JP2004233344A - Irreversible multi-coloring heat-sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an irreversible multi-coloring heat sensitive material, capable of simultaneously controlling the heating temperature and the heating time with the heat-sensitive material useful, for example, for controlling the heating condition of a drink to be heated in a metal can or a plastic bottle. <P>SOLUTION: On a support, a precursor of normally colorless or hypochromic of two or more types of electron-donative dye stuffs coloring in different color tones to each other, and one or more coloring layers containing electron-donor compounds making the dyestuff precursor color are provided, wherein at least one or more kinds of the dye stuff precursors are made to exist in the coloring layer in a grain form having a coloring adjust layer on its surface, obtained by the addition polymerization of a vinyl monomer. At least two or more dye stuff precursors are made to exist in the coloring layer, are made to exist in the coloring layer in the grain form having the coloring adjust layer on its surface, obtained by the addition polymerization of the vinyl monomer. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to an irreversible multicolor thermometer material used, for example, when simultaneously controlling the heating temperature and the heating time of a beverage placed in a metal can or a plastic container that is heated and drunk.

  In recent years, in beverages sold at vending machines, etc., the demand for beverages that are heated and drunk has been increasing. Due to the development of dedicated warmers, etc., not only vending machines but also stores are heated and consumed. Beverage is being sold.

  When a beverage is heated and sold, it is necessary to control the heating time and the heating temperature in order to maintain the quality. For example, if the heating temperature of the beverage is set higher than the temperature suitable for the beverage for the purpose of shortening the heating time, the quality of the beverage may be deteriorated and the beverage may not be suitable for drinking.

  In addition, even if the heating time is improperly controlled and heated for an unnecessarily long time, the quality of the beverage may be deteriorated and the beverage may not be suitable for drinking.

  Therefore, there is a demand for a temperature indicating material that is used for the purpose of controlling the heating temperature and the heating time by sticking to the surface of a container such as a metal can or a plastic bottle and confirming the coloring state. In particular, there is a great demand for a temperature indicating material that can make the management of the heating state easier by developing different colors when the heating temperature is too high and when the heating time is too long.

As a temperature indicating material used for such a purpose, an irreversible temperature indicating material provided with a layer containing a colorless or pale color dye precursor, a coloring material and a thermoplastic substance has been proposed (for example, see Patent Document 1). .). However, this temperature indicating material develops a single color of blue or red when placed in an environment of about 60 ° C., which is a temperature suitable for drinking, and when the temperature becomes higher than about 60 ° C. It is not intended to control and distinguish the heating temperatures of the respective products. Furthermore, it is impossible to control the heating time. Although a temperature indicating material that changes color at different temperatures has been proposed (for example, see Patent Document 2), it cannot be used to control the heating time. Further, a temperature control member for a temperature indicating member whose color changes in response to a temperature has been proposed (for example, see Patent Document 3). You can't manage both time.
JP-A-11-140339 JP-A-10-197362 JP 2001-66196 A

  The present invention relates to an irreversible multicolor temperature-indicating material, for example, useful for managing the heating state of a beverage placed in a metal can or a plastic container that can be heated and drunk, heating temperature and heating time And irreversible multicolor thermometer materials that can be managed simultaneously by one thermometer material.

  The present inventors have conducted intensive studies and, as a result, have invented an irreversible polychromatic thermochromic material of the present invention that can solve the problems. That is,

  (1) On a support, two or more kinds of electron-donating, usually colorless or pale-colored dye precursors that form colors different from each other, and an electron-accepting compound that reacts upon heating to form the dye precursor are formed. In an irreversible multicolor thermochromic material having a color-forming layer comprising at least one layer, at least one of the dye precursors has a color-controlling layer obtained by addition polymerization of a vinyl monomer on the surface thereof. An irreversible multicolor thermochromic material characterized by being present in a color-forming layer in a form.

  (2) At least two or more of the dye precursors present in the color forming layer are present in the color forming layer in the form of particles having a color control layer obtained by addition polymerization of a vinyl monomer on the surface ( The irreversible multicolor thermometer material according to 1).

  (3) The irreversible polymorph described in (1) or (2), wherein the color-forming layer contains 3,3-bis (1-n-hexyl-2-methylindol-3-yl) phthalide as a dye precursor. It is a color indicating temperature material.

  (4) The irreversible polychromatic thermoelectric material according to any one of (1) to (3), wherein the color forming layer contains a urea urethane compound represented by the general formula 1 as an electron accepting compound.

  (5) The irreversible multicolor thermographic material according to any one of (1) to (3), wherein the color-forming layer contains 4-hydroxy-4'-isopropoxydiphenylsulfone as an electron-accepting compound.

  (6) The irreversible multicolor temperature-indicating material according to any one of (1) to (5), wherein the color-forming layer contains the amide derivative represented by the general formula (2).

(Wherein, A represents an alkyl group or an alkylamino group, and R ₁ and R ₂ may be the same or different substituents, and each represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, Represents an alkenyl group, an aralkyl group, or an allyl group.)

  Since the irreversible multicolor thermometer of the present invention develops a different color depending on the heating temperature, the heating temperature can be controlled by observing the color tone. Further, since the color density changes with the elapse of the heating time, the heating time can be managed. Therefore, unlike the temperature indicating materials that have been proposed so far, it is possible to simultaneously control the heating temperature and the heating time with one type of the temperature indicating material.

  The contents of the present invention will be described more specifically. The irreversible multicolor thermographic material of the present invention, on a support, two or more kinds of electron-donating usually colorless to light-colored dye precursors that develop colors different from each other, and reacts when heated to react the dye precursor. An irreversible multicolor thermochromic material having a color-forming layer comprising at least one layer containing a color-forming electron-accepting compound.

  In the irreversible multicolor thermosensitive material of the present invention, at least one or more of two or more kinds of electron-donating dye precursors that develop colors different from each other, a color control layer obtained by addition polymerization of a vinyl monomer. Is present in the color-forming layer in the form of particles having on the surface.

  By providing a coloring control layer on the dye precursor, it is possible to adjust the coloring temperature of each coloring to obtain an irreversible multicolor thermochromic material exhibiting different colorings at low-temperature heating and high-temperature heating. If such a temperature indicating material is used for heating state management of a beverage placed in a metal can or a plastic container to be heated and drunk, for example, when heated at a temperature suitable for drinking, Since the color develops in a different color tone when heated at a high temperature that is not suitable for drinking, it is possible to easily control the heating temperature.

  The irreversible multicolor thermochromic material of the present invention, two or more kinds of electron-donating dye precursors that develop colors different from each other are used in the form of dispersed particles for low-temperature coloring or particles having a coloring control layer on the surface. The dye precursor for high-temperature coloring is used in the coloring layer in the form of particles having a coloring control layer on the surface. When both the low-temperature coloring and the high-temperature coloring have a coloring control layer on the surface, the type of the coloring control layer or the thickness of the film is adjusted so that the low-temperature coloring side has higher sensitivity than the high-temperature coloring side. It can be changed and adjusted.

  By providing a coloring control layer on the dye precursor for low-temperature coloring, it is possible to adjust the coloring speed at the time of low-temperature heating. When a temperature indicating material containing such a dye precursor is used for controlling the heating state of a beverage placed in a metal can or a plastic container to be heated and drunk, for example, at a temperature suitable for drinking. Since the color density changes when heated for an appropriate time and when the quality of the beverage in the container is deteriorated due to being heated for a long time, it is possible to easily manage the heating time, Particularly preferred.

  The dye precursor for low-temperature coloring of the present invention has a color tone of reddish to yellowish or one or more of greenish to bluedish, and is appropriately used in combination. Since the color of the material tends to be a dark color due to color mixture at a high temperature, a light red-based to yellow-based color is preferably used on a low-temperature side. As the high-temperature coloring dye precursor, one or more dye precursors that develop a dark color such as a black color, a green color, and a blue color are used in appropriate combination.

  Specific examples of the dye precursor such as red, yellow, blue, green, and black are given below, but the present invention is not limited to these.

