JPS61290089A - Two color forming thermal recording material - Google Patents

Abstract

PURPOSE:To enhance color separation property of two colors and enable tones of the two colors to be freely selected, by providing an intermediate layer comprising a decolorizing agent as a main constitutent between the first and the second thermal color forming layer provided on a base and capable of forming respective colors with different tones. CONSTITUTION:The first color forming layer is provided on the base, the intermediate layer comprising a decolorizing agent is provided thereon in an amount of 5-15g/m<2> as solid components, and the second color forming layer is provided thereon. With this arrangement, only the second color forming layer provided in the upper layer is developed into color by ordinary or low-temperature printing energy, and then both the first and second color forming layers are developed into colores by high- temperature printing energy, accompanied by decoloration of the second color forming layer by the decolorizing layer, resulting in that apparently only the color of the first color forming layer is developed, whereby two colors are clearly developed. The decolorizing agent is a substance having an effect of eliminating images when made to act on developed color images formed through a reaction of a leuco dye with a color developer, and may be one of known decolorizing agents such as a nitrogen-containing organic crystalline compound, a polyether compound and a polyamine compound.

Description

[Detailed description of the invention] 〔Technical field〕 The present invention relates to a two-color thermosensitive recording material.

[Prior art]

A thermosensitive recording material is a material in which a thermosensitive coloring layer that forms 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 (main coloring agent) having a lactone ring, lactam ring, spiropyran ring, etc. in the heat-sensitive coloring layer, and a developer that develops color by reacting with the leuco dye when heated. Coloring agent (coloring 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. It is used in In recent years, applications for two-color heat-sensitive recording materials have been expanding, including labels, paper tickets, and coupons.

It has also been used for tack paper, video printers, etc. Conventionally, most thermal recordings have been monochromatic, black or blue, except for those for recorders, but depending on the purpose of the recording, it is naturally desirable if it is possible to produce two colors that are partially different. This is a major market need.

Attempts have been made to obtain two-color recording, and various methods and materials 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 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 a specific example of these, the former is
Publication No. 9, Special Publication No. 49-4342, Special Publication No. 49-27
708, JP-A-48-86543, JP-A-49-65239, etc., and the latter is described in JP-A-50-17865 and JP-A-50-17.
866, Japanese Patent Publication No. 51-29024, and Japanese Patent Publication No. 51-87542.

Special Publication No. 54-36864, Special Publication No. 55-3651
Each of these is disclosed in Publication No. 9, etc.

However, in the case of the former multicolor thermosensitive recording paper,
During high-temperature coloring, the color tones that can be specifically achieved are red-black, blue-black, etc. because the color is mixed with the color tone of the low-temperature coloring layer, but the disadvantage is that the high-temperature coloring tone is limited to black threads with full strength. There is. On the other hand, in the case of the latter multicolor thermosensitive recording paper, the combination of color tones can be freely selected, but when coloring at high temperatures, higher fatty acid alcohol, polyether, polyethylene, etc. glycol derivatives,
Acetamide, stearamide, phthalonitrile as nitrogen-containing organic compounds, guanidine derivatives as amine derivatives, morpholine derivatives, etc. have been proposed, but these substances still have a low decoloring effect and do not work well in the low-temperature coloring layer during high-temperature coloring. It may not be possible to completely erase the color tones, resulting in color mixing or bleeding in the low-temperature coloring layer. To deal with this, multi-layer coating of a high-temperature coloring layer, a decoloring agent layer, and a low-temperature coloring layer is applied.
In addition, it is necessary to make the color erasing agent layer sufficiently thick, and it is also necessary to significantly reduce the sensitivity of the high temperature color forming layer. That is, it is necessary to significantly increase the coloring start temperature of the high temperature coloring layer. However, when the coloring start temperature of the low-temperature coloring layer and the coloring starting temperature of the high-temperature coloring layer are about the same, or when the two coloring layers are simply laminated, or a small amount of intermediate layer is provided between the two coloring layers. In some cases, sufficient two-color separation cannot be achieved.

