-terephthaloylbis-diacetylaminoethylamine, N,N'-isophthaloylbis-diacetylaminoethylamine, N,N'-terephthaloylbis(4-methylpiperidine).

N,N'-terephthaloyl bis(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'-phthaloylbis(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'-isophthaloylbis(2,6-dimethylpiperidine), N,Fll'-phthaloylbis(2,6-dimethylpiperidine), N,N'-terephthaloylbis(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'-terephthaloylbis(4-butylpiperidine), N,N'-isophthaloylbis(4-ethylpiperidine), N,N'-isophthaloylbis(4-n-propylpiperidine), N , N'-isophthaloyl bis(4-butylpiperidine), N,N'-isophthaloyl bis(4-butylpiperidine).

N,N'-phthaloylbis(4-ethylpiperidine)
, N,N'-phthaloylbis(4-propylpiperidine).

N,N'-phthaloylbis(4-butylpiperidine)
, N,N'-terephthaloylbis(3-hydroxymethylpiperidine).

N,N'-Isophthaloylbis(3-hydroxymethylpiperidine).

N,N'-phthaloylbis(3-hydroxymethylpiperidine), N,N'-terephthaloylbis(5-ethyl-2-methylpiperidine), N,N'-isophthaloylbis(5-ethyl-2- methylpiperidine).

N,N'-phthaloylbis(5-ethyl-2-methylpiperidine), N,N'-terephthaloylbis(N-ethyl-N'
-cyclohexylamine), N,N'-inphthaloylbis(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-phthyl-N'
-cyclohexylamine), N,N'-phthaloylbis(N-butyl-N'-cyclohexylamine), N,N'-terephthaloylbis(4-ethyloxymethylpiperidine), N,N'-isophthaloylbis (4-ethyloxymethylbiveridine), N,N'-terephthaloylbis(4-ethyloxyethylpiperidine), N,N'-isophthaloylbis(4-ethyloxyethylbiperidine), 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'-terephthaloylbis(4-phenylpropylpiperidine), N,N' -isophthaloylbis(4-phenylpropylpiperidine), N,N'-phthaloylbis(4-phenylpropylpiperidine), and the like.

In the general formula (V), R1 and R2 represent alkyl, cycloalkyl, aryl, or aralkyl which may have a substituent, and the alkyl is usually a linear or branched chain having 1 to 18 carbon atoms. Examples of the cycloalkyl include cyclohexyl, examples of the aryl include phenyl, tolyl, and xylyl, and examples of the aralkyl include benzyl and phenethyl. These substituents can further have other substituents, such as alkyl, aryl, halogen, alkoxy, aryloxy,
Examples include substituents such as aralkyloxy, acyl, acyloxy, alkoxycarbonyl, carbamoyl, and acylamino. Yl and Yl are linear or branched alkylene groups having 1 to 18 carbon atoms.

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

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

N,N'-bis(cyclohexylaminoprobyl)piperazine.

N,N'-bis(hexyloylaminopropyl)piperazine.

N-benzoylaminopropyl-N'-cyclohexylaminoethylpiperazine.

N-benzoylaminopropyl-N'-benzoylaminobutylbiperazine, N-(P-chlorobenzoylaminoamyl)-N'-benzoylaminopropylpiperazine, N-cyclohexylaminopropyl-N'-cyclohexyl Siloylaminobutylbiperazine, N-naphthoylaminopropyl-N'-benzoylaminopropylpiperazine, N-butyroylaminopropyl-N'-benzoylaminopropylpiperazine, N-lauroylaminopropyl-N'-benzoyl Aminoprobylpiperazine, N-stearoylaminopropyl-N'-benzoylaminopropylpiperazine, N-butyroylaminopropyl-N'-cyclohexyloylaminobutylbiperazine, N-naphthoylaminopropyl-N'-lauroyl Aminopropylpiperazine, N-naphthoylaminopropyl-N'-stearoylaminopropylbiperazine, etc.

Further, as a specific example 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 group, for example.

These include:

N,N',N'-tribenzoyl-diethylenetriamine.

N,N',N'-tribenzoyl-dipropylenetriamine, N,N',N',N~-tetrabenzoyl-triethylenetetramine.