  Examples of red coloring dyes include 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide and 3,3-bis (1-n-butyl-2-methylindol-3-yl). ) Tetrachlorophthalide, 3,3-bis (1-n-butylindol-3-yl) phthalide, 3,3-bis (1-n-pentyl-2-methylindol-3-yl) phthalide, 3, 3-bis (1-n-hexyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-n-octyl-2-methylindol-3-yl) phthalide, 3,3-bis ( 1-methyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-propyl-2-methylindole) -3-yl) phthalide, , 3-Bis (2-methylindol-3-yl) phthalide, rhodamine B-anilinolactam, rhodamine B- (o-chloroanilino) lactam, rhodamine B- (p-nitroanilino) lactam, 3-dimethylamino-6-methyl -7-chlorofluorane, 3-dimethylamino-7-methylfluorane, 3-dimethylamino-7-methoxyfluorane, 3-dimethylamino-7-chlorofluorane, 3-ethylamino-7-methylfluorane , 3-diethylamino-5-methyl-7-dibenzylaminofluoran, 3-diethylamino-6-methylfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-6-methyl-7-chlorofluoran , 3-diethylamino-6-methyl-7-chloro-8-benzylfluoro 3-diethylamino-6,7-dimethylfluoran, 3-diethylamino-6,8-dimethylfluoran, 3-diethylamino-7-methylfluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino- 7-chlorofluorane, 3-diethylamino-7-methylethoxyfluoran, 3-diethylamino-7- (N-acetyl-N-methyl) aminofluoran, 3-diethylamino-7-p-methylphenylfluoran, 3 -Diethylamino-7,8-benzofluoran, 3-diethylaminobenzo [a] fluoran, 3-diethylaminobenzo [c] fluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-chlorofluor Oran, 3- (N-ethyl-N-isoamyl) amino-7,8-benzof Fluoran, 3- (N-ethyl-N-isoamyl) amino-7-methylfluoran, 3- (N-ethyl-N-isoamyl) amino-benzo [a] fluoran, 3- (N-ethyl-Nn -Octyl) amino-6-methyl-7-chlorofluoran, 3- (N-ethyl-Nn-octyl) amino-7-methylfluoran, 3- (N-ethyl-Nn-octyl) amino -7-chlorofluoran, 3- (N-ethyl-NNn-octyl) amino-7,8-benzofluoran, 3- (N-ethyl-N-4-methylphenyl) amino-7-methylfluor Oran, 3- (N-ethyl-N-4-methylphenyl) amino-7,8-benzofluoran, 3- (N-ethyl-N-ethoxyethyl) amino-7-chlorofluoran, 3- (N -Ethyl-N-ethoxy Tyl) amino-7,8-benzofluoran, 3-di-n-butylamino-6-methyl-7-chlorofluorane, 3-di-n-butylamino-6-methyl-7-bromofluoran, 3-di-n-butylamino-7-methylfluoran, 3-di-n-butylamino-7-chlorofluorane, 3-di-n-butylamino-7,8-benzofluoran, 3-diallyl Amino-7,8-benzofluorane, 3-diallylamino-7-chlorofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-pyrrolidylamino-7-methylfluorane, 3,6-bis ( Red-coloring dyes such as diethylaminofluoran) -γ- (4′-nitro) anilinolactam.

  Examples of yellow coloring dyes include 3,6-dimethoxyfluoran, 3-cyclohexylamino-6-chlorofluorane, 2,6-diphenyl-4- (4-dimethylaminophenyl) -pyridine, and 2,2-bis ( 4- (2- (4-diethylaminophenyl) quinazolyl) oxyphenyl) propane, 4-chloro-N- (4- (N- (4-methylbenzyl) -N-methylamino) benzylidene) aniline, 1- (2 Yellow-color-forming dyes such as -quinolyl) -2- (3-methoxy-4-dodecyloxyphenyl) ethene and 1- (4-n-dodecyloxy-3-methoxyphenyl) -2- (2-quinolyl) ethylene;

  When 3,3-bis (1-n-hexyl-2-methylindol-3-yl) phthalide is contained as a low-temperature coloring dye precursor, it is heated at a temperature of about 60 ° C. to 70 ° C. suitable for drinking. This method is particularly preferable because a sufficient color density can be obtained when the above process is performed.

  Examples of the blue coloring dye include 3- (1-ethyl-2-methylindol-3-yl) -3- (4-diethylaminophenyl) phthalide and 3- (1-ethyl-2-methylindol-3-yl). -3- (2-Methyl-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-aminophenyl)- 4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-methylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2- Methylindol-3-yl) -3- (2-ethoxy-4-ethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- ( 2-ethoxy-4-dimethyl Aminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl -2-Methylindole-3-yl) -3- (2-ethoxy-4-dipropylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-dibutylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-dipentylaminophenyl ) -4-Azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-dihexylaminophenyl) -4-azaphthalide, 3- (1-ethyl- 2- (Childindole-3-yl) -3- (2-ethoxy-4-diallylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2 -Ethoxy-4-dicyclohexylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-dimethoxycyclohexylaminophenyl) -4- Azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-pyrrolidylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methyl) Indole-3-yl) -3- (3-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2, 3 -Diethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (4-diethylaminophenyl) -4-azaphthalide, 3- (1- Ethyl-2-methylindol-3-yl) -3- (2-chloro-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl)- 3- (3-chloro-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-bromo-4-diethylaminophenyl) -4 -Azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (3-bromo-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methyl) Indole-3-yl) -3- (2-ethyl-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2- Propyl-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (3-methyl-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindole-3-yl) -3- (2-nitro-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindole-3-yl) Yl) -3- (2-allyl-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-hydroxy-4-diethylaminophenyl -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-cyano-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2- Methylindol-3-yl) -3- (2-cyclohexylethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- ( 2-methylethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-cyclohexylethyl-4-diethylaminophenyl) -4- Azaphthalide, 3- (2-ethylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-chloro) Indole-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-bromoindol-3-yl) -3- (2- Ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-ethylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-propylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methoxyindol-3-yl) Yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-ethoxyindol-3-yl) -3- (2-ethoxy-4-diethylamido) Phenyl) -4-azaphthalide, 3- (1-ethyl-2-phenylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl- 2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -7-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4,7-diazaphthalide, 3- (1-ethyl-4,5,6,7-tetrachloro-2-methylindol-3-yl) -3- ( 2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-4-nitro-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl)- 4 Azaphthalide, 3- (1-ethyl-4-methoxy-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-4 -Methylamino-2-methylindole-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-4-methyl-2-methylindole) -3-yl) -3- (2-Ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) 4-azaphthalide, 3- (1-chloro-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-bromo-2 -Methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-methyl-2-methylindol-3-yl) -3- ( 2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-methyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -7-azaphthalide, 3- (1-propyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-butyl-2-methylindole- 3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-butyl-2-indol-3-yl) -3- (2-ethoxy-4-diethylamino Enyl) -7-azaphthalide, 3- (1-pentyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-hexyl- 2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-hexyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -7-azaphthalide, 3- (1-octyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide , 3- (1-octyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -7-azaphthalide, 3- (1-octyl-2-me (Lindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4,7-diazaphthalide, 3- (1-nonyl-2-methylindol-3-yl) -3- ( 2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-methoxy-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethoxy-2-methylindole-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-phenyl-2-methylindole- 3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-pentyl-2-methylindol-3-yl) -3- (2-ethoxy-4- The Ethylaminophenyl) -7-azaphthalide, 3- (1-heptyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -7-azaphthalide, 3- (1- Nonyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -7-azaphthalide, 3- (4-dimethylamino-2-methylphenyl) -3- (4- Dimethylaminophenyl) -6-dimethylaminophthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-n-hexyloxy-4-diethylaminophenyl) -4-azaphthalide, And blue-developing dyes such as 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide.