〔the purpose〕

An object of the present invention is to provide a two-color heat-sensitive recording material that has good color separation between the two colors and allows the two-color color tones to be freely selected.

〔composition〕

According to the present invention, the first layer that develops different colors on the support
and a two-color coloring thermosensitive recording material in which an intermediate layer is provided between a second thermosensitive coloring layer and the coloring layer, the intermediate layer containing a decoloring agent as a main component and having a solid content of 5 to 15 g/ni'. A two-color thermosensitive recording material is provided.

In the two-color thermosensitive recording material of the present invention, a first coloring layer is provided on a support, an intermediate layer containing a decoloring agent is provided on top of the first coloring layer with a solid content of 5 to 15 g#rl'', and In such a two-color heat-sensitive recording material, only the upper second coloring layer develops color with normal or low-temperature printing energy, and then the second coloring layer develops color with high-temperature printing energy. 1
and the second coloring layer develops color, but at the same time the decoloring layer decolors the second coloring layer, so only the coloring of the first coloring layer appears, resulting in clear two-color development. be able to. The two-color coloring according to the present invention is characterized by the fact that two colors can be freely selected regardless of the first and second coloring layers, and the two-color coloring is not affected much by the thermal sensitivity of the coloring layer alone. There is. To explain the latter in more detail, it can be said that the thermal sensitivity of the coloring layer is most influenced by the melting temperature of the coloring system, and most influenced by the melting points of the individual compounds constituting the coloring system. Therefore, components such as leuco dyes, color developers, thermofusible substances, etc. used in coloring systems with high melting points have slow thermal sensitivity, while components with low melting points have high thermal sensitivity. Therefore, if the solid content of the intermediate layer is not controlled, it is important to adjust the thermal sensitivity of the first and second coloring layers, and there are major restrictions on the individual melting points of the materials used, so material selection is difficult. It is very difficult to obtain a coloring layer with the desired sensitivity. The present invention solves these difficulties by controlling the solid content of the intermediate layer. That is, when the second coloring layer is colored with normal or low-temperature energy, the amount of heat transferred to the first coloring layer is very small because there is an intermediate filling between the coloring layers. Since the first coloring layer does not develop any color, the resulting product has excellent color separation properties.

In this case, when the solid content of the intermediate layer is less than 5 g/rl, the amount of heat transfer is large and the coloring of the first coloring layer is significant, so color mixing is likely to occur.
When the amount exceeds g#rF, the amount of heat transfer decreases when high temperature is applied, and a very large heat application is required to develop the high temperature color, making it impractical. According to the present invention, even if the thermal sensitivities of the first coloring layer and the second coloring layer are approximately the same, it is possible to obtain a two-color recording with extremely excellent color separation. The advantage is that there are almost no restrictions on the selection range of materials.

The intermediate layer in the present invention requires the use of a decolorizing agent, and other additive materials include organic and inorganic fillers, hydrophilic and hydrophobic resins, thermofusible substances, and the like. In addition, as for the layer structure of the intermediate layer, in addition to a single layer, it is also possible to have a laminated type in which one layer or two or more layers are divided into a layer mainly containing a decolorizing agent and a layer mainly containing other materials. . A more stable intermediate layer structure is a laminated structure consisting of one layer mainly containing a decolorizing agent and a lower layer mainly containing a thermoplastic substance and/or filler.

The decoloring agent used in the present invention refers to a decoloring agent that has the effect of erasing an image when it acts on a colored image formed by the reaction between a leuco dye and a color developer, and is generally a nitrogen-containing organic crystalline compound, a polyether compound, Various conventionally known compounds such as polyamine compounds can be mentioned, but preferred examples include:
Compounds represented by the following general formulas (1), (II), (m) and (IV).