1.7-Dibenzoyl-4-methyl-diethylenetriamine.

1.9-Dibenzoyl-5-methyl-dipropylenetriamine.

1.7-diα-naphthoyl-4-methyl-diethyltriamine, 1.7-diα-naphthoyl-4-cyclohexyl-diethylenetriamine, i,N′,N1-tripivaloyl-diethylenetriamine.

N, N', N', N'-tetraacetyl-triethylenetetramine.

N, N', N', N~-tetracyclohexyloyl-triethylenetetramine, ethylenediaminetetraacetic acid tetraanilide.

Ethylenediaminetetraacetic acid tetracyclohexylamide.

Ethylenediaminetetraacetic acid tetra-2-ethylhexylamide, Ethylenediaminetetraacetic acid tetralaurylamide.

ethylenediaminetetraacetic acid tetrastearylamide, Ethylenediaminetetraacetic acid tetrapiperidide.

Ethylenediaminetetraacetic acid tetra-ε-cabrolactamide, etc.

The decolorizing agents used in the present invention may be used alone or in the form of a mixture of two or more.

The decoloring agent used in the present invention may be present at a position where it can decolor the coloring system of the second thermosensitive coloring layer when coloring the first thermosensitive coloring layer with high thermal energy, and generally,
An intermediate layer (decoloring agent layer) may be provided between the second thermosensitive coloring layer and the first thermosensitive coloring layer, and the decoloring agent layer may be contained in this intermediate layer, or it may be contained in the first thermosensitive coloring layer.

In the present invention, the coloring agent used in the second thermosensitive coloring layer forms a stable image with low energy heating.

Any dye may be used as long as it is easily decolored by a decoloring agent under high-energy heating, and in the case of the present invention, a basic leuco dye is used. The coloring agent used in the first thermosensitive coloring layer may be any coloring agent as long as it is not easily erased by the decoloring agent. Therefore, the coloring agent used in the first thermosensitive coloring layer is not limited to leuco dyes, but may be other than conventionally known coloring agents. A thermosensitive coloring system is also used.

The two-color heat-sensitive recording material of the present invention has high background whiteness;
In addition to maintaining its whiteness over time, the low-temperature color development image density is high, and the image density is maintained over time. The high-temperature colored image is clear without color mixture, and is stable both initially and over time. In the two-color heat-sensitive recording material of the present invention, if necessary, the space between the decoloring agent layer and the first thermosensitive coloring layer, between the decoloring agent layer and the second thermosensitive coloring layer, or the coloring layer containing the decoloring agent is provided. An intermediate layer, for example, a layer containing a thermofusible substance, a water-soluble resin, a latex resin, and/or a filler, etc. may be provided between the first heat-sensitive coloring layer and the second heat-sensitive coloring layer. A protective layer may be provided on the coloring layer in the form of one layer or multiple layers.Furthermore, in the present invention, a back coat layer may be provided on the back side of the support, and an adhesive layer may be provided and a release paper It can also be made into a magnetic ticket paper by providing a magnetic layer.

The basic leuco dye used in the second heat-sensitive coloring layer of the present invention may be applied alone or in a mixture of two or more types, and such basic leuco dyes are applied to this type of heat-sensitive material. One example is.

Leuco compounds of triphenylmethane-based, fluoran-based, phenothiazine-based, auramine-based, and spiropyran-based dyes are preferably used. Specific examples of such basic leuco dyes include those shown below.

3.3-bis(P-dimethylaminophenyl)-phthalide, 3.3-bis(P-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet lactone).

3.3-bis(p-dimethylaminophenyl)-6-dibutylaminophenyl, 3.3-bis(p-dimethylaminophenyl)-6-chlorophthalide, 3.3-bis(p-dibutylaminophenyl) phthalide, 3-Cyclohexylamino-6-chlorofluorane.

3-diethylamino-6-chloro-7-methylfluorane.

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-ditylamino)-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-dibutylamino-7-(o-fluoroanilino)fluorane, 3-N-methyl-N-amylamino-6-methyl-7-
Anilinofluorane.

3-N-Methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane.

