JPS6242880A - Multicolor thermal recording material - Google Patents

Abstract

PURPOSE:To obtain a multicolor image excellent in color separability, by providing an intermediate layer containing a specific petroleum resin between at least one thermal color forming layer and the adjacent color erasing layer. CONSTITUTION:A plurality of thermal color forming layers respectively different in color forming energy and forming colors in different hues are successively laminated to a support so that a layer low in color forming energy is formed as an upper layer and a color erasing layer is provided between the adjacent thermal color forming layers. Hereupon, an intermediate layer containing a petroleum resin with a softening point of 70-150 deg.C and MW of 600-2,000 is provided to at least one space between the thermal color forming layers and the adjacent color erasing layer. By this method, even if energy is lowered in allowing the high temp. side thermal color forming layer provided under the petroleum resin-containing intermediate layer to form a color, color erasing action is sufficiently applied to the low temp. side thermal color forming layer provided on said petroleum resin-containing intermediate layer.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a multicolor heat-sensitive recording material, and more specifically, the present invention relates to a multicolor heat-sensitive recording material, and more specifically, a multicolor heat-sensitive recording material in which heat-sensitive color-forming layers each having a different color-forming heat energy and a different color tone are sequentially laminated on a support. The present invention relates to the formed multicolor 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 (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 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, Japanese Patent Publication No. 49-4342, Japanese Patent Publication No. 49-27108,
JP-A-48-86543, JP-A-49-6523
9, etc., and the latter was published in the Special Publication No. 1973.
-17865 Publication, Special Publication No. 50-17866,
Special Publication No. 51-29024, Special Publication No. 51-8754
Publication No. 2, Japanese Unexamined Patent Application Publication No. 18048/1983, Japanese Patent Publication No. 1983
-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 combination of color tones can be freely selected, but when the coloring layer on the high temperature side is colored, an eraser containing a decoloring agent that erases the coloring layer on the low temperature side is used. It is necessary to provide a color layer. In this case, if the decoloring layer and the thermosensitive coloring layer are in direct contact with each other, the coloring image (particularly the coloring image formed by the coloring layer on the low temperature side) may be decolored. For this reason, it is desirable to provide an intermediate layer between the coloring layer and the color erasing layer, and it has been proposed to use polyvinyl alcohol, styrene-butadiene resin, vinylidene chloride, etc. as such an intermediate layer. However, when this type of intermediate layer is used, although it has the effect of suppressing changes in colored images over time, the decoloring of the low-temperature coloring layer does not proceed sufficiently during high-temperature coloring, resulting in color mixing. There were drawbacks.

〔the purpose〕

An object of the present invention is to overcome the above-mentioned drawbacks, to provide a multicolor thermosensitive recording material that has excellent color separation properties and does not cause color mixing.

〔composition〕

According to the present invention, a plurality of thermosensitive coloring layers each having different coloring energy and producing different tones are sequentially laminated on a support so that the one with the smaller coloring energy becomes two layers, and the adjacent thermosensitive coloring layers In a multicolor heat-sensitive recording material with a decoloring layer provided between each layer, the softening point is 70.
Provided is a multicolor thermosensitive recording material characterized in that an intermediate layer containing a petroleum resin having a temperature of ~150°C and a molecular weight of 600 to 2,000 is provided between a thermosensitive coloring layer and an adjacent color erasing layer. .

In the present invention, the petroleum resin contained in the intermediate layer is
The raw material is petroleum-based unsaturated hydrocarbons present in high-temperature pyrolysis oil such as naphtha, and is obtained by polymerizing it with an acidic catalyst.
000 thermoplastic resins, including polyethylene resins, polypropylene resins, polyisobutylene resins, polycyclopentadiene resins, coumaron indene resins, terpene resins, as well as styrene, vinyl 1-toluene, α- Examples include polymers and copolymer resins such as methylstyrene, indene, isoprene, piperylene, 2-methyl-1-butene, and 2-methyl-2-butene.