Having 3 or more amide groups in the molecule, or 2 or more"-
The use of compounds having an amide group and one or more tertiary amino groups, such as N,N'-dithiocicaprolactam, is advantageous.

General formula (I) 2 General formula (■) 2 General formula (■) 2 General formula (■): General formula (1), (II), (III) and (IV)
Medium, R□, R2, R3, R4, R5, R6, R7, R8
, R9 and Lo are alkyl which may have a substituent,
cycloalkyl, aryl or aralkyl, R
The terminals of 5 and R6 and R7 and R8 may be bonded to each other to form a cyclic structure. Further, A represents a divalent aliphatic group or an aromatic group, X--Xl and x2 are carbonyl or sulfonyl, and Yl and (2) represent alkylene.

The alkyl represented by R1 to RIO usually includes a straight chain or branched chain having 1 to 18 carbon atoms, the cycloalkyl includes cyclohexyl, and the aryl includes phenyl and tolyl. , xylyl, etc., and examples of aralkyl include benzyl, phenethyl, etc. These substituents may further have other substituents, such as alkyl, aryl, halogen, alkoxy, aryloxy, acyl, acyloxy, alkoxycarbonyl, carbamoyl, Examples include acylamino. In addition, general formulas (1), (■) and (IV
) may also have one or more substituents bonded to it, such as alkyl, aryl, halogen, alkoxy, aryloxy, acyl, acyloxy, alkoxycarbonyl, carbamoyl, and acylamino.

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-N'-p-chlorobenzoylpiperazine, N-benzoylaminoethyl-N'-benzoylpiperazine, N-benzoylaminopropyl-N'-benzoylpiperazine, N-benzoylaminobutyl-N '-Benzoylaminopropyl-N'-cyclohexylpiperazine, N-cyclohexylaminopropyl-N'-cyclohexyloylpiperazine.

N-Benzoylaminoamyl-N'benzoylpiperazine.

N-(ρ-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, ■-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'-benzoylbiperazine, 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 (It) include the following.

N,N'-bis(benzenesulfonyl)piperazine,
N,N'-bis(p-methylbenzenesulfonyl)piperazine, N,N'-bis(p-isopropylbenzenesulfonyl)piperazine, N,N'-'bis(ρ-chlorobenzenesulfonyl)
Piperazine, N,N'-bis(O-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'-benzenesulfonylpiperazine, N-octylsulfonyl-N'-benzenesulfonylpiperazine, N-(0-chlorobenzenesulfonyl)-N ′ -benzenesulfonylpiperazine.

N-lauroyl-N'-benzenesulfonylpiperazine, N-lauroyl-N'-(p-methylbenzenesulfonyl)piperazine, N-benzoyl-N'-benzenesulfonylpiperazine, N-(o-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(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(m-chlorobenzoyl)piperazine, N,N'-bis(0-chlorobenzoyl)piperazine, N,N'-bis(p-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(p-phenylbenzoyl)piperazine, N,N'-bis(p-methoxycarbonylbenzoyl)piperazine, N,N'-bis( P-impropoxycarbonylbenzoyl)piperazine, N,N'-bis(P-octadecylcarbamoylbenzoyl)piperazine, and the like.

In the general formula (m), R5, R6, R7 and R8 are.

As mentioned above, represents substituted or unsubstituted alkyl, cycloalkyl, aryl or aralkyl, and R5 and R6
Alternatively, R7 and R8 can be bonded at their terminal ends to form a ring, but in this case, the alkyl is preferably a straight or branched chain having 4 to 8 carbon atoms. It will be done. Also.