  Examples of green coloring dyes include 3-dimethylamino-6-chloro-7-dibenzylaminofluoran, 3-dimethylamino-6-methyl-7-n-octylaminofluoran, and 3-dimethylamino-7-di Benzylaminofluoran, 3-dimethylamino-7-n-octylaminofluoran, 3-diethylamino-6-methyl-7-benzylamino-fluoran, 3-diethylamino-6-methyl-7-dibenzylaminofluoran, 3-diethylamino-6-methyl-7-n-octylaminofluoran, 3-diethylamino-6-methyl-7- (N-cyclohexyl-N-benzylamino) fluoran, 3-diethylamino-6-methyl-7- ( 2-chloroanilino) fluoran, 3-diethylamino-6-methyl-7- (2-trifluoro Tylanilino) fluoran, 3-diethylamino-6-methyl-7- (3-trifluoromethylanilino) fluoran, 3-diethylamino-6-methyl-7- (2-ethoxyanilino) fluoran, 3-diethylamino-6- Methyl-7- (4-ethoxyanilino) fluoran, 3-diethylamino-6-chloro-7-anilinofluoran, 3-diethylamino-6-chloro-7- (2-chloroanilino) fluoran, 3-diethylamino-6 -Chloro-7-dibenzylaminofluoran, 3-diethylamino-6-ethylethoxy-7-anilinofluoran, 3-diethylamino-7-anilinofluoran, 3-diethylamino-7-methylanilinofluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethyl Mino-7-n-octylaminofluoran, 3-diethylamino-7-p-chloroanilinofluoran, 3-diethylamino-7-p-methylphenylanilinofluoran, 3-diethylamino-7- (N-cyclohexyl -N-benzylamino) fluoran, 3-diethylamino-7- (2-chloroanilino) fluoran, 3-diethylamino-7- (3-trifluoroanilino) fluoran, 3-diethylamino-7- (2-trifluoromethylani Lino) fluoran, 3-diethylamino-7- (2-ethoxyanilino) fluoran, 3-diethylamino-7- (4-ethoxyanilino) fluoran, 3-diethylamino-7- (2-chlorobenzylanilino) fluoran, 3- (N-ethyl-NN-propyl) amino-6-chloro -7-dibenzylaminofluoran, 3- (N-ethyl-NN-propyl) amino-7-dibenzylaminofluoran, 3- (N-ethyl-NN-hexyl) amino-7-ani Linofluoran, 3- (N-ethyl-N-4-methylphenyl) amino-6-methyl-7-dibenzylaminofluoran, 3- (N-ethyl-N-4-methylphenyl) amino-6 Methyl-7- (N-methyl-N-benzyl) aminofluoran, 3- (N-ethyl-N-4-methylphenyl) amino-7- (N-methyl-N-phenyl) aminofluoran, 3- (N-ethyl-N-4-methylphenyl) amino-7-dibenzylaminofluoran, 3-dibutylamino-6-chloro-7- (2-chloroanilino) fluoran, 3-dibutylamino-6-methyl 7- (2-chloroanilino) fluoran, 3-dibutylamino-6-methyl-7- (2-fluoroanilino) fluoran, 3-dibutylamino-7- (2-fluoroanilino) fluoran, 3-dibutylamino- 7- (2-chloroanilino) fluoran, 3-dibutylamino-7- (2-chlorobenzylanilino) fluoran, 3- (N-methyl-Nn-hexyl) amino-7-anilinofluoran, 3- (N-propyl-Nn-hexyl) amino-7-anilinofluoran, 3- (N-ethoxy-Nn-hexyl) amino-7-anilinofluoran, 3- (Nn-pentyl) -N-allyl) amino-6-methyl-7-anilinofluoran, 3- (Nn-pentyl-N-allyl) amino-7-anilinofluoran, 3- [p- (p- Nilinoanilino) anilino] -6-methyl-7-chlorofluoran, 3-anilino-7-dibenzylaminofluoran, 3-anilino-6-methyl-7-dibenzylaminofluoran, 3-pyrrolidino-7-di Benzylaminofluoran, 3-pyrrolidino- (7-cyclohexylanilino) fluoran, 3-dibenzylamino-6-methyl-7-dibenzylaminofluoran, 3-dibenzylamino-7-dibenzylaminofluoran, 3-dibenzylamino-7- (2-chloroanilino) fluoran, 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide, 3,6-bis (dimethylamino) fluorene-9-spiro- Green coloring dyes such as 3 '-(6'-dimethylamino) phthalide;

  Examples of black coloring dyes include 3-dibutylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-7- (2-chloroanilino) fluoran, and 3-diethylamino-6-methyl-7-anilinofuran. Oran, 3-diethylamino-6-methyl-7-xylidinofluoran, 3-diethylamino-7- (2-chloroanilino) fluoran, 3-diethylamino-7- (2-carbomethoxy-phenylamino) fluoran, 3- ( N-cyclohexyl-N-methyl) amino-6-methyl-7-anilinofluoran, 3- (N-cyclopentyl-N-ethyl) amino-6-methyl-7-phenylaminofluoran, 3- (N- Isoamyl-N-ethyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-p-toluidino)- -Methyl-7-anilinofluoran, 3- (N-ethyl-p-toluidino) -6-methyl-7- (p-toluidino) fluoran, 3- (N-methyl-N-tetrahydrofurfuryl) amino- 6-methyl-7-phenylaminofluoran, 3- (N-ethyl-N-tetrahydrofurfuryl) amino-6-methyl-7-phenylaminofluoran, 3-pyrrolidino-6-methyl-7-phenylaminofluor Oran, 3-pyrrolidino-6-methyl-7-p-butylphenylaminofluoran, 3-piperidino-6-methyl-7-phenylaminofluoran, 3-dipentylamino-6-methyl-7-anilinofluoran , And the like.

  These dye precursors are used in the form of dispersed particles or particles having a color control layer on the surface for low-temperature coloring, and used in the form of particles having a color control layer on the surface for high-temperature coloring. . What is used in the form of dispersed particles for low-temperature coloring is generally wet-dispersed in a sand mill, a ball mill or the like using water as a dispersion medium so that the dispersed particles have a particle size of 0.1 μm or more and 5 μm or less, preferably 0.3 μm or more and 2 μm or less. Crushed. By setting the content in this range, the background fog and the color density are both good, which is preferable.

  On the other hand, particles having a color control layer on the surface are prepared by adding a vinyl monomer and a polymerization initiator to a dispersion of a dye precursor previously dispersed by a sand mill, a ball mill, or the like, and heating as necessary to obtain dispersed particles. And a color control layer is formed around the substrate. In this case, when the dispersed particle diameter of the dye precursor is smaller than 0.1 μm, the amount of the color control layer is relatively increased as compared with the dye precursor, and the color forming ability of the dye precursor tends to be reduced. Therefore, it is considered to contribute to prevention of background fogging. Conversely, if the dispersed particles of the dye precursor are larger than 5 μm, the color development sensitivity is further reduced by the color control layer. Therefore, the dispersed particle diameter of the dye precursor provided with the color control layer is preferably 0.1 μm or more and 5 μm or less. The vinyl monomer used here is a compound having at least one vinyl bond (carbon-carbon double bond) in the molecule, and the vinyl bond being an active site and capable of addition polymerization.

  Various states can be considered as a mixed state when the vinyl monomer is added to the dispersion of the dye precursor. That is, 1) Most of the dispersion of the dye precursor and the vinyl monomer are phase-separated to form separate phases or are in an emulsified state, but a very small amount of the vinyl monomer contains the dispersion of the dye precursor. 2) a state in which the dispersion of the dye precursor and the vinyl monomer are completely dissolved and completely phase-separated, 3) most or all of the dispersion of the vinyl monomer In these states, if a very small amount of the vinyl monomer of 1) is dissolved in the dispersion of the dye precursor and the polymerization is carried out, the other states are obtained. In this case, a more uniform and dense color-developing layer can be formed on the surface of the particles of the dye precursor, as compared with the case where the polymerization is carried out in the above step. Such a state can be realized by appropriately selecting the type of the dispersion medium for dispersing the particles of the dye precursor and the type of the vinyl monomer.

  The vinyl monomer includes a compound having one vinyl bond and a compound having two or more vinyl bonds. By changing the content of the compound having two or more vinyl bonds, the heat sensitivity characteristic of the color control layer can be freely changed. Compared to those polymerized with only one compound having one vinyl bond, the color control layer using a compound having two or more vinyl bonds together has a stronger cross-linked structure and develops color when formed into an irreversible multicolor thermochromic material. The starting temperature can be higher. The combination ratio of the compound having two or more vinyl bonds is 1% by mass to 70% by mass, preferably 10% by mass to 50% by mass with respect to the total mass of the vinyl monomer. Within this range, it is possible to arbitrarily adjust the coloring characteristics such as the coloring start temperature.

  The total amount of the vinyl monomer based on the dispersed particles of the dye precursor is preferably 0.5% by mass or more and 1000% by mass or less. A coating having a sufficient function as a layer is obtained. By increasing or decreasing the amount of the vinyl monomer, the coloring speed of the coloring control layer can be changed.

  Specific examples of the compound having only one vinyl bond in the present invention include styrene, α-methylstyrene, α-methoxystyrene, m-bromostyrene, m-chlorostyrene, o-bromostyrene, o-chlorostyrene, and p-type. -Bromostyrene, p-chlorostyrene, p-methylstyrene, p-methoxystyrene, 2-vinylpyridine, isobutene, 3-methyl-1-butene, butyl vinyl ether, methyl vinyl ketone, nitroethylene, vinylidene cyanide, ethylene, Propylene, vinyl chloride, vinyl acetate, acrolein, methyl acrolein, acrylamide, N-methylol acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide, N-octadecyl acrylamide, α-ethyl acetoxy acrylate, α-chloro Ethyl acrylate, α-methyl methyl acrylate, methyl α-cyanoacrylate, methyl α-phenylacrylate, benzyl acrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid Lauryl, tridecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-butoxyethyl acrylate, ethoxyethoxyethyl acrylate, methyl triglycol acrylate, Cyclohexyl acrylate, tetrahydrofurfuryl acrylate, cyanoethyl acrylate, ferrocenylmethyl acrylate, glycidyl acrylate, heptafluorobutyl acrylate, methyl acrylate, octyl acrylate, trif Methyl fluoroacrylate, 2-chloroethyl acrylate, 2-nitrobutyl acrylate, acrylic acid, α-bromoacrylic acid, 2-hydroxyethyl acryloyl phosphate, acrylonitrile, allyl glycidyl ether, allyl acetic acid, allyl alcohol, allyl benzene, N -Allyl stearyl amide, 1-butene, 2-butene, N-vinylcaprolactam, ethyl N-vinylcarbamate, N-vinylcarbazole, crotonaldehyde, crotonic acid, 1,1-diphenylethylene, tetrafluoroethylene, diethyl fumarate , 1-hexene, 1-vinylimidazole, 1-vinyl-2-methylimidazole, indene, diethyl maleate, maleic anhydride, maleimide, methacrylamide, benzyl methacrylate, methacrylate Ethyl acrylate, ferrocenylmethyl methacrylate, glycidyl methacrylate, isopropyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methacrylic acid -2-ethylhexyl, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, methyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacryl 2-ethoxyethyl acid, tetrahydrofurfuryl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 3-chloro-2-hydr methacrylate Roxypropyl, methacrylic acid, methacryloxyethyl phosphate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, N-methylol methacrylamide, methacrylonitrile, methacryloyl acetone, 2-isopropenyl-2-oxazoline, 2-vinylquinoline, benzoic acid Examples thereof include vinyl acid, vinyl dodecyl ether, vinyl ethyl sulfoxide, vinyl formate, vinyl isobutyl ether, vinyl laurate, and vinyl phenyl ether, but the present invention is not limited thereto.

