JP2003268347A - Temperature history display and manufacturing method thereof - Google Patents

Abstract

(57) [Problem] To provide a temperature history display body capable of reliably and irreversibly displaying a temperature history over a predetermined temperature or more with a simple structure. I have. According to the present invention, when exposed to a temperature exceeding a predetermined temperature, a thermosensitive substance melts to cause an irreversible change in a thermosensitive layer on which information is recorded, and a temperature history can be displayed. The present invention relates to a temperature history table and a method for manufacturing the same.
That is, the present invention provides, on a support, a heat-sensitive layer containing a dye precursor and a developer for coloring the dye precursor, a penetrating layer, and a temperature-sensitive layer containing a temperature-sensitive substance having a melting point at a specific temperature. The present invention relates to a temperature history display body formed and a method of manufacturing the same.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a temperature history display using a heat sensitive recording method capable of displaying a temperature history due to an irreversible change when exposed to a predetermined temperature, and its manufacture. It is about the method.

[0002]

2. Description of the Related Art With the development of freezing technology and refrigeration technology, many cold-preserved foods have been able to maintain their quality and safety for a long period of time. Further, with the development and popularization of cryogenic transportation technology, various kinds of cryopreserved foods have been commercialized.

In recent years, the safety of food has become a more serious problem. The number of people affected by biological factors is about 10,000 each year, and the number of people is increasing year by year despite improvement in food handling. It is considered that this factor is due to an increase in the number of people who have weak resistance to bacteria, that is, due to excessive sterilization or the like, a decrease in immunity to bacteria, or a social tendency not to use additives. Accidents due to bacteria are closely related to the number of bacteria, and generally, if it is 10 ⁵ or less per 1 g of food,
It is believed that healthy people do not develop the disease. Bacterial division requires three conditions: proper temperature, water and nutrients. Absence of any one of these will prevent division. Therefore, in order to suppress the division of bacteria and suppress the number of bacteria, methods such as low temperature (generally, bacteria do not divide at 3 ° C or lower) and salt drying have been adopted.

As a method for suppressing bacterial division that does not affect the taste of food and does not require added chemicals, a method of low-temperature storage has been particularly attracting attention. The greatest challenge of this method is to maintain the specified constant temperature. For example, if it is kept at a storage temperature of 3 ° C and the temperature changes to 10 ° C above this temperature, the number of bacteria in E. coli doubles in 2 hours and the water content in the food expands. By doing so, a gap is created between the foods, and the nutrients of the foods are pushed out to the food surface by the capillary phenomenon. Next, when the temperature is lowered, some of the water leaked to the surface is again drawn into the food, so that bacterial contamination spreads to the inside of the food. In addition, when bacteria also change from a low temperature state to an appropriate temperature, a reaction occurs to accelerate the division rate. That is, it is better not to raise or lower the temperature for food preservation.

Looking at the distribution of foods, it is not difficult to maintain the temperature at 3 ° C. in a food factory.
However, once the food leaves the factory and is in the transportation stage, maintaining this temperature becomes much more difficult. Even in a truck equipped with a refrigeration system, it is difficult to keep the temperature constant under direct sunlight, and the temperature varies. Also, it is not easy to always keep the temperature below 3 ° C in the state of being sold at supermarkets, convenience stores and other retail stores.

At present, it is not possible for the consumer to know what temperature history the food has undergone before the consumer consumes the food. Various efforts have been made to know the temperature history of food, and one of them is the development of a temperature history display. For example, in Japanese Patent Laid-Open No. 10-287863, a temperature history display body that irreversibly develops color by reaction of a plurality of substances at a predetermined temperature is provided with a color former, a thermometer layer, and a developer layer. The invention of a history display is disclosed. In this invention, the color developer layer and the developer layer are separated by a thermometric agent layer, and when the temperature exceeds a predetermined temperature, the thermometric agent is dissolved and the color former layer and the developer layer come into contact to develop color,
Since this color development reaction occurs irreversibly, it is possible to know whether or not the temperature is equal to or higher than a predetermined temperature by the color development of the temperature history display body. This method is irreversible and effective, but it requires the use of a color former and a color developer, which not only complicates the structure of the temperature history indicator but also increases the cost. Therefore, it is not a practical method. Also, in other temperature history display bodies, temperature-sensitive colorants and color-developing agents are used in all of them, and the current situation is that they have not come into practical use.

On the other hand, in recent years, it has become more and more common to print the date of manufacture of food, the expiration date of food, etc. on a thermal recording paper and attach it to the product. According to this method, it is possible to print necessary items at the time of production according to the type of food and the date of production, and it has been applied to many foods. But,
Such printed matter shows the situation at the time of manufacture, and could not show the temperature control during the distribution and storage of the product.

[0008]

SUMMARY OF THE INVENTION According to the present invention, when exposed to a temperature exceeding the control temperature for a predetermined time or longer, the thermosensitive layer undergoes an irreversible change, making the information recorded on the thermosensitive layer unreadable. It is an object to provide a temperature history display body. Another object of the present invention is to provide a temperature history display which is easy to produce industrially.