A is an aliphatic group or an aromatic group, but in the case of an aliphatic group,
Usually, it is a substituted or unsubstituted alkylene having 1 to 8 carbon atoms, and in the case of an aromatic group, it is a substituted or unsubstituted arylene such as phenylene, tolylene, xylylene, etc. In this case, the substituent is as described above. halogen, acylamino,
Examples include alkoxycarbonyl, 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 acid diamide, N, N, N', N'-tetraoctylsuccinic acid diamide, N, N, N', N'-tetralaurylsuccinic acid diamide, N, N,N',N'-tetrastearyl succinic acid diamide, N,N,N',N'-tetraphenyl adipic acid diamide, N,N,N',N'-tetra-p-butylphenyl adipic acid diamide, N,N,N',N'-tetrabutyladipate diamide, N,N,N',N'-tetraoctyladipate diamide, N,N,N',N'-tetralauryladipate diamideN,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 '-dimethyladipate diamide, N,N,N',N'-tetracyclohexyladipate diamide, N,N'-dimethyl-N,N'-dicyclohexylsperate diamide, N,N'-dimethyl-N , N'-dicyclohexylsebacic acid diamide, N,N'-dimethyl-N,N'-dicyclohexylmalonic acid diamide, N,N,N',N'-tetrabenzyl adipic acid diamide, adipoyldipiperidine, adiboyl dipipecoline, adipoyldi-ε-caprolactam, adipoyldi-
Pyrrolidone, Adiboyldipiperidone, Sebacoyldi-epsilon-caprolactam, Sebacoyldi-piperidone, Adipoyl-di-3-chloro-epsilon-caprolactam.

Succinyl-di-3-croto-1-caprolactam, N,N'-terephthaloyl bispiperidine, N,N'
-Isophthaloyl bispiperidine.

N,N'-phthaloyl bispiperidine, 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'-terephthaloy Rubis-4-propylpiperazine, N,N'-isophthaloylbis-4-propylpiperazine, N,N'-phthaloyl-4-propylpiperazine, N
, N'-terephthaloyl biscaprolactam, N, N
'-Isophthaloyl biscaprolactam, N, N'
- Phthaloyl biscaprolactam.

N,N'-terephthaloylbis-3-chlorocaprolactam, N,N'-isophthaloylbis-3-chlorocaprolactam, N,N'-phthaloylbis-3-chlorocaprolactam, N,N'-terephthalolbis Valerolactam, N, N
'-Isophthaloyl bisvaleractam, N, N'
-phthaloylbiscaprolactam, ~N/-terephthaloylbispyrrolidine, N,N'-isophthaloylbispyrrolidine, N,N'-phthaloylbispyrrolidine.

N, N'-terephthaloyl bis-diethylamine,
N,N'-Isophthaloylbis-diethylamine.

N,N'-phthaloylbis-diethylamine, N,N
' -Terephthaloyl bis-dipropylamine.

N,N'-isophthaloylbis-dipropylamine 5
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'-terephthaloylbis-dibenzylamine,
N,N'-isophthaloylbis-dibenzylamine,
N,N'-terephthaloylbis-dioctylamine,
N,N'-isophthaloylbis-dioctylamine,
N,N'-terephthaloylbis-jethoxypropylamine, 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'-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'-isophthaloylbis(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,N'-phthaloylbis(2,6-dimethylpiperidine), N,N'-terephthaloylbis(4-benzylpiperidine) ), N,N'-isophthaloylbis(4-benzylpiperidine), N,N'-phthaloylbis(4-benzylpiperidine).

N,N'-terephthaloyl bis(4-methoxycarbonylpiperidine), N,N'-isophthaloyl bis(4-methoxycarbonylpiperidine), N,N'-terephthaloyl bis(2-methoxycarbonylpiperidine) .