In the present invention, petroleum resin is contained in one or more intermediate layers. The intermediate layer is formed between at least one of the plurality of heat-sensitive color forming layers and an adjacent decoloring layer. For example, in a three-color thermosensitive recording material in which a high-temperature coloring layer, a first decolorizing layer, a medium-temperature coloring layer, a second decolorizing layer, and a low-temperature coloring layer are laminated in this order on a support, the intermediate layer is the high-temperature coloring layer. Formed in at least one of between the first color erasing layer, between the first color erasing layer and the medium temperature color forming layer, between the medium temperature color forming layer and the second color forming layer, and between the second color erasing layer and the low temperature color forming layer. It is preferably formed at least on the side of the color-erasing layer, that is, between the first color-erasing layer and the medium-temperature coloring layer and between the second color-erasing layer and the low-temperature coloring layer. In the present invention, at least one of such intermediate layers contains a petroleum resin as described above. As a result, even if the energy is lowered when coloring the high-temperature side heat-sensitive coloring layer provided below the petroleum resin-containing intermediate layer, the coloring of the low-temperature side heat-sensitive coloring layer provided above the petroleum resin-containing intermediate layer can be decolorized. The effect is sufficiently strong.

As the decolorizing agent used in the present invention, those conventionally used can be used, but (a) the following general formula (1), (IT) or (TV
) Piperazine derivatives represented by (b) the following general formula (
m) a disubstituted amide compound of a dihydric carboxylic acid, and (c) having three or more amide groups in the molecule, or having two or more amide groups and one or more tertiary amine groups; It is preferable to use at least one kind selected from the compounds.

General formula (I) 2 General formula (■) 2 General formula (■) 2 General formula (■): In the general formula (1), (II), (m) and (TV),
R1, R2, R3, R4, R5-R6, R7, R8, R
9 and RIO are alkyl, cycloalkyl, aryl or aralkyl which may have a substituent, and R5
The terminals of 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, X, and x2 are carbonyl or sulfonyl, and yl and Y2 represent alkylene. The alkyl represented by R1 to RIO is usually
Examples include straight or branched chains having 1 to 18 carbon atoms; cycloalkyl includes cyclohexyl; aryl includes phenyl, tolyl, xylyl, etc.; aralkyl includes benzyl, Examples include phenethyl. These substituents can further have other substituents, such as alkyl, aryl, halogen, alkoxy,
Examples include aryloxy, acyl, acyloxy, alkoxycarbonyl, carbamoyl, and acylamino. In addition, general formulas (1), (II) and (I
The piperazine ring in V) also includes alkyl, aryl,
One or more substituents such as halogen, alkoxy, aryloxy, acyl, acyloxy, alkoxycarbonyl, carbamoyl, and acylamino may be bonded.

Specific examples of the compound represented by the general formula (I) 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+
, -methylbenzoylpiperazine, N-phenyl-N/ , -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, N-lauryl-N'-benzenesulfonylpiperazine, N-stearyl-N '-benzenesulfonylpiperazine, N-phenyl-N'-butylsulfonylpiperazine, N-phenyl-N'-laurylsulfosulpiperazine, N-phenyl-N'-stearylsulfonylpiperazine, N-phenyl-N'-cyclohexyl Sulfonylpiperazine.