[0009]

DISCLOSURE OF THE INVENTION The present invention provides a heat-sensitive layer containing a dye precursor and a developer for developing the color of the dye precursor, a permeation layer, and a temperature-sensitive layer containing a temperature-sensitive substance having a melting point at a specific temperature. The present invention relates to a temperature history display body characterized by being sequentially formed. More specifically, the present invention relates to a temperature history display body characterized in that when the environmental temperature of the temperature history display body exceeds the melting point of the temperature sensitive material, the temperature sensitive material causes an irreversible change in the heat sensitive layer. In the temperature history display of the present invention, a barrier layer may be further formed on the temperature sensitive layer, if necessary. Further, the present invention is to produce an intermediate product in which a heat-sensitive layer and a permeation layer are sequentially formed on a support, and to form the temperature-sensitive layer or the temperature-sensitive layer and the barrier layer at the time of attaching the intermediate product to an object. The present invention relates to a method for manufacturing a temperature history display body. A preferred method for producing a temperature history display of the present invention is characterized by forming a temperature-sensitive layer or a temperature-sensitive layer and a barrier layer after performing heat-sensitive recording on the above-mentioned intermediate product.

Next, an embodiment of the present invention will be described with reference to the drawings. FIG. 1 shows the structure of the laminated body of the temperature history display body of the present invention. This temperature history display has a thermosensitive layer (2), a permeation layer (3) and a temperature sensitive layer (4) formed on a support (1). The temperature-sensitive layer (4) is a layer containing a temperature-sensitive substance having a specific melting point, the permeation layer (3) is a layer into which the melted temperature-sensitive substance permeates, and the heat-sensitive layer (2) is a dye precursor and a main component. It is a layer containing a color developing agent that develops a dye precursor. FIG. 2 shows a temperature history display medium in which a barrier layer (5) is formed on the temperature history display body described above. FIG. 3 shows a temperature history display of the present invention in the case where the barrier layer (5) and the support (1) have an adhesive layer (6) which can be attached. In the temperature history display of the present invention, when the environmental temperature becomes higher than a predetermined temperature, the temperature-sensitive substance penetrates the permeation layer (3) and reaches the heat-sensitive layer (2), causing an irreversible change in the heat-sensitive layer. At the very least, the information recorded in the thermosensitive layer cannot be read. As an irreversible change of the heat-sensitive layer to make the information recorded on the heat-sensitive layer unreadable, it is possible for human or machine to read the character information and graphic information (including bar code information) recorded on the heat-sensitive layer. There is no particular limitation as long as it can be changed to an impossible state. For example, a melted temperature-sensitive substance disperses or decolorizes a dye that is coloring to display information recorded in the heat-sensitive layer. A method of destroying the recorded information by such as is simple and preferable.

Next, details of the components of the present invention will be described. The support used in the present invention is not particularly limited, and can be selected and used as needed. For example,
Paper, various non-woven fabrics, woven fabrics, plastic films such as polyethylene terephthalate and polypropylene, laminated paper laminated with synthetic resins such as polyethylene and polypropylene, synthetic paper, metal foil such as aluminum, glass, etc., or composite sheets combining these It can be optionally used depending on the purpose. These may be opaque, transparent, or translucent, and the background may appear white or other specific color, or a white pigment or colored dye / pigment may be contained in the support to improve smoothness, It may be applied to. In addition, a conductive layer for improving runnability in a printing machine may be provided in advance on the back surface of the support, or a functional layer such as a magnetic recording layer or an inkjet recording layer may be applied.

The heat-sensitive layer according to the present invention comprises a dye precursor, a color developer that develops the color of the dye precursor, and conventionally known additives such as a binder, a sensitizer, a pigment and a surfactant. The coating liquid containing the above is applied onto the support, and if necessary, an intermediate layer between the support and the heat-sensitive layer or a protective layer is applied on the heat-sensitive layer. In the present invention, when an intermediate layer or a protective layer is formed on the heat sensitive layer, the intermediate layer and the protective layer are collectively referred to as a heat sensitive layer. In the present invention, as a material in the combination of the dye precursor and the color developer, the dye precursor is not limited to hues such as black, red, blue and green, and for optical reading having absorption in the near infrared region. The dye precursors of are also used. Specifically, those listed below are used.

As the black color-developing dye, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-7- (2-chloroanilino) fluorane, 3
-Diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-xylidinofluorane, 3-diethylamino-7- (2-chloroanilino) fluorane, 3-diethylamino-7- (2 −
Carbomethoxy-phenylamino) fluorane, 3-
(N-cyclohexyl-N-methyl) amino-6-methyl-7-anilinofluorane, 3- (N-cyclopentyl-N-ethyl) amino-6-methyl-7-phenylaminofluorane, 3- (N -Isoamyl-N-ethyl)
Amino-6-methyl-7-anilinofluorane, 3-
(N-ethyl-p-toluidino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7- (p-toluidino) fluorane, 3- (N -Methyl-N-tetrahydrofurfuryl)
Amino-6-methyl-7-phenylaminofluorane,
3- (N-ethyl-N-tetrahydrofurfuryl) amino-6-methyl-7-phenylaminofluorane, 3-
Pyrrolidino-6-methyl-7-phenylaminofluorane, 3-pyrrolidino-6-methyl-7-p-butylphenylaminofluorane, 3-piperidino-6-methyl-
Black coloring dyes such as 7-phenylaminofluorane and 3-dipentylamino-6-methyl-7-anilinofluorane.