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

N,N'-phthaloylbis(2-methoxycarbonylpiperidine), N,N'-terephthaloylbis(4-ethylpiperidine), N,N'-terephthaloylbis(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'-isophthaloylbis(4-butylpiperidine), N,N'-phthaloylbis(4-ethylpiperidine)
, N,N'-phthaloylbis(4-propylpiperidine), N,N'-phthaloylbis(4-butylpiperidine), N,N'-terephthaloylbis(3-hydroxymethylpiperidine), N,N'-iso Phthaloylbis(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'-isophthaloylbis(N-ethyl-N'-
cyclohexylamine), N,N'-phthaloylbis(N-ethyl-N'-cyclohexylamine), N,N'-terephthaloylbis(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'-cyclohexylamic), N,N'-terephthaloylbis(4-ethyloxymethylpiperidine), N,N'-isophthaloylbis(4-ethyl roxymethylpiperidine).

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

N,N'-isophthaloyl bis(4-ethyloxyethylpiperidine), N,N'-terephthaloyl bis(2-methoxyethylpiperidine), N,N'-isophthaloyl bis'(2-methoxyethyl piperidine), N,N'-terephthaloyl bis(4-methoxyethylpiperidine), N,N'-(isophthaloyl bis(4-methoxyethylpiperidine), N,N'-terephthaloyl bis(4-methoxyethylpiperidine) 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.

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

N,N'-bis(benzoylaminoethyl)piperazine, N,N'-bis(benzoylaminopropyl)piperazine, N,N'-bis(benzoylaminobutyl)piperazine, N,N'-bis(cyclobexylamino N,N'-bis(hexyloylaminopropyl)piperazine, N-benzoylaminopropyl-N'-cyclohexylaminoethylpiperazine, N-benzoylaminopropyl-N'-benzoylaminobutylpiperazine.

N-(P~dichloronzoylaminoamyl) -N'
-benzoylaminopropylpiperazine, N-cyclohexylaminopropyl to N'-cyclohexylaminobutylpiperazine, N-naphthoylaminopropyl-N'-benzoylaminopropylpiperazine.

N-butyroylaminopropyl-N'-benzoylaminopropylpiperazine, N-lauroylaminopropyl-N'-benzoylaminopropylpiperazine, N-stearoylaminopropyl-N'-benzoylaminopropylpiperazine.

N-butyroylaminopropyl-N'-cyclohexyloylaminobutylpiperazine, N-naphthoylaminopropyl-N'-lauroylaminopropylpiperazine.

N-naphthoylaminopropyl-N'-stearoylaminopropylpiperazine and the like.

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

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-di-alpha-naphthoyl-4-methyl-diethyltriamine.

■, 7-diα-naphthoyl-4-cyclohexyl-diethylenetriamine, N, N', N"-tripivaloyl-diethylenetriamine, N, N', N', N"-tetraacetyl-triethylenetetramine, N, N', N ', m-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-C-cabrolactamide and the like.

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

The coloring dye used in the second thermosensitive coloring layer of the present invention is preferably a basic leuco dye, and these leuco dyes may be used alone or in combination of two or more. As such leuco dyes, leuco compounds of dyes applied to this type of heat-sensitive materials, such as 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-ethylamino) -6-Methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 2-(N-(3'-trifluoromethylphenyl)
amino)-6-ethylaminofluorane, 3-(N-
Methyl-N-cyclohexylamino)-6-methyl-7
-chlorofluorane, 3-(N-methyl-N-cyclohexylamino)-7-
Chlorofluorane, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-chlorofluorane.