N-phenyl-N'-benzylsulfonylpiperazine, N-phenyl-N'-(p-methylbenzenesulfonyl)piperazine, 1l-N-butyl-N'-(p-methylbenzenesulfonyl)piperazine, N-benzoylaminopropyl -N'-benzenesulfonylpiperazine, N-benzoylaminopropyl-N/, -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 (I) 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(P-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-(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, M, N' -bis(p-methylphenylacetyl)pipe=15- radine, N, N' -bis(phenylacetyl)piperazine, N
, N'-bis(buenylpropionyl)piperazine, N,N'-bis(benzoyl)piperandine, 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-methylbenzoyl)piperazine, N,N'-bis(m-methylbenzoyl)piperazine, N,N'-bis(0-methylbenzoyl)piperazine, N,N'-bis(0 -acetyloxybenzoyl)piperazine, N,N'-bis(O-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 (at), R5, R6, t, and R8 represent substituted or unsubstituted alkyl, cycloalkyl, aryl, or aralkyl, and R5 and R6 or R7 and R8 are bonded at their terminal ends, respectively. It is also possible to form a ring. The alkyl usually includes a straight or branched chain having 4 to 8 carbon atoms, the cycloalkyl includes cyclohexyl, the aryl includes phenyl, tolyl, xylyl, etc. Examples of aralkyl 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, aryloxy, and aralkyloxy. A is an aliphatic group or an aromatic group; in the case of an aliphatic group, it is usually substituted or unsubstituted alkylene having 1 to 8 carbon atoms; in the case of an aromatic group, it is substituted or unsubstituted phenylene, tolylene, It is arylene such as xylylene, and in this case, examples of the substituent include the above-mentioned halogen, acylamino, 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 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'-dimethyladipate amide, N,N,N',N'-tetracyclohexyladipate diamide, N,N'-dimethyl-N,N'- Dicyclohexylsperate diamide, N,N'-dimethyl-N,N'-dicyclohexylsepacic acid diamide, N,N'-dimethyl-N,N'-dicyclohexylmalonic acid diamide, N,N,N',N' -tetrabenzyladipic acid diamide, adipoyldipiperidine, adiboyldipipecoline, adipoyldi-ε-caprolactam, adipoyldi-
Pyrrolidone.

adiboyldipiperidone, Sebacoil di-ε-caprolactam, Sebacoil di-piperidone, Adipoyl-di-3-chloro-ε-caprolactam, Succinyl-di-3-chloro-ε-caprolactam, etc.

N,N'-terephthaloyl bispiperidine, N,N'
-Isophthaloylbispiperidine, 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'-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'
-Isophthaloylbisvaleractam, N,N''-phthaloylbiscaprolactam, N,N'-terephthaloylbispyrrolidine, N,N'-isophthaloylbispirolidine, N,N'-phthaloylbispyrrolidine, N
, N'-terephthaloylbis-diethylamine, N,
N'-Isophthaloylbis-diethylamine, N,N
' -phthaloylbis-diethylamine, N, N' -
Terephthaloylbis-dipropylamine, N,N'-Isophthaloylbis-dipropylamine, N,N'-Terephthaloylbis-dibutylamine, N
, N'-isophthaloylbisulfdibutylamine, 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'-Isophthaloyl Loylbis-dioctylamine, N,N'-terephthaloylbis-diyl-oxypropylamine, N,N'-terephthaloylbis-4-chlorobutylamine, N,N'-terephthaloylbis-dibenzoylamino Ethylamine, N,N'-Isophthaloylbis-dibenzoylaminoethylamine, N,N'-Terephthaloylbis-benzoylaminopropylamine, N,N'-Isophthaloylbis-benzoylaminopropylamine, N,N '-Terephthaloyl bis-diacetylaminoethylamine, N,N'-isophthaloyl bis-diacetylaminoethylamine.

N,N'-terephthaloyl bis(4-methylpiperidine), N,N'-terephthaloyl bis(3-methylpiperidine), N,N'-terephthaloyl bis(3,5-dimethylpiperidine), N , N'-terephthaloylbis(2-methylpiperidine), N,N'-terephthaloylbis(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'-isophthaloyl bis(3,5-dimethylpiperidine), N,N'-phthaloyl bis(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'-terephthaloylbis(4-methoxycarbonylpiperidine), N,N' -Isophthaloylbis(4-methoxycarbonylpiperidine), N,N'-terephthaloylbis(2-methoxycarbonylpiperidine), N,N'-isophthaloylbis(2-methoxycarbonylpiperidine), N,N '-phthaloyl bis(2-methoxycarbonylpiperidine), N,N'-terephthaloyl bis(4-ethylpiperidine), N,N'-terephthaloyl bis(4-propylpiperidine), N,N'-terephtha Loylbis(4-butylpiperidine), N,N'-Isophthaloylbis(4-ethylpiperidine), N,N'-Isophthaloylbis(4-Normalpropylpiperidine), N,N'-Isophthaloylbis rubis(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'-isophthaloylbis(3-hydroxymethylpiperidine), N,N'-phthaloylbis(3-hydroxymethyl-
27=piperidine), N,N'-terephthaloylbis(5-ethyl-2-methylpiperidine), N,N'-isophthaloylbis(5-ethyl-2-methylpiperidine), N,N'- Phthaloyl bis(5-ethyl-2-methylpiperidine), N,N'-terephthaloyl bis(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'-cyclohexylamine), N,N'-terephthaloylbis(4-ethyloxymethylpiperidine), N,N'-isophthaloylbis (4-ethyloxymethylpiperidine), N,N'-terephthaloylbis(4-ethyloxyethylpiperidine), N,N'-isophthaloylbis(4-ethyloxyethylpiperidine), N,N '-terephthaloylbis(2-methoxyethylpiperidine), N,N'-isophthaloylbis(2-methoxyethylpiperidine), N,N'-terephthaloylbis(4-methoxyethylpiperidine), N, N'-(isophthaloyl bis(4-methoxyethyl biveridine), N,N'-terephthaloyl bis(4-phenylpiperidine), N,N'-isophthaloyl bis(4-phenylpiperidine), N,N'-phthaloylbis(4-phenylpiperidine), N,N'-terephthaloylbis(4-phenylpropylpiperidine), N,N'-isophthaloylbis(4-phenylpropylpiperidine), N,N '-phthaloyl bis(4-phenylpropylpiperidine), etc.