As the red color-forming dye, 3,3-bis (1
-N-butyl-2-methylindol-3-yl) phthalide, 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-methylindol-3-yl) phthalide, 3,3-bis (2methylindol-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-dibenzylaminofluorane, 3-
Diethylamino-6-methylfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6-methyl-7-chloro-8-benzylfluorane, 3-diethylamino-6,7-dimethylfluorane, 3-diethylamino-6,8-dimethylfluorane, 3-diethylamino-7-methylfluorane, 3-
Diethylamino-7-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylethoxyfluorane, 3-diethylamino-7- (N-acetyl-N-methyl) aminofluorane, 3- Diethylamino-7-p-methylphenylfluorane, 3-diethylamino-7,8-benzofluorane, 3-diethylaminobenzo [a] fluorane, 3-
Diethylaminobenzo [c] fluorane, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-chlorofluorane, 3- (N-ethyl-N-isoamyl) amino-7,8-benzofluorane , 3- (N-ethyl-
N-isoamyl) amino-7-methylfluorane, 3-
(N-Ethyl-N-isoamyl) amino-benzo [a]
Fluorane, 3- (N-ethyl-Nn-octyl) amino-6-methyl-7-chlorofluorane, 3- (N-
Ethyl-N-n-octyl) amino-7-methylfluorane, 3- (N-ethyl-N-n-octyl) amino-
7-chlorofluorane, 3- (N-ethyl-Nn-octyl) amino-7,8-benzofluorane, 3- (N
-Ethyl-N-4-methylphenyl) amino-7-methylfluorane, 3- (N-ethyl-N-4-methylphenyl) amino-7,8-benzofluorane, 3- (N-
Ethyl-N-ethoxyethyl) amino-7-chlorofluorane, 3- (N-ethyl-N-ethoxyethyl) amino-7,8-benzofluorane, 3-di-n-butylamino-6-methyl- 7-chlorofluorane, 3-di-n
-Butylamino-6-methyl-7-bromofluorane,
3-di-n-butylamino-7-methylfluorane, 3
-Di-n-butylamino-7-chlorofluorane, 3-
Di-n-butylamino-7,8-benzofluorane, 3
-Diallylamino-7,8-benzofluorane, 3-diallylamino-7-chlorofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-pyrrolidylamino-7-methylfluorane, 3,6- Red coloring dyes such as bis (diethylaminofluorane) -γ- (4'-nitro) anilinolactam.

Examples of blue-coloring dyes 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-methylindole-
3-yl) -3- (2-ethoxy-4-methylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-)
Methylindole-3-yl) -3- (2-ethoxy-
4-ethylaminophenyl) -4-azaphthalide, 3-
(1-Ethyl-2-methylindol-3-yl) -3
-(2-Ethoxy-4-dimethylaminophenyl) -4
-Azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindo) -Lul-3-yl) -3- (2-ethoxy-4-dipropylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindole-3
-Yl) -3- (2-ethoxy-4-dibutylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-)
Methylindole-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-methylindol-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-methylindole-
3-yl) -3- (2-ethoxy-4-pyrrolidylaminophenyl) -4-azaphthalide, 3- (1-ethyl-
2-Methylindol-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-methylindolyl-3-yl) -3- (2-bromo-4-diethylaminophenyl) -4-azaphthalide, 3- (1
-Ethyl-2-methylindolyl-3-yl) -3-
(3-Bromo-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethyl-4-diethylaminophenyl) -4-azaphthalide , 3- (1-ethyl-2)
-Methylindole-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-methylindol-3-yl) -3- (2-nitro-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methyl) Indole-3-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)
-Methylindole-3-yl) -3- (2-methylethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindole-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-chloroindol-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-ethylindo) -Lul-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-propylindole-3
-Yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-)
Methoxyindole-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide,
3- (1-Ethyl-2-ethoxyindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-phenylindole- 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-methylindole-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-methyl) Indole-3-yl) -3- (2-
Ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-4-methylamino-2-methylindol-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-methylindole-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-methylindo) -Le-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-methylindo) -Ru-3-yl) -3- (2-
Ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-butyl-2-indole-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -7-azaphthalide, 3- ( 1-Pentyl-2-methylindole-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-methylindo-) Ru-3-yl) -3- (2-
Ethoxy-4-diethylaminophenyl) -4,7-diazaphthalide, 3- (1-nonyl-2-methylindo-)
L-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-diethylaminophenyl) -7-azaphthalide, 3- (1-heptyl-2-methylindolyl- 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, 3,3-bis (p-dimethylaminophenyl)
A blue-coloring dye such as -6-dimethylaminophthalide.