3-(N-isoacyl-N-ethyl)amino-7-(0
-chloroanilino)fluoran, 3-(N-hexyl-N-methyl)amino-7-(0-
chloroanilino)fluoran 3-(N,N-diethylamino)-5-methyl-7-(
N.

N-dibenzylamino)fluoran.

Benzoylleucomethylene blue.

6'-Chloro-8'-methoxy-benzoindolino-pyrylospirane, 6'-bromo-3'-methoxy-benzoindolino-pyrylospirane, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3- (2'-methoxy-5'-chlorophenyl)phthalide, 3-(2'-hydroxy-4'-diethylaminof,
enyl)-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)fluoran.

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)fluoran, 3-(N-ethyl-P-toluidino)-7-(α-phenylethylamino)fluoran, 3- Diethylamino-7-(o-methoxydicarbonylphenylamino)fluoran.

3-diethylamino-5-methyl-7-(α-phenylethylamino)fluoran.

3-diethylamino-7-piperidinofluorane, 2-
Chloro-3-(N-methyltoluidino)-7-(p-n
-butylanilino)fluorane.

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, specific examples of basic leuco dyes preferably contained in the high-temperature coloring layer include:

3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-
Examples include cyclohexylamino-6-chlorofluorane, 3-diethylaminobenzo[α]fluorane, and the like.

In the present invention, the first thermosensitive color forming layer forming the high temperature color forming layer may contain an acidic leuco dye, for example, an acylated lactone type or sultone type leuco dye as shown below.

Examples of color developers that can develop color by reacting with the basic leuco dye described above under heat include the following.

N,N'-diphenylthiourea, N-P-ethylphenyl-N'-phenylthiourea, N-P-butylphenyl-N'-phenylthiourea, N,N'-di-lylorophenylthiourea, N , N'-Gip, -chlorophenylthiourea, N,N'-G-p,-trifluoromethylphenylthiourea, N,N'-9-rs-methylphenylthiourea, 4,4'-isopropylidenediphenol , 4.4'-isopropylidene bis(2
-chlorophenol), 4,4'-isopropylidene bis(2,6-dibromophenol), 4,4'-isopropylidene bis(2,6-dichlorophenol), 4.
4'-isopropylidene bis(2-methylphenol)
.

4.4'-isopropylidene bis(2,6-dimethylphenol), 4,4'-isopropylidene bis(2-t
ert-butylphenol), 4.4'-5ec-
Butylidene diphenol, 4,4'-cyclohexylidene bisphenol, 4,4'-cyclohexylidene bis(2-methylphenol), 4-tart-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, α-naphthol , β-naphthol,
3,5-xylenol, thymol, methyl-4-hydroxybenzoate, 4-hydroxyacetophenone, novolac type phenolic resin, 2,2'-thiobis(4,
6-dichlorophenol), catechol, resorcinol,
Hydroquinone, pyrogallol, phloroglycine, phloroglycin carboxylic acid, 4-tert-octylcatechol, 2,2'-methylenebis(4-chlorophenol), 2,2'-methylenebis(4-methyl-6-t,e
rt-butylphenol), 2゜2'-dihydroxydiphenyl, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, ARMbenzyl p-hydroxybenzoate, P-chloro p-hydroxybenzoate Benzyl, p-hydroxybenzoic acid-0-chlorobenzyl, p-hydroxybenzoic acid-P-
Methylbenzyl, n-octyl P-hydroxybenzoate, benzoic acid, l-hydroxy-2-naphthoic acid, 2-
Hydroxy-6-naphthoic acid, 4-hydroxydiphenylsulfone, 4-hydroxy-4'-chlorodiphenylsulfone, bis(4-hydroxyphenyl)sulfide, and the like.

In the present invention, the coloring system in the first thermosensitive coloring layer is not particularly limited, and in addition to the leuco system described above, various systems such as those shown below can be used.

(a) Combination of long-chain aliphatic iron salts such as ferric stearate and ferric myristylate with phenols such as gallic acid and ammonium salicylate.

(b) Organic acid heavy metal salts such as nickel, cobalt, lead, copper, iron, mercury, and silver salts such as acetic acid, stearic acid, and palmitic acid, and alkaline earth metals such as calcium sulfide, strontium sulfide, and potassium sulfide. A combination with a sulfide, or a combination of the organic acid polymerized metal salt and an organic chelating agent such as S-diphenylcarbazide or diphenylcarbazone.