In the general formula (IV), R9 and RIO represent alkyl, cycloalkyl, aryl, or aralkyl which may have a substituent. The alkyl is usually
Examples include linear or branched chains having 1 to 18 carbon atoms, cycloalkyl includes cyclohexyl, aryl includes phenyl, tolyl, xylyl, etc., and aralkyl includes benzyl, phenethyl, etc. etc. These substituents can further have other substituents, such as alkyl, aryl, halogen, alkoxy, aryloxy, aralkyloxy, acyl, acyloxy, alkoxycarbonyl, carbamoyl, Examples include substituents such as acylamino. Yl and V2 are linear or branched alkylene groups having 1 to 18 carbon atoms.

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(cyclohexylamino N,N'-bis(hexyloylaminopropyl)piperazine, N-benzoylaminopropyl-N'-cyclohexylaminoethylpiperazine, N-benzoylaminopropyl-N'-benzoylaminobutylpiperazine, N -(P-chlorobenzoylaminoamyl)-N'-benzoylaminopropylpiperazine, N-cyclohexylaminopropyl-N'-cyclohexyloylaminobutylpiperazine, N-naphthoylaminopropyl-N'-benzoylaminopropyl Piperazine, N-butyroylaminopropyl-N'-benzoylaminopropylpiperazine, N-lauroylaminopropyl-N'-benzoylaminopropylpiperazine, N-stearoylaminopropyl-N'-benzoylaminopropylpiperazine, N-butyroylamino Propyl-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' -1-ribenzoyl diethylene 1
-triamine, N, N', N"-1-ribenzoyl-dipropylene triamine, N, N', N', N"'-tetrabenzoyl-1~
Liedylenetetramine, 1.7-dibenzoyl-4-methyl-diethylenetriamine, 1.9-dibenzoyl-5-methyl-dipropylenetriamine, 1.7-diα-naphthoyl-4-methyl-diethyl l
-riamino, ], 7-di-α-naph-1-yl-4-cyclohexyl-
Diethylenetriamine, N, N', N#-tripivaloyl-diethylenetriamine, N, N', N", N"'-tetraacetyl-triethylenetetramine, N, N', N', N"'-tetracyclohexyloyl-tri Ethylenetetramine, ethylenediaminetetraacetic acid tetraanilide, ethylenediaminetetraacetic acid tetracyclohexylamide, ethylenediaminetetraacetic acid tetra-2-ethylhexylamide, ethylenediaminetetraacetic acid tetralaurylamide, ethylenediaminetetraacetic acid tetrastearylamide, ethylenediaminetetraacetic acid tel-rapiperidide, ethylenediamine 4-acetic acid tetra-ε-cabrolactamide, etc.

In addition, polyethers, polyethylene glycol derivatives, solid alcohols, aliphatic or aromatic amines, guanidine derivatives, morpholine derivatives, etc. can be used as decolorizing agents.