As the green color-forming dye, 3-dimethylamino-6-chloro-7-dibenzylaminofluorane, 3
-Dimethylamino-6-methyl-7-n-octylaminofluorane, 3-dimethylamino-7-dibenzylaminofluorane, 3-dimethylamino-7-n-octylaminofluorane, 3-diethylamino-6- Methyl-7-benzylamino-fluorane, 3-diethylamino-6-methyl-7-dibenzylaminofluorane, 3
-Diethylamino-6-methyl-7-n-octylaminofluorane, 3-diethylamino-6-methyl-7-
(N-cyclohexyl-N-benzylamino) fluorane, 3-diethylamino-6-methyl-7- (2-chloroanilino) fluorane, 3-diethylamino-6-methyl-7- (2-trifluoromethylanilino) fluorane, 3-diethylamino-6-methyl-7- (3-trifluoromethylanilino) fluorane, 3-diethylamino-6-methyl-7- (2-ethoxyanilino) fluorane, 3-diethylamino-6-methyl-7- (4
-Ethoxyanilino) fluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-diethylamino-6-chloro-7- (2-chloroanilino) fluorane, 3-diethylamino-6-chloro-7-di Benzylaminofluorane, 3-diethylamino-6-ethylethoxy-7-anilinofluorane, 3-diethylamino-7-anilinofluorane, 3-diethylamino-
7-methylanilinofluorane, 3-diethylamino-
7-dibenzylaminofluorane, 3-diethylamino-7-n-octylaminofluorane, 3-diethylamino-7-p-chloroanilinofluorane, 3-diethylamino-7-p-methylphenylanilinofluorane, 3-diethylamino-7- (N-cyclohexyl-
N-benzylamino) fluorane, 3-diethylamino-7- (2-chloroanilino) fluorane, 3-diethylamino-7- (3-trifluoroanilino) fluorane, 3-diethylamino-7- (2-trifluoromethylanilino) ) Fluoran, 3-diethylamino-7-
(2-Ethoxyanilino) fluorane, 3-diethylamino-7- (4-ethoxyanilino) fluorane, 3-
Diethylamino-7- (2-chlorobenzylanilino)
Fluoran, 3- (N-ethyl-Nn-propyl) amino-6-chloro-7-dibenzylaminofluorane,
3- (N-ethyl-Nn-propyl) amino-7-dibenzylaminofluorane, 3- (N-ethyl-Nn)
-Hexyl) amino-7-anilinofluorane, 3-
(N-ethyl-N-4-methylphenyl) amino-6-
Methyl-7-dibenzylaminofluorane, 3- (N-
Ethyl-N-4-methylphenyl) amino-6-methyl-7- (N-methyl-N-benzyl) aminofluorane, 3- (N-ethyl-N-4-methylphenyl) amino-7- (N -Methyl-N-phenyl) aminofluorane, 3- (N-ethyl-N-4-methylphenyl) amino-7-dibenzylaminofluorane, 3-dibutylamino-6-chloro-7- (2-chloroanilino ) Fluoran, 3-dibutylamino-6-methyl-7- (2-chloroanilino) fluorane, 3-dibutylamino-6-
Methyl-7- (2-fluoroanilino) fluorane, 3
-Dibutylamino-7- (2-fluoroanilino) fluorane, 3-dibutylamino-7- (2-chloroanilino) fluorane, 3-dibutylamino-7- (2-chlorobenzylanilino) fluorane, 3- (N -Methyl-
Nn-hexyl) amino-7-anilinofluorane,
3- (N-propyl-Nn-hexyl) amino-7-
Anilinofluorane, 3- (N-ethoxy-Nn-hexyl) amino-7-anilinofluorane, 3- (N-
n-pentyl-N-allyl) amino-6-methyl-7-
Anilinofluorane, 3- (N-n-pentyl-N-allyl) amino-7-anilinofluorane, 3- [p-
(P-anilinoanilino) anilino] -6-methyl-7
-Chlorofluorane, 3-anilino-7-dibenzylaminofluorane, 3-anilino-6-methyl-7-dibenzylaminofluorane, 3-pyrrolidino-7-dibenzylaminofluorane, 3-pyrrolidino- ( 7-cyclohexylanilino) fluorane, 3-dibenzylamino-6-methyl-7-dibenzylaminofluorane, 3-
Dibenzylamino-7-dibenzylaminofluorane,
3-dibenzylamino-7- (2-chloroanilino) fluorane, 3,3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide, 3,6-bis (dimethylamino) fluorene-9-spiro- 3'-
Green color-forming dyes such as (6′-dimethylamino) phthalide.

As the dye having absorption in the near infrared region,
3,3-bis [1- (4-methoxyphenyl) -1-
(4-Dimethylaminophenyl) ethylene-2-yl]
-4,5,6,7-Tetrachlorophthalide, 3,3-bis [1- (4-methoxyphenyl) -1- (4-pyrrolidinophenyl) ethylene-2-yl] -4,5,6 , 7
-Tetrachlorophthalide, 3,3-bis [1,1-bis (4-pyrrolidinophenyl) ethylene-2-yl]-
4,5,6,7-tetrabromophthalide, 3- [1,1
-Bis (p-diethylaminophenyl) ethylene-2-
Il] -6-dimethylaminophthalide, 3,6-bis (dimethylamino) fluorene-9-spiro-3′-
(6'-Dimethylamino) phthalide, 3- [p- (p-
Dimethylaminoanilino) anilino] -6-methylfluorane, 3- [p- (p-dimethylaminoanilino) anilino] -6-methyl-7-chlorofluorane, 3-
(Pn-Butylaminoanilino) -6-methyl-7-
Chlorofluorane, 3- [p- (p-anilinoanilino) anilino] -6-methyl-7-chlorofluorane,
3-p- (p-chloroanilino) anilino-6-methyl-7-chlorofluorane, 3- (Np-tolyl-N-
Ethylamino) -6,8,8-trimethyl-9-ethyl-8,9-dihydro- (3,2, e) pyridfluorane, 3-di (n-butyl) amino-6,8,8-trimethyl-8. , 9-Dihydro- (3,2, e) pyridfluorane, 3'-phenyl-7-N-diethylamino-2,
Absorption in the near infrared region of 2'-spirodi- (2H-1-benzopyran), bis (p-dimethylaminostyryl) -p-trisulfonylmethane, 3,7-bis (dimethylamino) -10-benzoylphenothiazine, etc. And a dye having These dye precursors can be used alone or in combination of two or more as required.