  Further, specific examples of the compound having two or more vinyl bonds include polyethylene glycol diacrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and octaethylene glycol diacrylate; Polyethylene glycol dimethacrylates such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4 -Acryloxydiethoxyphenyl) propane, 2,2-bis (4-acryloxytriethoxyphenyl) propa 2,2-bis (4-acryloxypolyethoxyphenyl) propanes, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxy jp22 sidiethoxyphenyl) propane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propanes such as 2,2-bis (4-methacryloxytriethoxyphenyl) propane, allyl acrylate, 1,3-butanediol diacrylate, 1,4- Butanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, N, N'-methylenebisacrylamide, allyl methacrylate, 1,3- Butane Diol methacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, dipropylene glycol dimethacrylate, diallyl phthalate, diallyl chlorendate, butadiene, butadiene-1-carboxylate, butadiene-1,4-dicarboxylic acid Diethylate, diallylmelamine, diallyl phthalate, N, N-divinylaniline, divinylether, divinylbenzene, divinylnaphthalene, 1,3-butanediol dimethacrylate, isoprene, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylol Ethanetrimethacrylate, trimethylolpropanetrimethacrylate, triallyl cyanurate, triallyl isocyanurate, triary Lutrimellitate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate and the like can be mentioned, but the present invention is not limited thereto.

  The above-mentioned vinyl compounds according to the present invention can be used alone or in combination of two or more. When two or more kinds are used in combination, as described above, a combination of a compound having one vinyl bond and a compound having two or more vinyl bonds is preferable. Compounds having two or more compounds can be used in combination.

  When some or all of these vinyl monomers are methacrylic acid esters, the methacrylic acid esters and their polymers have good adhesion to the dye precursor-dispersed particles provided with the color-controlling layer, and have an aqueous dispersion medium. It has good solubility in water and good polymerizability, so it is possible to efficiently coat the surface of the dye precursor dispersed particles by addition polymerization, and furthermore, it has a function of adjusting color development characteristics such as color development start temperature. And are particularly preferably used in the present invention.

  Known polymerization initiators can be used for the addition polymerization of the vinyl monomer, and the polymerization reaction is not particularly limited in terms of the mode of radical polymerization, anionic polymerization, or cationic polymerization, but radical polymerization is particularly preferably used. Can be During the polymerization, the system may be heated as required. Specific examples of the polymerization initiator for radical polymerization are shown below. Peroxides such as hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, potassium persulfate, and persulfates such as ammonium persulfate; 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2, Azo compounds such as 2'-azobis (2-methylpropionamidine) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid), a combination of hydrogen peroxide and ferrous salt, persulfate and sodium acid sulfite Combination, cumene hydroxyperoxide and ferrous salt combination, benzoyl peroxide and diethylaniline Combinations, combinations of peroxide and metal alkyl, such as redox initiators such as a combination of oxygen and an organometallic alkyl. These are not limited to use alone, and may be used as a mixture.

  The polymerization initiator of the radical polymerization is not particularly limited as long as it generates an active radical by heat or light energy other than the above, but when the dye precursor particles are dispersed in an aqueous dispersion medium, It is particularly preferable to use a water-soluble polymerization initiator such as potassium persulfate, ammonium persulfate, and 2,2'-azobis (2-methylpropionamidine) dihydrochloride.

  The amount of the polymerization initiator to be added is not particularly limited as long as the vinyl monomer starts the addition polymerization. It is preferably from 001% by mass to 10% by mass.

  The electron-accepting compound used in the irreversible multicolor thermosensitive material of the present invention is generally represented by an acidic substance used in a pressure-sensitive recording material or a heat-sensitive recording material, but is not limited thereto. Examples thereof include phenol derivatives, aromatic carboxylic acid derivatives, N, N'-diallylthiourea derivatives, allylsulfonylurea derivatives, polyvalent metal salts such as zinc salts of organic compounds, benzenesulfonamide derivatives, urea urethane compounds and the like. it can.

  Specific examples of such electron-accepting compounds include the following compounds, but are not limited thereto.If necessary, they may be used alone or in combination of two or more. Can be used.

  4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 4-hydroxydiphenylsulfone, -Hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-4'-methoxydiphenylsulfone, 4-hydroxy-4'-ethoxydiphenylsulfone, 4-hydroxy-4'-n-butoxydiphenylsulfone, 4-hydroxy-4 '-Benzyloxydiphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (3,5-dichloro-4-hydroxyphenyl) sulfone, 3,4-di Droxydiphenylsulfone, 3,4-dihydroxy-4'-methyldiphenylsulfone, 3,4,4'-trihydroxydiphenylsulfone, 3,4,3 ', 4'-tetrahydroxydiphenylsulfone, 2,3,4 -Trihydroxydiphenylsulfone, 3-phenylsulfonyl-4-hydroxydiphenylsulfone, 2,4-bis (phenylsulfonyl) phenol,

  4-phenylphenol, 4-hydroxyacetophenone, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) hexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexane, 1,1-bis (4-hydroxyphenyl)- 2-ethylhexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-di- [2- (4 -Hydroxyphenyl) -2-propyl] benzene, 1,3-di- [2- (3,4-dihydroxyphenyl) -2-propyl] be Benzene, 1,4-di- [2- (4-hydroxyphenyl) -2-propyl] benzene, 4,4′-hydroxydiphenylether, 3,3′-dichloro-4,4′-hydroxydiphenylsulfide, bis ( 2-hydroxynaphthyl) methane,

  Methyl 2,2-bis (4-hydroxyphenyl) acetate, butyl 2,2-bis (4-hydroxyphenyl) acetate, 4,4'-thiobis (2-tert-butyl-5-methylphenol). Dimethyl 4-hydroxyphthalate, benzyl 4-hydroxybenzoate, methyl 4-hydroxybenzoate, benzyl gallate, stearyl gallate, pentaerythritol tetra (4-hydroxybenzoate) ester, pentaerythritol tri (4-hydroxybenzoate) ) An ester, a dehydration condensation product of a polycondensation product of 2,2-bis (hydroxymethyl) -1,3-propanediol and 4-hydroxybenzoic acid,

  N, N'-diphenylthiourea, 4,4'-bis [3- (4-methylphenylsulfonyl) ureido] diphenylmethane, N- (4-methylphenylsulfonyl) -N'-phenylurea, N- (benzenesulfonyl ) -N ′-[3- (4-toluenesulfonyloxyphenyl)] urea, N- (4-toluenesulfonyl) -N ′-[3- (4-toluenesulfonyloxyphenyl)] urea,

  Salicylanilide, 5-chlorosalicylanilide, salicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, 4- [2 ′-(4-methoxyphenoxy) ethyloxy] salicylic acid, 3- (octyloxycarbonylamino) salicylic acid or a metal salt of these salicylic acid derivatives,

  N- (4-hydroxyphenyl) -4-toluenesulfonamide, N- (2-hydroxyphenyl) -4-toluenesulfonamide, N-phenyl-4-hydroxybenzenesulfonamide and the like.

  When the urea urethane compound represented by the above general formula 1 or 4-hydroxy-4′-isopropoxydiphenyl sulfone is used as the electron accepting compound, the irreversible polychromatic color having a large change in color density with respect to a change in heating temperature. It is particularly preferable because a temperature indicating material can be obtained. When such a temperature indicating material is used for controlling the heating state of a beverage placed in a metal can or a plastic container that can be heated and drunk, for example, the heating temperature can be easily controlled. .

  The color-forming layer constituting the irreversible multicolor thermochromic material of the present invention can contain a heat-fusible substance in order to improve its thermal response.

  Specifically, synthesis of paraffin wax, microcrystalline wax, polyethylene wax, carnauba wax and the like, and natural waxes, N-stearyl urea, benzyl-2-naphthyl ether, m-terphenyl, 4-benzylbiphenyl, 2, 2'-bis (4-methoxyphenoxy) diethyl ether, α, α'-diphenoxyxylene, bis (4-methoxyphenyl) ether, diphenyl adipate, dibenzyl oxalate, di (4-methylbenzyl ester) oxalate, di (oxalate) (4-chlorobenzyl) ester, dimethyl terephthalate, dibenzyl terephthalate, phenyl benzenesulfonate, bis (4-allyloxyphenyl) sulfone, 1,2-di (3-methylphenoxy) ethane, 1,2-di Phenoxyethane, 4- Known heat-fusible substances such as acetylacetophenone, acetoacetic anilides, fatty acid anilides, and amide derivatives are exemplified, but not limited thereto. These compounds can be used alone or in combination of two or more.