In the present invention, the coloring agent used in the low temperature side thermosensitive coloring layer is:
Any dye that forms a stable image when heated with low energy and is easily erased with a decoloring agent when heated with high energy is sufficient. In the case of the present invention, a basic leuco dye is used. The coloring agent used in the high-temperature side heat-sensitive coloring layer may be one that is not easily erased by a decoloring agent. Therefore, the coloring agent used in the high-temperature side heat-sensitive coloring layer is not limited to leuco dyes.
Other conventionally known heat-sensitive coloring systems may also be used.

The basic leuco dyes used in the low-temperature side 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. For example, leuco compounds of dyes 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-chlorphthalide, 3.3-bis(P-dibutylaminophenyl)phthalide, 3-cyclohexylamino-6-chlor Fluoran, 3-diethylamino-6-chloro-7-methylfluoran, 3-dimethylamino-5,7-dimethylfluoran, 3
-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7,8-benzfluorane, 3-diethylamino-6
-Methyl-7-chloro236=luorane, 3-(N-p-1~ly-N-ethylamino)-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluoran Oran, 2- (N-(3'-trifluoromethylphenyl)
amino)-6-dinithylaminofluorane.

2-(3,6-bis(diethylamino)-9-(o-
chloranilino)xantylbenzoic acid lactam), 3-
Diethylamino-6-methyl-7-(m-1 helichloromethylanilino)fluoran, 3-diethylamino-7-(o-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'-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-pendyltrifluoromethylaniυ)) fluorane, 3-pyrrolidino-7-(di-P-chlorophenyl)methylaminofluorane, 3-diethylamino-5-chloro-7-(α-phenylethylamino)fluoran, 3-(N-Ethyl-P-toluidino)-7-(α-)engineered methylethylamino)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-47-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 side coloring layer include 3-diethylamino-7-chlorofluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-7-chlorofluoran, and 3-diethylamino-7-chlorofluoran. Examples include cyclohexylamino-6-chlorofluorane, 3-diethylaminobenzo[α]fluorane, and the like.

In the present invention, the high-temperature side heat-sensitive coloring layer may contain an acidic leuco dye, for example, an acylated Rough-1-type or Zalton-type leuco dye as shown below.

In the present invention, examples of the color developer for the leuco dye in the high-temperature coloring layer and the low-temperature coloring layer include N,N'-diphenylthiourea, N-P-ethylphenyl-N'-phenylthiourea, N-P-butyl Phenyl-N'-phenylthiourea, N,N'-g1-chlorophenylthiourea, N,
N'-di-p-chlorophenylthiourea, N, N'
-di-m-trifluoromethylphenylthiourea, N,
N'-di-m-methylphenylthiourea, 4.4'
-isopropylidene diphenol, 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-tert-butylphenol), 4.4
'-5ee-butylidene diphenol, 4.11' -
Cyclohexylidenebis(2-methylphenol), 4
- tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, α-naphthol, β-naphthol, 3.5-xylenol, thymol,
Methyl-4-hydroxybenzoate, 4-hydroxyace1hephenone, novolac type phenolic resin, 2,
2'-thiobis(4,6-dichlorophenol), catechol, resorcinol, hydroquinone, pyroganol,
Phloroglucin, phloroglycin carboxylic acid, 4 +
: cr t, -octylcatechol, 2,2' -
Methylenebis(4-chlorophenol), 2,2'-methylenebis(4-methyl-6-terL-butylphenol), 2,2'-dihydroxydiphenyl, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, p- Butyl hydroxybenzoate, benzyl p-hydroxybenzoate, p-chlorobenzyl p-hydroxybenzoate, 0-chlorobenzyl p-hydroxybenzoate, p-methylbenzyl p-hydroxybenzoate,
n-octyl p-hydroxybenzoate, benzoic acid, zinc salicylate, 1-hydroxy-2-naphthoic acid, 2-
Hydroxy-6-naphthoic acid, zinc 2-hydroxy-6-naphthoic acid, 4-hydroxydiphenylsulfone, 4
-Hydroxy-4'-chlorodiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 0-sulfophthalimide, 5-isopropyl-〇-sulfophthalimide, 5-t-butyl-0-sulfophthalimide, 5-octyl-〇- In addition to sulfophthalimide and the like, guanidine-based organic base color developers shown below may also be used.