The color developer that develops the dye precursor constituting the heat-sensitive layer of the present invention is typically represented by a pressure-sensitive recording material or an electron-accepting compound used in the heat-sensitive recording material, but is not particularly limited. There is no such thing. For example, clay substances, phenol derivatives, aromatic carboxylic acids and their derivatives,
Urea derivatives such as N, N′-diarylthiourea and N-sulfonylurea, and polyvalent metal salts thereof can be used. As a concrete example, acid clay, activated clay,
Clay substances such as zeolite, bentonite, kaolin, p
-Phenylphenol, p-hydroxyacetophenone, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, 3-phenylsulfonyl- 4-hydroxydiphenyl sulfone, 4-hydroxy-4'-benzenesulfonyloxydiphenyl sulfone, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-Hydroxyphenyl) hexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) cyclododecane, 2,
2-bis (4-hydroxyphenyl) propane, 2,2
-Bis (4-hydroxyphenyl) hexane, 2,2-
Bis (4-hydroxyphenyl) octane, 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] benzene , 1,4-di- [2- (4-hydroxyphenyl) -2-propyl] benzene, 4,4'-dihydroxydiphenyl ether, N- (2-hydroxyphenyl) benzenesulfonamide, N- (2-hydroxyphenyl) ) -P-toluenesulfonamide, N- (4
-Hydroxyphenyl) benzenesulfonamide, N-
(4-hydroxyphenyl) -p-toluenesulfonamide, N- (p-toluenesulfonyl) -N '-(3-
p-toluenesulfonyloxyphenyl) urea, 4,
4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 3,3'-dichloro-
4,4'-dihydroxydiphenyl sulfone, 3,3 '
-Diallyl-4,4'-dihydroxydiphenyl sulfone, 3,3'-dichloro-4,4'-dihydroxydiphenyl sulfide, methyl 2,2-bis (4-hydroxyphenyl) acetate, 2,2-bis (4- Hydroxyphenyl) butyl acetate, 4,4'-thiobis (2-t-butyl-5-methylphenol), benzyl p-hydroxybenzoate, chlorobenzyl p-hydroxybenzoate, 4
-Dimethyl hydroxyphthalate, benzyl gallate, stearyl gallate, salicylanilide, 5-chlorosalicylanilide, novolac phenol resin, modified terpene phenol resin, 3,5-di-t-butylsalicylic acid, 3,5-di-t -Nonylsalicylic acid, 3,5-didodecylsalicylic acid, 3-methyl-5-t-dodecylsalicylic acid, 5-cyclohexylsalicylic acid, 3,5-bis (α, α-dimethylbenzyl) salicylic acid, 3-methyl-5- ( α-methylbenzyl) salicylic acid, 4-n-
Octyloxycarbonylamino salicylic acid, 4- {2
Examples thereof include-(4-methoxyphenoxy) ethoxy} salicylic acid and their metal salts such as zinc, nickel, aluminum and calcium. However, the color developer according to the present invention is not limited to these. If necessary, two or more kinds can be used in combination.

The use ratio of the dye precursor and the developer is appropriately determined depending on the kind and combination thereof, and 100 to 700 parts by mass of the developer with respect to 100 parts by mass of the total amount of the dye precursor, It is preferably used in a proportion of 150 to 400 parts by mass. The sensitizer is preferably a compound having a melting point of 60 ° C to 200 ° C, and examples of such a compound include waxes such as N-hydroxymethylstearic acid amide, behenic acid amide, stearic acid amide and palmitic acid amide, 2- Naphthol derivatives such as benzyloxynaphthalene, p-benzylbiphenyl, 4-allyloxybiphenyl, biphenyl derivatives such as m-terphenyl, 1,2-bis (3-methylphenoxy) ethane,
Polyether compounds such as 2,2′-bis (4-methoxyphenoxy) diethyl ether and bis (4-methoxyphenyl) ether; carbonic acid such as diphenyl carbonate, dibenzyl oxalate and bis (p-methylbenzyl) oxalate. Examples thereof include oxalic acid diester derivatives, and these sensitizers are usually dispersed in an aqueous dispersion medium at an average particle diameter of 0.1 to 5 μm, preferably 0.1 to 2 μm, and used in combination of 1 or 2 or more. Can be used.