  In particular, when the amide derivative represented by the general formula 2 is contained in the color-forming layer as a thermoplastic, the color-forming start temperature of the high-temperature color-forming dye precursor is not changed, and the low-temperature color-forming dye precursor is not changed. This is preferable because the thermal responsiveness can be greatly improved.

In Formula 2, A represents an alkyl group or an alkylamino group, and the alkyl group or the alkylamino group is an alkenyl group, an allyl group, an alkoxy group, a halogen atom, a hydroxyl group, an acyl group, an acyloxy group, or an acylamino group. And the like. R ₁ and R ₂ may be the same or different and each represent a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkenyl group, an aralkyl group, or an allyl group.

  Specific examples of the compound represented by the general formula 2 include lauric amide, palmitic amide, stearic amide, behenic amide, erucic amide, N-palmityl palmitic amide, and N-stearyl stearamide. N-stearyl-12-hydroxystearic acid amide, N-oleyl-12-hydroxystearic acid amide, N-methylolstearic acid amide, N-methylolbehenic acid amide, methylenebisstearic acid amide, methylenebislauric acid amide, methylenebis (12-hydroxystearic acid amide), ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebisisostearic acid amide, ethylenebis (12-hydroxystearic acid amide), d Lenbisbehenic acid amide, hexamethylenebisstearic acid amide, hexamethylenebisbehenic acid amide, hexamethylenebis (12-hydroxystearic acid amide), butylene bisstearic acid amide, methylenebisoleic acid amide, ethylenebisoleic acid amide, ethylene bis Erucamide, hexamethylenebisoleamide, 1,3-xylylenebisstearic acid amide, N-butyl-N'-stearyl urea, N-phenyl-N'-stearyl urea, N, N'-distearyl urea However, the compounds represented by the general formula 2 according to the present invention are not limited thereto, and these compounds may be used alone or in combination of two or more as necessary. Can be used.

  The color-forming layer constituting the irreversible multicolor thermochromic material of the present invention is obtained by mixing each aqueous dispersion obtained by pulverizing each color-forming component, a resin, etc., coating on a support, and drying. Can be

  As the resin used for the color forming layer, various resins used in ordinary coating can be used.

  Specifically, starches, hydroxymethylcellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium alginate, polyvinylpyrrolidone, polyacrylamide, acrylamide / acrylate copolymer, acrylamide / acryl Acid ester / methacrylic acid terpolymer, alkali salt of polyacrylic acid, alkali salt of polymaleic acid, alkali salt of styrene / maleic anhydride copolymer, alkali salt of ethylene / maleic anhydride copolymer, isobutylene / Water-soluble resin such as alkali salt of maleic anhydride copolymer, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene Polymer, acrylonitrile / butadiene / styrene terpolymer, polyvinyl acetate, vinyl acetate / acrylate copolymer, ethylene / vinyl acetate copolymer, polyacrylate, styrene / acrylate copolymer, Examples thereof include water-dispersible resins such as polyurethane, but are not limited thereto.

  In the coloring layer, as a pigment, diatomaceous earth, talc, kaolin, calcined kaolin, heavy calcium carbonate, precipitated calcium carbonate, magnesium carbonate, zinc oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, titanium dioxide, barium sulfate, Inorganic pigments such as zinc sulfate, amorphous silica, amorphous calcium silicate and colloidal silica, and organic pigments such as melamine resin filler, urea-formalin resin filler, polyethylene powder and nylon powder can be used.

Various auxiliaries can be added to the coloring layer as needed. As an auxiliary agent, a metal salt of a higher fatty acid such as zinc stearate and calcium stearate, a lubricant such as paraffin, polyethylene wax, polyethylene oxide and caster wax; Agents, antioxidants such as hindered phenols and hindered amines, and surfactants including high molecular weight anionic and nonionic surfactants as dispersing / wetting agents, as well as fluorescent dyes, defoamers, etc. However, the present invention is not limited to these. Dry coating amount of the color layer is preferably ^{1~20g / m 2, 2~10g / m} 2 is more preferable.

  As the support used in the present invention, paper is mainly used, but in addition to paper, various woven fabrics, nonwoven fabrics, synthetic resin films, synthetic resin laminated paper, synthetic paper, metal foil, vapor-deposited sheets, or laminating these, etc. The composite sheet combined with the above can be used arbitrarily according to the purpose.

The irreversible multicolor thermographic material of the present invention may have one or more undercoat layers composed of a single layer or a plurality of layers of pigments or resins between the support and the color forming layer, if necessary. If irreversible multicolor temperature indicating material in the present invention is provided with a undercoat layer, the coating amount of the undercoat layer is preferably ^{1~30g / m 2, 3~20g / m} 2 is more preferable.

  As the pigment for the undercoat layer, calcined kaolin is generally used. In addition, diatomaceous earth, talc, kaolin, heavy calcium carbonate, precipitated calcium carbonate, magnesium carbonate, zinc oxide, aluminum oxide, and hydroxide Inorganic pigments such as aluminum, magnesium hydroxide, titanium dioxide, barium sulfate, zinc sulfate, amorphous silica, amorphous calcium silicate, colloidal silica, melamine resin filler, urea-formalin resin filler, polyethylene powder, nylon powder, etc. Organic pigments can be used.

  As the resin of the undercoat layer, various water-soluble resins or water-dispersible resins used in ordinary coating can be used. For example, starches, hydroxymethylcellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium alginate, polyvinylpyrrolidone, polyacrylamide, acrylamide / acrylate copolymer, acrylamide / acrylate / Methacrylic acid terpolymer, alkali salt of polyacrylic acid, alkali salt of polymaleic acid, alkali salt of styrene / maleic anhydride copolymer, alkali salt of ethylene / maleic anhydride copolymer, isobutylene / maleic anhydride Water-soluble resin such as alkali salt of copolymer, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer Body, acrylonitrile / butadiene / styrene terpolymer, polyvinyl acetate, vinyl acetate / acrylate copolymer, ethylene / vinyl acetate copolymer, polyacrylate, styrene / acrylate copolymer, polyurethane And other water-dispersible resins.

The irreversible multicolor thermographic material of the present invention improves the image storability by providing a color developing layer and then further providing one or more protective layers mainly composed of a water-soluble resin or a water-dispersible resin thereon. be able to. Further, a resin that forms a film with an electron beam or ultraviolet light may be used. Dry coating amount of the protective layer is preferably ^{0.2~10g / m 2, 0.5~5g / m} 2 is more preferable.

  The water-soluble resin or water-dispersible resin of the protective layer is appropriately selected from conventionally known water-soluble polymers or water-dispersible resins. That is, examples of the water-soluble resin include polyvinyl alcohol, modified polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as hydroxyethylcellulose, methylcellulose, ethylcellulose and carboxymethylcellulose, polyvinylpyrrolidone, polyacrylamide, acrylamide / acrylic acid ester copolymer , Acrylamide / acrylic ester / methacrylic acid terpolymer, alkali salt of polyacrylic acid, alkali salt of polymaleic acid, alkali salt of styrene / maleic anhydride copolymer, alkali salt of ethylene / maleic anhydride copolymer And alkali salts of isobutylene / maleic anhydride copolymer, sodium alginate, gelatin, casein, and acid neutralized products of chitosan.

  Examples of the water-dispersible resin include styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, acrylonitrile / butadiene / styrene terpolymer, polyvinyl acetate, vinyl acetate / An acrylate copolymer, an ethylene / vinyl acetate copolymer, a polyacrylate, a styrene / acrylate copolymer, a polyurethane, or the like can be used.

  The protective layer can contain a pigment as needed. Specific examples of the pigment include diatomaceous earth, talc, kaolin, calcined kaolin, heavy calcium carbonate, precipitated calcium carbonate, magnesium carbonate, zinc oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, titanium dioxide, barium sulfate, and sulfuric acid. Inorganic pigments such as zinc, amorphous silica, amorphous calcium silicate and colloidal silica, and organic pigments such as melamine resin filler, urea-formalin resin filler, polyethylene powder and nylon powder can be used.

  Various assistants can be added to the protective layer as needed. Examples of the auxiliary include metal salts of higher fatty acids such as zinc stearate and calcium stearate, lubricants such as paraffin, polyethylene wax, polyethylene oxide, and caster wax, and benzophenone-based and benzotriazole-based ultraviolet absorbers for the purpose of improving light resistance. Agents, antioxidants such as hindered phenols and hindered amines, and surfactants including high molecular weight anionic and nonionic surfactants as dispersing / wetting agents, as well as fluorescent dyes, defoamers, etc. However, the present invention is not limited to these.

  Further, on the back surface of the support, an ink receiving layer having suitability for an ink jet printer and a back coat layer for the purpose of preventing blocking, curling, and charging can be provided.