In the present invention, the coloring system in the high-temperature side thermosensitive coloring layer is not particularly limited, and in addition to the above-mentioned leuco system, various types 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, cobal I, lead, copper, iron, mercury, silver salts such as acetic acid, stearic acid, palmitic acid, calcium sulfide, strontium sulfide,
A combination with an alkaline earth metal sulfide such as potassium 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) 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-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.

=48 In the present invention, various commonly used binders can be used as appropriate in order to bond and support each heat-sensitive color forming layer and decoloring agent layer on a support. For example, polyvinyl alcohol, starch, and Derivatives, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylic amide/acrylic ester copolymer, acrylic amide/acrylic ester/methacrylic acid ternary copolymer, styrene/matric anhydride copolymer alkali salt, isobutylene/maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin,
In addition to water-soluble polymers such as casein, polyvinyl acetate, polymethane, styrene/butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride/vinyl acetate copolymer, polybutyl methacrylate, ethylene/
Latex such as vinyl acetate copolymer, styrene/butadiene/acrylic copolymer, etc. can be used.

In addition, in the present invention, each heat-sensitive color forming layer and color erasing agent layer may further contain auxiliary additive components commonly used in this type of heat-sensitive recording material, such as fillers, surfactants, heat-fusible It can be caused by using a sexual substance (or lubricant) etc. 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 carboxylic acids and amines, phenyl benzoate, higher linear glycols, dialkyl 3,4-epoxy-hexahydrophthalates, higher ketones, and other thermofusible organics. Examples include compounds having a melting point of about 50 to 200°C.

〔effect〕

The multicolor heat-sensitive recording material of the present invention has the above-mentioned structure, and has excellent color separation properties by providing an intermediate layer containing a petroleum resin between at least one heat-sensitive coloring layer and an adjacent color erasing layer. Provides a multicolored image.

〔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 Dispersion A was obtained by grinding and dispersing the following compositions using a sand grinder so that the volume average particle diameter was 2 to 3 μm.
-F was obtained.

[Dispersion A]

3-(N-ethyl-N-amylamino)-6-methyl-
7-Aniritsufluoran (black) 20 parts 1
0% hydroxyethylcellulose aqueous solution 2o water
60
// [Dispersion B] 3.3'-dichlorophenylthiourea 10 parts 5 l- N-stearylbenzamide 10 parts Calcium carbonate 10 // Polyvinyl alcohol lO% aqueous solution 20 water
501/[
Dispersion C] 3-diethylamino-7-lyrofluorane (red) 2
0 parts 10% hydroxyethyl cellulose aqueous solution 201/water
60 [Dispersion D] 3.3-Dichlorophenylthiourea 10 parts Calcium carbonate lQn Polyvinyl alcohol 10% aqueous solution 20! I water
60 [Dispersion E] Crystal violet lactone (blue) 20 parts 10%
Hydroxyethylcellulose aqueous solution 201! water
60I
I [Dispersion F] Bisphenol A 10 parts
52= Calcium carbonate 10 parts 10
% hydroxyethylcellulose aqueous solution 15/I water
65
〃10 parts of dispersion A prepared as above, 87 parts of dispersion
0 parts and 20 parts of water were mixed and stirred to obtain a thermosensitive coloring layer forming liquid for low temperature coloring. Separately, 10 parts of dispersion C, 070 parts of dispersion, and 20 parts of water were mixed and stirred.
A thermosensitive coloring layer forming liquid for medium temperature coloring was obtained.

Further, 10 parts of the dispersion F1, 20 parts of the dispersion F2O, and 20 parts of water were each taken and mixed and stirred to obtain a thermosensitive coloring layer forming liquid for high temperature coloring.

Further, a decolorizing agent layer forming liquid for forming a decolorizing agent layer was prepared at the following ratio.