The binder used in the heat-sensitive layer according to the present invention is not particularly limited, but specifically, starches, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol. , Polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, sodium polyacrylate, polyethylene terephthalate, polybutylene terephthalate, chlorinated polyether, allyl resin, furan resin, ketone resin, oxybenzoyl polyester, polyacetal , Polyetheretherketone, polyethersulfone, polyimide, polyamide, polyamideimide, polyaminobismaleimide, polymethylpen , Polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfone, polysulfone, polyarylate, polyallyl sulfone, polybutadiene, polycarbonate, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyurethane, phenol resin, urea resin, Melamine resin, melamine formalin resin, benzoguanamine resin, bismaleimide triazine resin, alkyd resin, amino resin, epoxy resin,
Unsaturated polyester resin, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, ethylene / vinyl acetate copolymer, acrylic acid amide / acrylic acid ester copolymer, acrylic acid amide / Acrylic acid ester / methacrylic acid terpolymer, alkali salt of styrene / maleic anhydride copolymer, alkali salt or ammonium salt of ethylene / maleic anhydride copolymer, and other various polyolefin resins are considered.

The pigment used in the heat-sensitive layer according to the present invention may be an inorganic or organic pigment, but is not particularly limited. Specifically, diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide,
Urea-formalin resin may be used, and these may be used alone or in combination of two or more kinds. In addition, higher fatty acid metal salts such as zinc stearate and calcium stearate, waxes such as paraffin, oxidized paraffin, polyethylene, oxidized polyethylene, stearic acid amide and castor wax, and surfactants such as sodium dioctylsulfosuccinate,
Also, a fluorescent dye or the like can be contained.

Further, an antioxidant and an ultraviolet absorber may be added for the purpose of improving light resistance. Examples of antioxidants include, but are not limited to, hindered amine-based antioxidants, hindered phenol-based antioxidants, sulfide-based antioxidants, and the like. Further, examples of the ultraviolet absorber, organic UV absorbers such as benzotriazole-based UV absorbers, salicylic acid-based UV absorbers, benzophenone-based UV absorbers, and inorganic UV-rays such as zinc oxide, titanium oxide, and cerium oxide. Examples of the absorbent include, but are not limited to.

The material constituting the heat-sensitive layer of the present invention is obtained by mixing each dispersion obtained by finely pulverizing a color-forming component with a binder, coating on a support and drying to obtain a heat-sensitive recording layer. You can The layer structure of the heat-sensitive layer may be a single layer or multiple layers. The method for forming the heat-sensitive layer on the support is not particularly limited, and it can be formed by a conventional method. For example, coating devices such as an air knife coater, various blade coaters, various bar coaters, various curtain coaters, and various printing methods such as planographic printing, letterpress printing, intaglio printing, flexo, gravure, and screen can be used.

The permeation layer according to the present invention has a role of permeating the melted temperature-sensitive substance to reach the heat-sensitive layer. The permeation layer is mainly composed of a pigment and a binder, to which additives such as a curing agent are added. By controlling the type and particle size of the pigment used in the permeation layer, the type of binder, the ratio of pigment to binder, and the thickness of the coating layer, it is possible to control the time required for the temperature-sensitive substance to reach the heat-sensitive layer. Is preferred. The pigment used in the permeation layer is not particularly limited, but those listed as the pigments used in the heat-sensitive layer can be used. Further, the binder used in the present permeation layer is not particularly limited, but those listed as the binder used in the heat-sensitive layer can be used. Further, the method for forming the permeation layer is not particularly limited, but the coating devices listed in the method for forming the heat-sensitive layer can be used.

The temperature-sensitive layer according to the present invention has a melting point in a specific temperature range, preferably has a sharp melting point in a specific temperature range, and when melted, passes through the permeation layer and is irreversible to the heat-sensitive layer. It is mainly composed of temperature-sensitive substances that change.
The temperature-sensitive substance may consist of a specific compound alone or a mixture of a plurality of compounds. Further, an additive or the like can be added to the temperature-sensitive layer for the purpose of imparting another characteristic.

The temperature-sensitive substance used in the temperature-sensitive layer of the present invention is a compound or polymer compound having a melting point at a specific temperature, and causes an irreversible change in the heat-sensitive layer. The range of the melting point of the temperature-sensitive substance is the center value ± 1.5 ° C.
The following is preferable, and more preferably ± 1.0 ° C. or less. However, from the viewpoint of sensing the temperature, a material having a relatively narrow melting point range is preferable, but a substance capable of permeating the permeation layer and changing the heat-sensitive layer when the temperature exceeds a predetermined temperature may be used, and not all of them are required. It does not mean that the temperature-sensitive substance must be completely melted when it exceeds a predetermined temperature. Therefore, the temperature-sensitive substance of the present invention may be composed of one type of chemical substance, or may be a mixture of two or more types of substances. The information recorded in the thermosensitive layer due to the irreversible change of the thermosensitive substance on the thermosensitive layer should not be unreadable by human eyes or mechanical reading means such as a bar code reader. There is a case where the color is developed, a case where the information density recorded in the heat sensitive layer is changed, and the like. For example,
If the barcode is recorded on the heat-sensitive layer and exposed to a temperature outside the predetermined range, the density of the barcode becomes thin, or the printed portion is blurred, and the barcode cannot be read. In this case, the melted temperature-sensitive substance acts on the dye contained in the heat-sensitive layer, the dye precursor, the color developer, the binder, the pigment and other additives to dissolve, swell, diffuse these components, It undergoes irreversible changes due to the action of penetration and the like. Further, when the information recorded in the thermosensitive layer cannot be sufficiently irreversibly changed only by the melted temperature-sensitive substance, an additive for giving a sufficient irreversible change is added to the temperature-sensitive substance. It is also possible. The method of recording on the heat-sensitive layer of the intermediate is not particularly limited, but optical recording methods such as laser and flash are also conceivable in addition to thermal recording using a thermal head or a thermal stamp.