(c) Heavy metal sulfates such as silver, lead, mercury, thorium sulfates, Na-tetrathionate, sodium thiosulfate,
In combination with sulfur compounds such as thiourea.

(d) a ferric fatty acid salt such as ferric stearate;
Combination with aromatic polyhydroxy compounds such as 3,4-dihydroxytetraphenylmethane.

(e) A combination of an organic noble metal salt such as silver oxalate or mercury oxalate and an organic polyhydroxy compound such as polyhydroxy alcohol, glycerin, or glycol.

(f) Combinations of organometallic salts such as silver behenate and silver stearate and aromatic organic ring-forming agents such as protocatechuic acid, spiroindane, and hydroquinone.

(g) A combination of an aliphatic ferric salt such as ferric pelargonic acid or ferric laurate, and a thiocetyl tribamide or an inthiocetyl tribamide derivative.

(h) A combination of an organic acid lead salt such as lead caproate, lead pelargonate, or lead behenate and a thiourea derivative such as ethylenethiourea or N-dodecylthiourea.

(S) A combination of a higher fatty acid heavy metal salt such as ferric stearate or copper stearate and zinc dialkyldithiocarpanate.

(n) Those that form oxazine dyes, such as the combination of resorcinol and nitroso compounds.

(l) Combination of aromatic diazo compound and coupler.

(w) Combination of formazan compound and metal salt.

In the present invention, in order to bond and support each heat-sensitive color forming layer and decoloring agent layer on a support, various commonly used binders can be used as appropriate. For example, polyvinyl alcohol, starch and its derivatives, methoxy Cellulose, hydroxyethyl cellulose.

Cellulose derivatives such as carboxymethylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylic amide/acrylic ester copolymer, acryl amide/acrylic ester/methacrylic acid ternary copolymer, styrene maleic anhydride Acid copolymer alkali salt, inbutylene/maleic anhydride copolymer alkali salt, polyacrylamide,
In addition to water-soluble polymers such as sodium alginate, gelatin, and casein, polyvinyl acetate, polyurethane, styrene/butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride/vinyl acetate copolymer, polybutyl methacrylate, Latex such as ethylene/vinyl acetate copolymer, styrene/butadiene/acrylic copolymer, etc. can be used.

Furthermore, in the present invention, each thermosensitive color forming layer and decoloring agent layer may further contain auxiliary additive components, such as fillers, which are commonly used in this type of thermosensitive recording material, if necessary.

A surfactant, a thermofusible substance (or lubricant), etc. can be used in combination. In this case, fillers include 1, 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-formalin 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,
Benzoic acid phenyl ester, higher linear glycol, 3,
50-200 of dialkyl 4-epoxy-hexahydrophthalate, higher ketones, other thermofusible organic compounds, etc.
Examples include those with a melting point of about ℃.

To obtain the heat-sensitive recording material of the present invention, Paper 1: Synthetic paper.

It can be obtained by applying and drying 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 a plastic film, 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. Also.

After coating and drying, the upper layer may be applied after calendering. The amount of dye attached to the high temperature coloring layer is 0.3g/rrr
~1. Og/n? , the amount of decolorizing agent attached to the decolorizing agent layer is.

L, Og/rrr to 10 g/rrr, and the amount of the low-temperature coloring layer deposited is 0.2 g/m2 to 0.5 g/-, based on the leuco dye deposited as a dry product, as described above.

When a protective layer is provided, the amount of adhesion is 0.5g/bo~5. O
g/m2 is preferred. When providing an intermediate layer between the decoloring agent layer and the low temperature coloring layer and/or between the decoloring agent layer and the high temperature coloring layer,
The former is preferably 0.5 g/d to 5.0 g/i, and the latter is preferably 1 g/d to 10 g/i.

〔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 prepare dispersions A to D.