  The irreversible multicolor temperature-indicating material of the present invention can be used as an adhesive label by providing an adhesive layer on a coloring surface or a back surface.

  The pressure-sensitive adhesive layer of the irreversible multicolor thermosensitive material of the present invention contains a pressure-sensitive adhesive as a main component, and examples of the pressure-sensitive adhesive include a synthetic rubber-based emulsion-based pressure-sensitive adhesive, an acrylic emulsion-based pressure-sensitive adhesive, and a natural rubber-based pressure-sensitive adhesive. Examples include a solvent-based pressure-sensitive adhesive, an acrylic solvent-based pressure-sensitive adhesive, and a silicon-based solvent-based pressure-sensitive adhesive, but are not limited thereto.

  As a method of providing an adhesive layer on the irreversible multicolor thermometer material of the present invention, a pressure-sensitive adhesive may be directly applied to the coloring surface of the thermometer material, or the back surface, and may be dried, or the adhesive may be applied on a release paper in advance and dried. And a temperature indicating material.

  The method for forming the coloring layer, the protective layer, the undercoat layer, or the adhesive layer is not particularly limited, and it can be formed according to a conventionally known technique. As a specific example, a coating liquid is applied by a method such as air knife coating, rod blade coating, bar coating, blade coating, gravure coating, curtain coating, and E-bar coating, and color is formed by drying. A layer, protective layer or undercoat layer can be formed. Further, each layer may be formed by various printing machines or the like using a method such as planographic printing, letterpress printing, flexographic printing, gravure printing, screen printing, and hot melt printing.

  Next, the present invention will be described in more detail with reference to examples. However, it is not limited to these. The parts and percentages shown below are all based on mass, and the coating amounts are absolutely dry coating amounts.

<Dispersion A>
200 g of 3- (N-ethyl-N-isoamyl) amino-benzo [a] fluoran was dispersed in a mixture of 200 g of a 10% aqueous solution of polyvinyl alcohol and 600 g of water, pulverized by a bead mill until the average particle diameter became 1 μm, and the dispersion was dispersed. A was obtained.

<Dispersion B>
50 g of 3-dibutylamino-6-methyl-7-anilinofluoran was dispersed in 850 g of a 2.5% aqueous polyvinyl alcohol solution, and pulverized by a bead mill until the average particle diameter became 1 μm to obtain a dispersion. This dispersion was transferred to a polymerization vessel, 40 g of methyl methacrylate and 10 g of ethylene glycol dimethacrylate were added, and the temperature was raised to 70 ° C. while stirring. 50 parts of a 1% aqueous potassium persulfate solution as a polymerization initiator was added thereto, and the mixture was reacted for 6 hours while stirring. Then, this was cooled to room temperature to obtain a dispersion B of dye precursor particles having a low-sensitivity color-developing layer on the surface.

<Dispersion C>
200 g of bis (3-allyl-4-hydroxyphenyl) sulfone was dispersed in a mixture of 200 g of a 10% aqueous solution of polyvinyl alcohol and 600 g of water, and pulverized by a bead mill until the average particle diameter became 1 μm to obtain a dispersion C.

<Dispersion D>
200 g of oxalic acid-di (p-methylbenzyl) was dispersed in a mixture of 200 g of a 10% aqueous solution of polyvinyl alcohol and 600 g of water, and pulverized with a bead mill until the average particle diameter became 1 μm to obtain a dispersion D.

<Dispersion E>
200 g of amorphous silica was dispersed in 800 g of a 0.2% aqueous solution of sodium polyacrylate and stirred for 10 minutes with a homomixer to obtain a dispersion E.

Preparation of Coloring Layer Coating Solution The above dispersions were mixed at the ratio shown below, water was added so that the coating solution concentration became a 17% aqueous solution, and the mixture was sufficiently stirred to prepare a coloring layer coating solution. .
Dispersion A 20 parts Dispersion B 100 parts Dispersion C 75 parts Dispersion D 75 parts Dispersion E 70 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 90 parts

Preparation of Irreversible Multicolor Thermometer Material On one side of a high-quality neutral paper having a basis weight of 50 g / m ² , the coating amount of the solid content of the color forming layer coating solution is 6 g / m ² , and after drying, An acrylic emulsion-type pressure-sensitive adhesive (Sebian A AST467 63%, manufactured by Daicel Chemical Industries, Ltd.) is applied to the surface opposite to the surface on which the color-forming layer is applied so that the solid content is 30 g / m ² , and then dried and irreversible. A multicolor temperature indicating material was obtained.

  In the preparation of the irreversible multicolor thermometer material of Example 1, an irreversible multicolor thermometer material was prepared in the same manner as in Example 1 except that an acrylic emulsion-type pressure-sensitive adhesive was applied to the same surface as the color-forming layer application surface. did.

<Dispersion F>
200 g of 3,3-bis (1-n-hexyl-2-methylindol-3-yl) phthalide was dispersed in a mixture of 200 g of a 10% aqueous polyvinyl alcohol solution and 600 g of water, and the average particle diameter was reduced to 1 μm with a bead mill. The mixture was pulverized to obtain a dispersion liquid F.

  An irreversible multicolor thermochromic material was produced in the same manner as in Example 1 except that 20 parts of the dispersion A was used in place of 20 parts of the dispersion A in the preparation of the coating solution for the color-forming layer of Example 1.

<Dispersion G>
200 g of 4,4′-bis [(4-methyl-3-phenoxycarbonylaminophenyl) ureido] diphenyl sulfone was dispersed in a mixture of 200 g of a 10% aqueous solution of polyvinyl alcohol and 600 g of water, and pulverized by a bead mill until the average particle diameter became 1 μm. Thus, a dispersion G was obtained.

  An irreversible multicolor thermochromic material was produced in the same manner as in Example 1 except that 75 parts of the dispersion C was used instead of 75 parts of the dispersion C in the preparation of the color-forming layer coating liquid of Example 1.

  In the preparation of the color forming layer coating solution of Example 1, the irreversible type was prepared in the same manner as in Example 1 except that 20 parts of the dispersion F was used instead of 20 parts of the dispersion A, and 75 parts of the dispersion G was used instead of 75 parts of the dispersion C. A multicolor thermometer was prepared.

<Dispersion H>
200 g of 4-hydroxy-4′-isopropoxydiphenyl sulfone was dispersed in a mixture of 200 g of a 10% aqueous solution of polyvinyl alcohol and 600 g of water, and pulverized by a bead mill until the average particle diameter became 1 μm to obtain a dispersion liquid H.

  An irreversible multicolor thermochromic material was produced in the same manner as in Example 1 except that 75 parts of the dispersion C was used instead of 75 parts of the dispersion C in the preparation of the coating solution for the color forming layer of Example 1.

  In the preparation of the color forming layer coating liquid of Example 1, the irreversible type was prepared in the same manner as in Example 1 except that 20 parts of the dispersion F was used instead of 20 parts of the dispersion A, and 75 parts of the dispersion H was used instead of 75 parts of the dispersion C. A multicolor thermometer was prepared.

<Dispersion I>
100 g of stearic acid amide was dispersed in a mixture of 100 g of a 10% aqueous solution of polyvinyl alcohol and 800 g of water, and pulverized by a bead mill until the average particle size became 5.0 μm, to obtain a dispersion liquid I.

In the preparation of the color-forming layer coating liquid of Example 1, the dispersion liquid I was added to the coating liquid, and the color-forming layer coating liquid was prepared by changing the mixing ratio of each dispersion as follows. In the same manner, an irreversible multicolor thermometer was prepared.
Dispersion A 20 parts Dispersion B 100 parts Dispersion C 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 90 parts

In the preparation of the color-forming layer coating solution of Example 1, the dispersion I was added to the coating solution, the dispersion F was used in place of the dispersion A, and the mixing ratio of each dispersion was changed as described below. An irreversible multicolor thermostat was prepared in the same manner as in Example 1, except that a layer coating solution was prepared.
Dispersion F 20 parts Dispersion B 100 parts Dispersion C 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% Completely saponified polyvinyl alcohol aqueous solution 90 parts

In the preparation of the color forming layer coating liquid of Example 1, the dispersion liquid I was added to the coating liquid, the dispersion liquid G was used in place of the dispersion liquid C, and the mixing ratio of each dispersion liquid was changed as follows to form a color. An irreversible multicolor thermostat was prepared in the same manner as in Example 1, except that a layer coating solution was prepared.
Dispersion A 20 parts Dispersion B 100 parts Dispersion G 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 90 parts

In the preparation of the color-forming layer coating liquid of Example 1, the dispersion liquid I was added to the coating liquid, the dispersion liquid F was used instead of the dispersion liquid A, and the dispersion liquid G was used instead of the dispersion liquid C. An irreversible multicolor thermochromic material was produced in the same manner as in Example 1, except that the mixing ratio of was changed as described below to produce a coloring layer coating solution.
Dispersion F 20 parts Dispersion B 100 parts Dispersion G 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% Completely saponified polyvinyl alcohol aqueous solution 90 parts

  In preparing the color forming layer coating liquid of Example 1, 20 parts of the dispersion A was used instead of 20 parts of the dispersion A, 75 parts of the dispersion G was used instead of 75 parts of the dispersion C, and 150 parts of the dispersion I was used instead of 75 parts of the dispersion D. Except for the above, an irreversible multicolor thermometer was prepared in the same manner as in Example 1.