The temperature-sensitive substance of the present invention is not particularly limited as long as it can be melted by being exposed to a predetermined temperature and can permeate the permeation layer to reach the heat-sensitive layer, but it is preferable. It is preferable that the melted temperature-sensitive substance can directly or indirectly act on the dye in the heat-sensitive layer to make the information recorded in the heat-sensitive layer unreadable. Also,
When the melted temperature-sensitive substance does not directly or indirectly act on the dye of the thermosensitive layer, an additive that acts on the temperature-sensitive substance can be added. As the additive, those which directly or indirectly act on the dye or the dye precursor and which can be dissolved in the temperature-sensitive substance are preferable, and examples thereof include a radical generator, a pH adjuster, and a sensitizer. To be When such an additive is added to the temperature-sensitive substance, it may change not to the melting point of the temperature-sensitive substance itself but to the melting point of the mixture or composition. It is necessary to confirm the melting point of the product. The temperature-sensitive substance of the present invention includes alcohols, fatty acids, ketones, ethers, esters, amines,
Organic substances such as unsaturated aldehydes, aromatic hydrocarbons, aromatic alcohols, aromatic carboxylic acids, cyclohexane derivatives, cyclohexanol derivatives, urea compounds and their salts, chlorides, hydroxides, etc. Inorganic substances are preferable, when using the temperature display history body of the present invention in food products, pharmaceuticals, etc., those having high safety to the human body are more preferable, but even if the safety is not sufficient, the barrier layer It can be used by fully considering the sealing property with a support or a support.

The temperature-sensitive substance of the present invention has a melting point of 3 ° C. to 10 ° C. when used with a temperature-sensitive substance especially at low temperatures.
C. substances such as dimethyl sulfoxide (melting point, about 10 ° C.), oleic acid (melting point, about 10 ° C.),
Oleyl alcohol (melting point, about 4 ° C), 1-denacol (melting point, about 7 ° C), 5-isopropyl-2-methylphenol (melting point, about 4 ° C), os-butylphenol (melting point, 12 ° C), carba Crawl (melting point, 4 ° C), 2
-Chlorophenol (98%) (melting point, 12 ° C), m-
Cresol (melting point, 12 ° C), o-hydroacetophenone (melting point, 12 ° C), 2-methoxy-4-methylphenol (melting point, 6 ° C), o-nitroanisole (melting point,
10 ° C.) and the like, or a mixture of two or more thereof.

As the method for producing the temperature history display of the present invention, an intermediate product in which a heat-sensitive layer and a permeation layer are sequentially formed on a support is prepared, and when the intermediate product is attached to an object, the temperature-sensitive layer is formed. Alternatively, it can be produced by forming a temperature-sensitive layer and a barrier layer. More specifically, it is manufactured by performing thermosensitive recording on an intermediate product in which a thermosensitive layer and a permeation layer are sequentially formed on a support, and then forming a thermosensitive layer or a thermosensitive layer and a barrier layer. The formation of the temperature-sensitive layer of the present invention is carried out by preparing an intermediate product in which a permeation layer is formed on a support in advance, recording and printing necessary information on the intermediate product, and then applying the intermediate product to the melting point of the temperature-sensitive substance or less. It can be carried out by applying a temperature-sensitive substance kept at a melting point or higher to the intermediate product in the state of being placed under the environment of. Since the temperature-sensitive layer is formed in an environment at a temperature lower than the melting point of the temperature-sensitive substance, the temperature-sensitive substance is fixed on the permeation layer at the moment of application to the intermediate product. The temperature-sensitive layer does not have to be formed on the entire surface of the permeation layer, but can be formed partially at a required position.

The method for coating the temperature-sensitive layer of the present invention is not particularly limited, but it is conceivable to use an existing coating machine or printing machine. However, the present temperature-sensitive layer is formed by a large existing facility. In this case, it is necessary to keep the temperature inside the coating facility room at a low temperature, and to keep the temperature indication history display formed at a low temperature from the subsequent storage to the point of use. As a preferable method for forming the temperature-sensitive layer of the present invention, the intermediate product described above is manufactured by the existing facility, and the final use shape is finished. Just below the melting point of the hot substance.)
Alternatively, it is a method of forming a temperature sensitive layer after pasting. Specifically, a method of forming a film of a temperature-sensitive substance on the surface of a heated roll and transferring this film to the surface of the permeation layer of the intermediate product, or the molten temperature-sensitive substance is dropped or sprayed from the nozzle onto the surface of the permeation layer of the intermediate product. However, the method is not particularly limited as long as it is a method of applying and fixing the temperature-sensitive substance to the intermediate product in an atmosphere having a temperature below the melting point of the temperature-sensitive substance.