3-(N-ethyl-N-isoamylamino)-7-chlorofluorane, 2-(3,6-bis(diethylamino)9-(o-chloroanilino)xantylbenzoic acid lactam), 3-diethylamino-6-methyl -7-Cm-trichloromethylanilino)fluoran, 3-diethylamino-7-(o-chloroanilino)fluoran, 3-dibutylamino-7-(0-chloroanilino)fluoran, 3-dibutylamino-7-(0-fluoro anilino)fluoran, 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-pyrylosubiran, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-57-chlorophenyl)phthalide, 3-(2 '-Hydroxy-41-dimethylaminophenyl)-3-(2'-methoxy-5'-21-iphenyl)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)fluoran 53-pyrrolidino-7-(di-P-chlorophenyl)methylaminofluorane, 3-diethylamino-5-chloro-7-(α-phenylethylamino)fluoran, 3-(N-ethyl-pt-luidino)-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-(ρ
-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, 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-m-chlorophenylthiourea, N, N'-di-p-chlorophenylthiourea, N,N'-di-trifluoromethylphenylthiourea, N,N'-g1-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
art-butylphenol), 4.4'-5ec-
Butylidene diphenol, 4,4'-cyclohexylidene bisphenol, 4,4'-cyclohexylidene bis(2-methylphenol), 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, α-naphthol , β-naphthol, 3,
5-xylenol, thymol, methyl-4-hydroxybenzoate, 4-hydroxyacetophenone, novolak deaf phenolic resin, 2,2'-thiobis(4,6-
dichlorophenol), catechol, resorcinol, hydroquinone, pyrogallol.

Phloroglycin, phloroglycin carboxylic acid, 4-t
ert-octylcatechol, 2,2'-methylenebis(4-chlorophenol), 2,2'-methylenebis(
4-methyl-6-tert-butylphenol).

2.2'-dihydroxydiphenyl, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, p-
Butyl hydroxybenzoate, benzyl P-hydroxybenzoate, P-chlorobenzyl P-hydroxybenzoate, 〇-chlorobenzyl P-hydroxybenzoate, p-
p-methylbenzyl hydroxybenzoate, n-octyl p-hydroxybenzoate, benzoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-6-naphthoic acid, 4-hydroxydiphenylsulfone, 4-hydroxy- 4'-chlorodiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 0-sulfophthalimide, 5-isopropyl-〇-sulfophthalimide, 5-
Tertiary butyl-〇-sulfophthalimide, 5-octyl-〇-sulfophthalimide, etc.

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 heavy metal salt with 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) A combination of an organic metal salt such as silver behenate or silver stearate and an aromatic organic ring activator such as protocatechuic acid, spiroindane, or hydroquinone.

(g) A combination of an aliphatic ferric salt such as ferric pelargonic acid or ferric laurate and a thiocetyl-rubamide or isothiocetyl-rubamide 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 derivatives such as cellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylic amide/acrylic ester copolymer, acrylic amide/acrylic ester/methacrylic acid ternary copolymer , styrene/maleic anhydride copolymer alkali salt, isobutylene/maleic anhydride copolymer alkali salt,
In addition to water-soluble polymers such as polyacrylamide, sodium alginate, gelatin, and casein, polyvinyl acetate, polyurethane, styrene/butadiene copolymer, polyacrylic acid, polyacrylic ester, vinyl chloride/vinyl acetate copolymer, and Latex such as butyl methacrylate, 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, 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 galponic acid 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 ℃.

In order to obtain the two-color heat-sensitive recording material of the present invention, a color-forming dye, a color developer, a color erasing agent, a binder, etc. are dispersed or dissolved on one side of a support such as paper, synthetic paper, or plastic film. It can be obtained by applying the solution, drying it, 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 0.3g/rrF to 1.0g/rrF. The amount of the low-temperature coloring layer deposited is preferably large in order to increase the density, but it is preferably small in order to enhance the decoloring effect and reduce costs. The adhesion amount is preferably 0.2 g/rrF to 0.8 g/.

The ratio of dye to color developer is preferably 1:1 to 1:5 by weight. The amount of adhesion when providing a protective layer is 0.5g/rrf
~5. Og/- is preferred.

In the two-color thermosensitive recording material of the present invention, a back coat layer can be provided on the back surface of the support, and a release paper can be provided by providing a release mount via an adhesive layer.

〔effect〕

The two-color heat-sensitive recording material of the present invention has an intermediate layer containing a decolorizing agent and a filler with an adhesion amount of 5 to 15 g/rrf between the low-temperature coloring layer and the high-temperature coloring layer.