In the preparation of the color-forming layer coating solution of Example 1, the dispersion I was added to the coating solution, the dispersion H was used in place of the dispersion C, and the mixing ratio of each dispersion was changed as described below. An irreversible multicolor thermostat was prepared in the same manner as in Example 1, except that a layer coating solution was prepared.
Dispersion A 20 parts Dispersion B 100 parts Dispersion H 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% Completely saponified polyvinyl alcohol aqueous solution 90 parts

In the preparation of the color forming layer coating liquid of Example 1, the dispersion liquid I was added to the coating liquid, the dispersion liquid F was used instead of the dispersion liquid A, and the dispersion liquid H was used instead of the dispersion liquid C. An irreversible multicolor thermochromic material was produced in the same manner as in Example 1, except that the mixing ratio of was changed as described below to produce a coloring layer coating solution.
Dispersion F 20 parts Dispersion B 100 parts Dispersion H 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% Completely saponified polyvinyl alcohol aqueous solution 90 parts

<Dispersion J>
50 g of 3- (N-ethyl-N-isoamyl) amino-benzo [a] fluoran is dispersed in 850 g of a 2.5% aqueous polyvinyl alcohol solution, and pulverized by a bead mill until the average particle diameter becomes 1 μm to obtain a dispersion. Was. This dispersion was transferred to a polymerization vessel, 25 g of ethyl methacrylate was added, and the temperature was raised to 70 ° C. while stirring. To this was added 25 g of a 1% aqueous solution of potassium persulfate as a polymerization initiator, and the mixture was reacted for 6 hours while stirring. Then, this was cooled to room temperature to obtain a dispersion J of a low-temperature coloring dye precursor having a thin highly-sensitive coloring control layer on the surface.

In the preparation of the coloring layer coating liquid of Example 1, the dispersion liquid J was used in place of the dispersion liquid A, and the mixing ratio of each dispersion liquid was changed as described below to prepare the coloring layer coating liquid. In the same manner as in Example 1, an irreversible multicolor thermometer was prepared.
Dispersion J 76 parts Dispersion B 100 parts Dispersion C 75 parts Dispersion D 75 parts Dispersion E 70 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 168 parts

<Dispersion K>
50 g of 3,3-bis (1-n-hexyl-2-methylindol-3-yl) phthalide was dispersed in 850 g of a 2.5% aqueous polyvinyl alcohol solution, and pulverized by a bead mill until the average particle diameter became 1 μm. A dispersion was obtained. This dispersion was transferred to a polymerization vessel, 25 g of ethyl methacrylate was added, and the temperature was raised to 70 ° C. while stirring. To this was added 25 g of a 1% aqueous solution of potassium persulfate as a polymerization initiator, and the mixture was reacted for 6 hours while stirring. Then, this was cooled to room temperature to obtain a dispersion K of a dye precursor for low-temperature coloring, which was provided with a thin highly-sensitive color-forming control layer on the surface.

In the preparation of the coloring layer coating liquid of Example 1, the dispersion liquid K was used in place of the dispersion liquid A, and the mixing ratio of each dispersion liquid was changed as described below to prepare the coloring layer coating liquid. In the same manner as in Example 1, an irreversible multicolor thermometer was prepared.
Dispersion K 76 parts Dispersion B 100 parts Dispersion C 75 parts Dispersion D 75 parts Dispersion E 70 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 168 parts

With respect to the preparation of the color forming layer coating solution of Example 1, color was formed by using dispersion J instead of dispersion A and dispersion G instead of dispersion C, and changing the mixing ratio of each dispersion as follows. An irreversible multicolor thermometer was prepared in the same manner as in Example 1 except that a layer coating solution was prepared.
Dispersion J 76 parts Dispersion B 100 parts Dispersion G 75 parts Dispersion D 75 parts Dispersion E 70 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 168 parts

With respect to the preparation of the color forming layer coating solution of Example 1, the color was formed by using the dispersion K instead of the dispersion A and the dispersion G instead of the dispersion C, and changing the mixing ratio of each dispersion as follows. An irreversible multicolor thermometer was prepared in the same manner as in Example 1 except that a layer coating solution was prepared.
Dispersion K 76 parts Dispersion B 100 parts Dispersion G 75 parts Dispersion D 75 parts Dispersion E 70 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 168 parts

With respect to the preparation of the color forming layer coating solution of Example 1, color was formed by using dispersion J instead of dispersion A and dispersion H instead of dispersion C, and changing the mixing ratio of each dispersion as follows. An irreversible multicolor thermometer was prepared in the same manner as in Example 1 except that a layer coating solution was prepared.
Dispersion J 76 parts Dispersion B 100 parts Dispersion H 75 parts Dispersion D 75 parts Dispersion E 70 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 168 parts

With respect to the preparation of the color forming layer coating solution of Example 1, the color was formed by using the dispersion K instead of the dispersion A and the dispersion H instead of the dispersion C, and changing the mixing ratio of each dispersion as follows. An irreversible multicolor thermometer was prepared in the same manner as in Example 1 except that a layer coating solution was prepared.
Dispersion K 76 parts Dispersion B 100 parts Dispersion H 75 parts Dispersion D 75 parts Dispersion E 70 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 168 parts

In the preparation of the color-forming layer coating solution of Example 1, the dispersion solution I was added to the coating solution, the dispersion solution J was used in place of the dispersion solution A, and the mixing ratio of each dispersion solution was changed as follows to form a color. An irreversible multicolor thermostat was prepared in the same manner as in Example 1, except that a layer coating solution was prepared.
Dispersion J 76 parts Dispersion B 100 parts Dispersion C 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 168 parts

In the preparation of the color forming layer coating liquid of Example 1, the dispersion liquid I was added to the coating liquid, the dispersion liquid K was used in place of the dispersion liquid A, and the mixing ratio of each dispersion liquid was changed as described below. An irreversible multicolor thermostat was prepared in the same manner as in Example 1, except that a layer coating solution was prepared.
Dispersion K 76 parts Dispersion B 100 parts Dispersion C 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 168 parts

In the preparation of the color forming layer coating liquid of Example 1, the dispersion liquid I was added to the coating liquid, the dispersion liquid J was used instead of the dispersion liquid A, and the dispersion liquid G was used instead of the dispersion liquid C. An irreversible multicolor thermochromic material was produced in the same manner as in Example 1, except that the mixing ratio of was changed as described below to produce a coloring layer coating solution.
Dispersion J 76 parts Dispersion B 100 parts Dispersion G 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% Completely saponified polyvinyl alcohol aqueous solution 168 parts

In the preparation of the color forming layer coating liquid of Example 1, the dispersion liquid I was added to the coating liquid, the dispersion liquid K was used instead of the dispersion liquid A, and the dispersion liquid G was used instead of the dispersion liquid C. An irreversible multicolor thermochromic material was produced in the same manner as in Example 1, except that the mixing ratio of was changed as described below to produce a coloring layer coating solution.
Dispersion K 76 parts Dispersion B 100 parts Dispersion G 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 168 parts

In the preparation of the color forming layer coating liquid of Example 1, the dispersion liquid I was added to the coating liquid, the dispersion liquid J was used instead of the dispersion liquid A, and the dispersion liquid H was used instead of the dispersion liquid C. An irreversible multicolor thermochromic material was produced in the same manner as in Example 1, except that the mixing ratio of was changed as described below to produce a coloring layer coating solution.
Dispersion J 76 parts Dispersion B 100 parts Dispersion H 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% Completely saponified polyvinyl alcohol aqueous solution 168 parts

In the preparation of the color-forming layer coating liquid of Example 1, the dispersion liquid I was added to the coating liquid, the dispersion liquid K was used instead of the dispersion liquid A, and the dispersion liquid H was used instead of the dispersion liquid C. An irreversible multicolor thermochromic material was produced in the same manner as in Example 1, except that the mixing ratio of was changed as described below to produce a coloring layer coating solution.
Dispersion K 76 parts Dispersion B 100 parts Dispersion H 75 parts Dispersion D 37.5 parts Dispersion E 70 parts Dispersion I 75 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 168 parts

(Comparative Example 1)
An irreversible thermoelectric material was prepared in the same manner as in Example 1 except that in the preparation of the color-forming layer coating liquid of Example 1, the mixing ratio of each dispersion was changed to prepare a color-forming layer coating liquid as described below. .
Dispersion F 45 parts Dispersion C 75 parts Dispersion D 75 parts Dispersion E 70 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 83 parts

(Comparative Example 2)
An irreversible thermoelectric material was prepared in the same manner as in Example 1 except that in the preparation of the color-forming layer coating liquid of Example 1, the mixing ratio of each dispersion was changed to prepare a color-forming layer coating liquid as described below. .
Dispersion B 180 parts Dispersion C 75 parts Dispersion D 75 parts Dispersion E 70 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 95 parts

<Dispersion L>
200 g of 3-dibutylamino-6-methyl-7-anilinofluoran was dispersed in a mixture of 200 g of a 10% aqueous solution of polyvinyl alcohol and 600 g of water, and pulverized by a bead mill until the average particle diameter became 1 μm to obtain a dispersion J. Was.