[Dispersion liquid-A]

3-(N-ethyl-N-amylamino)-6-methyl-
7-anirithufluoran (black) 20 parts 10% hydroxyethyl cellulose aqueous solution 20 parts water
60 parts [Dispersion-B] 3.3'-Dichlorophenylthiourea 12 parts Stearic acid amide 6 parts Calcium carbonate 12 parts 10% polyvinyl alcohol aqueous solution 30 parts Water
40 parts [Dispersion-B] 3-diethylamino-7-chlorofluoran (red)
20 parts 10% hydroxyethyl cellulose aqueous solution 20 parts water
6
0 parts [Dispersion-B] Bisphenol A 12 parts Ethylene bisstearamide 6 parts Calcium carbonate 9 parts 10% polyvinyl alcohol aqueous solution 30 parts Water
43 parts or more of 10 parts of the dispersion A prepared in the above manner, 850 parts of the dispersion, and 40 parts of water were each taken and mixed and stirred to obtain a second thermosensitive coloring layer (thermosensitive coloring layer for low temperature) forming liquid.

On the other hand, 10 parts of dispersion C, 060 parts of dispersion, and 30 parts of water were each taken and mixed and stirred to obtain a first thermosensitive coloring layer (heatsensitive coloring layer for high temperature) forming liquid. Furthermore, a decolorizing agent layer forming liquid for forming a decolorizing agent layer was prepared at the following ratio.

[Decolorizer layer forming liquid]

N,N'-bis(benzoylaminopropyl)piperazine 20 parts 10% polyvinyl alcohol aqueous solution 20 parts water
60 parts or more of each solution was applied onto commercially available high-quality paper with a basis weight of about 52 g/day.
6g/rrr), erasing agent layer forming liquid (coating amount when dry: 2
．． 5g/rrr), low temperature heat-sensitive color forming layer forming liquid (dry coating amount: 1.7g/n()) were sequentially applied and dried, and then calendered to a smoothness of 500 to 1500 sec. A color-developing thermosensitive recording material was obtained.

Example 2 The dry coating amount of the low temperature thermosensitive coloring layer forming liquid of Example 1 was 1
, 3 g/rd, but in the same manner as in Example 1.

A two-color thermosensitive recording material of the present invention was obtained.

Comparative Example 1 The dry coating amount of the low temperature thermosensitive coloring layer forming liquid of Example 1 was 1
．． 3g/n? A comparative two-color heat-sensitive recording material was obtained in the same manner as in Example 1, except for the following.

Comparative Example 2 The dry coating amount of the low-temperature coloring layer forming liquid of Example 1 was 5
．． 1g/n? A comparative two-color heat-sensitive recording material was obtained in the same manner as in Example 1, except for the following.

G-[1
A dynamic color density test was conducted using a facsimile test machine, and the results are shown in Table 1 below.

The test machine was a Matsushita Electronic Components 8 dot/IIm.
It has a thermal head of
/1ine, sub-scan 3.859 /am, platen pressure 3. Regarding Okg/A-4 width, head input, coloring of the second thermosensitive coloring layer (low temperature coloring) is 1,0+iJ/dot,
Coloring in the first thermosensitive coloring layer (high temperature coloring) is performed in 3. The test was conducted under the condition of OmJ/dot.

Table-1 Degree of color mixing: ○...Good color separation ×...Color mixing [Effect] As is clear from Table-1, the proportion of dye used in the low-temperature thermosensitive coloring layer is defined within the scope of the present invention. The resulting heat-sensitive recording material has excellent low-temperature thermochromic image density and two-color separation; however, when used at a ratio outside the range of the present invention, the low-temperature thermochromic image density is low or the two-color separability is significantly reduced.

Claims (1)

[Claims] (1) Each coloring heat energy is different on the support,
and has a two-color thermosensitive coloring layer formed by stacking first and second thermosensitive coloring layers that develop colors in different tones such that the one with lower coloring heat energy is the upper layer, and the second thermosensitive coloring layer has In a two-color thermosensitive recording material in which a color erasing agent is present in a position capable of decoloring, the second thermosensitive coloring layer forming at least the upper layer of the two thermosensitive coloring layers is made of a basic leuco dye and a color developer. The basic leuco dye is used in an amount of 0.2 to 0 on a dry weight basis.
．． A two-color heat-sensitive recording material characterized by having a density of 5 g/m^2.