A two-color image with excellent color separation can be recorded.

〔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 [Liquid A] 3-(N-methyl-N-cyclohexylamino)-7-
Chlorofluorane 10 parts Polyvinyl alcohol 10% aqueous solution 10 parts Water
3011(A
2 parts] 3-dibutylamyl-7-(o-chloroanilino)fluoran 10 parts Polyvinyl alcohol 10% aqueous solution 10 Water
30〃(B
Solution Z] 4.4'-Dihydroxydiphenylsulfone 30 parts Polyvinyl alcohol 10% aqueous solution 30 Water
90〃
(Liquid B2) 3.3-Dichlorodiphenylthiourea 30 parts Polyvinyl alcohol 10% aqueous solution 30n water
90〃
[Liquid C] Silica powder 20 parts Zinc stearate 5 1,4-dibenzyloxynaphthalene 20 10% polyvinyl alcohol aqueous solution 22.5 #water
112.5 parts [D
Liquid] Isophthaloyl-bis-(N-cyclohexyl-N-methyl)amide (Decolorizer) 80 parts Polyvinyl alcohol 10% aqueous solution 8o Water
24o〃[E
Liquid] Polyvinyl alcohol 10% aqueous solution 20 parts Silica fine particles 0,5 // Zinc stearate o, 1 Water
1o〃〃
Liquid F] Polyvinylidene chloride latex 1 part (solid content 50%) High-density polyethylene wax dispersion 40! ! (solid content 25%) water
70II Furthermore, among the above [Liquid A] to [Liquid F], [A
Each of the dispersion liquids was prepared by uniformly dispersing and mixing Liquids] to [Liquid E] using a sand grinder and [Liquid F] using a stirrer.

Among the above-mentioned [Liquid A] to [Liquid F], first, CA1 solution]:
[Liquid B1]: Mix [Liquid C] in a ratio of 1:1:1,
A first coloring layer (high temperature coloring layer) coating liquid was prepared. this.

The amount of coloring dye attached to the high-quality paper with a basis weight of 70 g/rrr is 0.
Apply with a lab coating rod to 5g/rri.

It was dried to obtain a first coloring layer.

Next, the above-mentioned [Liquid D] was coated on the first coloring layer and dried to obtain a decolorizing agent layer so that the dry adhesion amount was 6 g/%.

Next, the CAz solution], (B2 solution) and [C solution] were added to 11
:1 to prepare a second coloring layer (low-temperature coloring layer) coating solution, and apply this onto the color erasing agent layer until the amount of coloring dye attached is 0.
．． It was coated with a lab coating rod at a rate of 50 g/rrr and dried to form a second coloring layer.

Next, the [Liquid E] is applied and dried on the second coloring layer so that the dry adhesion amount is 3 g/- to form a protective layer,
The surface was calendered to obtain a two-color heat-sensitive recording material.

The two-color heat-sensitive recording material obtained as described above was printed using a barcode printer with an applied energy of 0.9 mJ/dot to perform low-temperature coloring, and then was printed with an applied energy of 2.8 mJ/dot. When printing with applied energy and coloring at a high temperature, a clear image density of 1.0 was obtained at a low temperature.
A black image was obtained, and a clear vermilion red image (image density 1.0) without color mixture was obtained at high temperature. Both of these two colored images showed no deterioration over time and remained stable even when left indoors.

I also tried applying cottonseed oil and a plasticizer to the image area, but no change was observed in the image area or the background area even after several days had passed.

Example 2 Example 1 except that the above [Liquid F] was used to form an intermediate layer with a dry adhesion amount of 2.5 g/rrr between the decoloring agent layer and the second color forming layer. A two-color heat-sensitive recording material was obtained in the same manner as above. For this material, 1.0mJ/
First, we printed with the applied energy of dots to produce low-temperature coloring, and then printed with the applied energy of 3 OmJ/dot to produce high-temperature coloring.