(Comparative Example 3)
In the preparation of the color forming layer coating liquid of Example 1, except that the dispersion liquid L was used in place of the dispersion liquid B and the mixing ratio of each dispersion liquid was changed as described below to prepare the color forming layer coating liquid. In the same manner as in Example 1, an irreversible multicolor thermochromic material was produced.
Dispersion A 20 parts Dispersion L 25 parts Dispersion C 75 parts Dispersion D 75 parts Dispersion E 70 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 83 parts

(Comparative Example 4)
In the preparation of the coloring layer coating liquid of Example 1, the dispersion F was used instead of the dispersion A, and the dispersion L was used instead of the dispersion B, and the mixing ratio of each dispersion was changed as follows. An irreversible multicolor thermochromic material was prepared in the same manner as in Example 1 except that a coating solution for the color-forming layer was prepared.
Dispersion F 20 parts Dispersion L 25 parts Dispersion C 75 parts Dispersion D 75 parts Dispersion E 70 parts 40% zinc stearate dispersion 15 parts 10% completely saponified polyvinyl alcohol aqueous solution 83 parts

  Examples 1 to 26 and Comparative Examples 1 to 4 were subjected to the following evaluation. The results are shown in Tables 1 and 2.

(1) Heating temperature responsiveness The obtained irreversible polychromatic thermochromic material was heated at a temperature of 50 ° C and a heating temperature suitable for drinking at 60 ° C and 70 ° C, and a heating temperature of 100 ° C which was too high for drinking. After storage for 7 days under the above conditions, the color density of the color-forming layer was measured with a Macbeth RD-918 reflection densitometer (using a magenta filter). Further, the color tone of the coloring layer was visually observed. The results are shown in Table 1.

(2) Heating time responsiveness After the obtained irreversible polychromatic thermochromic material was stored at 60 ° C. for 3 days and 7 days, the color density of the color forming layer was measured with a Macbeth RD-918 reflection densitometer (using a magenta filter). did. Further, the color tone of the coloring layer was visually observed. The results are shown in Table 2.

  As is clear from Table 1, in Examples 1 to 26, when the heating temperature was 50 ° C., the color was undeveloped, and when heated at 60 ° C. or 70 ° C., which is a suitable heating temperature for drinking, it became pale red and red. When heated at 100 ° C., which is too high for drinking, a difference in heating temperature can be confirmed by developing black, whereas in Comparative Examples 1, 3 and 4, the heating temperature is 60 ° C. No difference in color tone between the case of 100 ° C and 100 ° C. Further, in Comparative Example 2, when heated at 60 ° C. or 70 ° C., sufficient color development was not obtained, and the material did not function as a temperature indicating material in these heating temperature ranges. This is because, in the irreversible multicolor thermochromic material of the present invention, at least one or more of the dye precursors contained in the color-forming layer has a color-controlling layer obtained by addition polymerization of a vinyl monomer on the surface. It is due to existence in the.

  Examples 3, 5, 7, 9, 11, 14, 16, 18, 20, 22, 24, and 26 correspond to Examples 1, 4, 6, 8, 10, 13, 15, 17, 19, 21, respectively. The red color density when heated at 60 ° C. and 70 ° C. is higher than 23 and 25. This is because the coloring layer contains 3,3-bis (1-n-hexyl-2-methylindol-3-yl) phthalide as a dye precursor.

  In Examples 1 to 3, 8 to 9, 15 to 16, and 21 to 22, the heating temperature was 60 ° C or 70 ° C. In 14, 17 to 20, and 23 to 26, the coloring density when heated at 60 ° C. becomes pale red, and a difference is visually observed between when heated at 70 ° C. and when visually observed, and the coloring temperature is narrower. It can be seen that an irreversible multicolor thermochromic material that can be managed in a range is obtained. This is because the coloring layer contains a urea urethane compound represented by the general formula 1 or 4-hydroxy-4'-isopropoxydiphenyl sulfone as an electron accepting compound.

  In Examples 8, 9, 10, 11, 13, and 14, the red color density when heated at 60 ° C. and 70 ° C. was higher than in Examples 1, 3, 4, 5, 6, and 7, respectively. I have. This is due to the inclusion of the amide derivative represented by the general formula 2 in the coloring layer.

  In Examples 10 and 11, as compared with Examples 4 and 5, respectively, the difference in color density between the case where heating was performed at 60 ° C and the case where heating was performed at 70 ° C was larger, and the difference between the heating temperatures was clearer. You can see that it is. This is because the coloring layer contains a urea urethane compound represented by the general formula 1 as an electron accepting compound, and further contains an amide derivative represented by the general formula 2 in the coloring layer.

  In Examples 13 and 14, as compared with Examples 6 and 7, respectively, the color density difference between when heated at 60 ° C. and when heated at 70 ° C. was larger, and the difference between the heating temperatures was clearer. You can see that it is. This is because the coloring layer contains 4-hydroxy-4'-isopropoxydiphenyl sulfone as an electron accepting compound, and further contains the amide derivative represented by the general formula 2 in the coloring layer. .

  As can be seen from Table 2, in Examples 15 to 26, the difference in color tone or color density between after heating for 3 days and after heating for 7 days was larger than that in Examples 1 to 14, The time difference is more clearly shown. This is because the high-sensitivity color-forming control layer is provided thinly on the surface of the low-temperature color dye precursor in the color-forming layer.

  As is apparent from Tables 1 and 2, two or more kinds of electron-donating, usually colorless or light-colored dye precursors that develop colors different from each other are formed on the support, and the dye precursors are colored by reacting when heated. An irreversible polychromatic thermochromic material having a color-forming layer comprising at least one layer containing an electron-accepting compound to be formed, wherein at least one of the dye precursors is obtained by addition polymerization of a vinyl monomer. It can be seen that an irreversible multicolor thermoelectric material capable of simultaneously controlling the heating temperature and the heating time can be obtained by being present in the coloring layer in the form of particles having the layer on the surface. Further, at least two or more of the dye precursors present in the color-forming layer are present in the color-forming layer in the form of particles having a color-controlling layer obtained by addition polymerization of a vinyl monomer on the surface. It can be seen that an irreversible multicolor thermometer material can be obtained in which the heating time can be more easily controlled. Further, by containing 3,3-bis (1-n-hexyl-2-methylindol-3-yl) phthalide as a dye precursor in the color-forming layer, an irreversible multicolor thermometer having higher heat responsiveness can be obtained. It can be seen that the material is obtained. Further, by containing a urea urethane compound represented by the general formula 1 or 4-hydroxy-4′-isopropoxydiphenyl sulfone as the electron-accepting compound in the color-forming layer, the heating temperature can be controlled in a narrower range. It can be seen that an irreversible multicolor thermometer material can be obtained. Further, it can be seen that the thermal responsiveness of the low-temperature coloring dye precursor is improved by including the amide derivative represented by the general formula 2 in the coloring layer.

Claims (6)

  1. A support comprising, on a support, two or more kinds of electron-donating, usually colorless or pale-colored dye precursors that develop colors different from each other, and an electron-accepting compound that reacts when heated to form the dye precursors. In an irreversible multicolor thermochromic material having a color-forming layer composed of at least one layer, at least one of the dye precursors is colored in the form of particles having a color-controlling layer obtained by addition polymerization of a vinyl monomer on the surface. An irreversible multicolor thermoelectric material characterized by being present in a layer.   2. The color forming layer according to claim 1, wherein at least two or more of the dye precursors present in the color forming layer are present in the color forming layer in the form of particles having a color control layer obtained by addition polymerization of a vinyl monomer on the surface. The irreversible multicolor thermometer material described.   3. The irreversible polymorph according to claim 1, wherein the color-forming layer contains 3,3-bis (1-n-hexyl-2-methylindol-3-yl) phthalide as a dye precursor. 4. Color temperature material. The irreversible polychromatic thermoelectric material according to any one of claims 1 to 3, wherein the color-forming layer contains a urea urethane compound represented by the general formula 1 as an electron-accepting compound.

  The irreversible multicolor thermosensitive material according to any one of claims 1 to 3, wherein the color-forming layer contains 4-hydroxy-4'-isopropoxydiphenyl sulfone as an electron-accepting compound. The irreversible multicolor thermostat according to any one of claims 1 to 5, wherein the color-forming layer contains an amide derivative represented by the general formula (2).

(Wherein, A represents an alkyl group or an alkylamino group, and R ₁ and R ₂ may be the same or different substituents, and each represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, Represents an alkenyl group, an aralkyl group, or an allyl group.)