[Decolorizer layer forming liquid]

Isophthaloyl bis(N-methyl-N-cyclohexylamine) 20 parts 10% polyvinyl alcohol aqueous solution 2o/I water
6
0 Next, the high temperature thermosensitive coloring layer forming liquid (dry coating amount: 5 g/m) was applied onto commercially available high-quality paper with a basis weight of approximately 52 g/m.
), decolorizer layer forming liquid (dry coating amount: 3 g#rl'), terpene resin latex (solid content: 40
%) (dry coating amount 3g #+?), medium temperature thermosensitive color forming layer forming liquid (dry coating amount 4.5 g/m), decoloring agent layer forming liquid (dry coating amount 3 g/m), intermediate layer Terpene resin latex (solid content 4%) as forming liquid (dry application amount 3
g / rrr ), low temperature thermosensitive coloring layer forming liquid (dry coating amount: 4 g #rF) was applied and dried, and then the smoothness was 50.
A multicolor heat-sensitive recording material of the present invention was prepared by calendering to a time of 0 to 1000 seconds.

Example 2 A multicolor thermosensitive recording material was prepared in the same manner as in Example 1 except that coumaron-indene resin latex was used instead of terpene resin latex as the intermediate layer forming liquid.

Example 3 A multicolor thermosensitive recording material was prepared in the same manner as in Example 1 except that styrene-indene resin latex was used instead of terpene resin latex to form the intermediate layer.

Comparative Example 1 A comparative heat-sensitive recording material was prepared in the same manner as in Example 1, except that polyvinylidene chloride was used instead of the terpene resin as the intermediate layer forming liquid.

Example 4 A two-color heat-sensitive recording material was prepared in the same manner as in Example 1, except that the low-temperature heat-sensitive coloring layer, the terpene latex intermediate layer on the second layer side, and the decolorizing agent layer on the upper layer side were removed.

Example 5 A two-color heat-sensitive recording material was prepared in the same manner as in Example 2, except that the low-temperature heat-sensitive coloring layer, the upper coumaron-indene resin intermediate layer, and the upper decolorizing agent layer were removed.

Example 6 A two-color heat-sensitive recording material was prepared in the same manner as in Example 3, except that the low-temperature heat-sensitive coloring layer, the upper styrene-indene resin intermediate layer, and the decolorizing agent layer on the first layer side were removed.

Comparative Example 2 A comparative heat-sensitive recording material was prepared in the same manner as in Comparative Example 1, except that the low-temperature thermosensitive coloring layer, the upper terpene latex intermediate layer, and the upper decolorizing agent layer were removed.

The multicolor heat-sensitive recording materials of Examples and Comparative Examples obtained as described above were tested for dynamic coloring characteristics using a G-m facsimile test machine.

The test machine was an 8 dot/m manufactured by Matsushita Electronic Components Co., Ltd.
It has a thermal head of m, and the heating element resistance is approximately 400Ω/
The color development test was conducted at a main scanning recording speed of 20 m.
The test was carried out under the following conditions: 5ec/1ine, sub-scanning speed of 3.852/mm, platen suppression of 3.0kg/cJ, and head input of 0.6W/dot. The coloring energy of the low temperature coloring layer is 1.
0+nJ, medium temperature coloring layer 2.抛、■、High temperature coloring layer is 3.3
It was done with mJ.

In addition, a Macbeth densitometer was used to measure the concentration.

As a result of the test, in Examples 1 to 3, the three constituent colors were clearly separated and colored, whereas in Comparative Example, the medium-temperature thermosensitive coloring layer and the high-temperature thermosensitive coloring layer exhibited mixed colors, and
The thermosensitive recording materials of Examples 4 to 6 are as follows.

As with the three-color type, the two colors were well separated and gave clear color development, whereas in Comparative Example 2, both colors were mixed.

As described above, the multicolor heat-sensitive recording material of the present invention has excellent color separation properties.

Claims (1)

[Claims] (1) A plurality of thermosensitive coloring layers each having different coloring energy and producing different tones are laminated one after another on a support such that the one with lower coloring energy becomes the upper layer, and each layer is erased between adjacent thermosensitive coloring layers. In a multicolor thermosensitive recording material provided with a color layer, a softening point of 70 to 150°C,
At least one intermediate layer containing a petroleum resin having a molecular weight of 600 to 2,000 is provided between the heat-sensitive coloring layer and the decoloring layer adjacent thereto.
A multicolor heat-sensitive recording material characterized by being provided with a.