A clear black image with an image density of 1.3 was obtained, and a clear vermilion red image (image density 1.0) with no color mixture was obtained at high temperature. This colored image remained stable even after being left in a constant temperature bath at 40° C. for 2 days.

Example 3 In Example 1, the above [Liquid F] was used between the decoloring agent layer and the second coloring layer and between the first coloring layer and the decoloring agent layer, and the dry adhesion amount was 2.5 g/ A two-color heat-sensitive recording material was obtained in the same manner as in Example 1, except that m intermediate layers were respectively formed. Regarding this sample, 1. When we printed with an applied energy of OmJ/dot to create low-temperature coloring, and then printed with an applied energy of 3.0 mJ/dot to create high-temperature coloring, a clear black image with an image density of 1.3 was obtained with low-temperature coloring. as well as,
Clear vermilion-red image with no color mixture due to high-temperature color development (image density 1)
．． 1) was obtained.

This colored image was stable even when left in a constant temperature bath at 40° C. for 2 days.

Examples 4 to 5 Instead of the decolorizing agent in [Liquid D] of Example 1, a 1=1 mixture of terephthaloyldipiperidide and terephthaloylbis-(N-isopropyl-N-cyclohexyl)amide (
Example 4) and terephthaloyl dipiperidide and N, N'
A two-color heat-sensitive recording material was prepared in the same manner as in Example 1 except that a 1=1 mixture of -dicyclohexyl-N' and -phenylguanidine (Example 5) was used. Regarding these samples, 1. When printing with applied energies of OmJ/dot (low-temperature coloring) and 2.8mJ/dot (high-temperature coloring), in both cases a clear black image with high image density was obtained with low-temperature coloring, and a clear vermilion image with no color mixture was obtained with high-temperature coloring. A red image was obtained. Further, even after being left in a constant temperature bath (40° C.) for 2 days, no deterioration of the image over time was observed.

Example 6 Instead of the fluoran compound in [Liquid A1] of Example 1,
A two-color heat-sensitive recording material was prepared in the same manner as in Example 1 except that 3-diethylamino-6,8-dimethylfluoran was used. For this sample, 1, OmJ/dot (low temperature color development), 1 and 2.8 mJ/dot (high temperature color development)
When printing was performed with an applied energy of , a clear, high-density black image was obtained at a low temperature, and a clear vermilion red image was obtained at a high temperature. Even when this sample was left in a constant temperature bath (40° C.) for 2 days, no deterioration of the image over time was observed.

Comparative Example 1 In Example 1, the amount of decolorizer applied (same as the intermediate layer) was
A product was obtained in the same manner except that it was set at 4.0 g/rr (+), and when a color development test was performed, the low temperature color development did not become pure black, but a black color with a strong reddish tinge.

Comparative Example 2 A product was obtained in the same manner as in Example 1 except that the amount of decolorizing agent applied was 17 g/m2, and a color development test was conducted. However, red color development was weak at high temperature, and the image density was 0.4.

Comparative Example 3 In Example 3, the amount of adhesion of the intermediate layer between the second coloring layer and the decoloring agent layer was set to 6 g/rrr, and the amount of adhesion of the intermediate layer between the first coloring layer and the decoloring agent layer was set to 6 g/rrr. Except that it was set to 6g/m.

A product was obtained in the same manner as in Example 3, and a color development test was performed on the product. The color tone developed at low temperatures was a pure black tone, but the color did not develop into red at high temperatures, and the color tone was a strong blackish red. .

Claims (1)

[Claims] (1) In a two-color thermosensitive recording material in which a first and second thermosensitive coloring layer that develops colors in different tones on a support and an intermediate layer is provided between the coloring layers, the intermediate layer mainly contains a decolorizing agent. As an ingredient,
A two-color heat-sensitive recording material characterized in that the amount of solid content deposited is 5 to 15 g/m^2.