The temperature history display of the present invention is preferably provided with a transparent barrier layer so that the temperature sensitive layer does not physically or chemically change. The barrier layer prevents the temperature-sensitive layer from being damaged by physical contact and being deteriorated in the external environment. Further, it is possible to prevent the temperature-sensitive substance from leaking from the temperature history display of the present invention. By changing the thickness and thermal conductivity of the barrier layer of the present invention, it is possible to control the time for which the ambient temperature is transmitted to the temperature sensitive layer. Furthermore, when trying to detect the temperature change of the temperature-sensitive layer from the outside of the barrier layer, not from the side of the object (for example, a container for food products) that is adhered to the support. A support material having a relatively high thermal conductivity can be used for the barrier layer, and a material having excellent heat insulating properties can be used for the barrier layer. As a preferable method for forming a barrier layer, a method in which an adhesive layer or a pressure-sensitive adhesive layer formed on the surface of a transparent film is used as a barrier layer and the adhesive layer or the pressure-sensitive adhesive layer surface is attached to the temperature-sensitive layer surface is exemplified. it can. The transparent film used in the method of the present invention is not particularly limited, but may be polyethylene, polypropylene or poly-4.
-Methylpentene-1, ionomer, polyvinyl chloride, polyvinylidene chloride, ABS resin, polystyrene,
AS resin, methacrylic resin, polyvinyl alcohol, E
VA, cellulosic plastic, epoxy resin, unsaturated polyester resin, phenol resin, urea / melamine resin, polyurethane resin, silicone resin, polyamide resin, polyacetal, polycarbonate, modified polyphenylene ether, polyester resin, fluororesin, polyphenylene sulfide, polysulfone , Polyarylate, polyetherimide, polyethersulfone,
Polyketone, polyester, polyamide imide, polyimide, polyallyl ether nitrile, polybenzimidal, paper, etc. can be used alone or in combination of two or more films, or a composite sheet combining these films can be used. Conceivable.

The adhesive used for the adhesive layer of the transparent film is not particularly limited, and a vinyl acetate adhesive,
Vinyl acetate / ethylene copolymer adhesives, acrylic adhesives, natural rubber adhesives, styrene / butadiene adhesives, urethane adhesives, vinyl chloride adhesives, ethylene / vinyl acetate copolymer adhesives, blocks A rubber adhesive or the like may be used alone or in combination. The pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer is not particularly limited, and may be a natural rubber-based pressure-sensitive adhesive, a synthetic isoprene rubber-based pressure-sensitive adhesive, an SBR rubber-based pressure-sensitive adhesive, a polyacrylic acid ester-based pressure-sensitive adhesive, or a combination thereof. Polymers, silicone rubber-based adhesives, vinyl ether copolymer-based adhesives, etc. may be used alone or as a mixture.

[0033]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The parts and% shown below are based on mass. The coating amount is an absolutely dry coating amount.

Example 1 (Production of an intermediate product comprising a support, a heat-sensitive layer and a permeation layer) (a) Preparation of a heat-sensitive layer coating liquid. A dye precursor having a black color tone, 3- (N, N'-
30 parts of dibutylamino) -6-methyl-7-anilinofluorane was pulverized with 69 parts of a 2.5% aqueous solution of polyvinyl alcohol in a ball mill for 24 hours to obtain a dye precursor dispersion liquid. Next, 70 parts of 4,4'-hydroxydiphenylpropane as a color developer and 70 parts of 2-benzyloxynaphthalene as a sensitizer were ground with a sand mill together with 420 parts of a 2.5% polyvinyl alcohol aqueous solution to obtain a volume average particle size. A dispersion liquid containing a developer of 2 μm or less was obtained.
After mixing the above two kinds of dispersions, the following additives are added with stirring and mixed well to prepare a heat-sensitive layer forming coating liquid. 50% calcium carbonate aqueous dispersion 180 parts 40% zinc stearate aqueous dispersion 25 parts 10% polyvinyl alcohol aqueous solution 272 parts water 300 parts

(B) Preparation of support. A coating solution having the following composition is applied to a high-quality paper having a basis weight of 40 g / m 2 so as to have a solid content smear of 9 g / m 2, and dried to prepare a heat-sensitive coated paper. Calcined Kaolin 100 parts 50% Styrene-butadiene latex aqueous dispersion 24 parts Water 200 parts

(C) Preparation of coating solution for permeation layer. A dispersion was prepared by adding 100 parts of colloidal silica to 400 parts of polyvinyl alcohol solution while stirring. This is crushed with a ball mill for 24 hours to prepare a permeation layer coating liquid.

(D) Preparation of thermal paper. The heat-sensitive layer coating liquid prepared in (a) is applied on the support prepared in (b) so that the solid content is 4 g / m ^2, and dried to prepare a heat-sensitive paper. (E) Manufacture of intermediate products. On the heat-sensitive layer surface of the heat-sensitive paper prepared in (d) above, the permeation layer coating liquid prepared in (c) was applied so that the coating amount after drying was 5 g / m ² to form a permeation layer. To produce an intermediate product.

Example 2 (Preparation of coating solution for temperature-sensitive layer) As the temperature-sensitive layer solution (solution A), dimethyl sulfoxide having a melting point of 10 ° C was used, and as the temperature-sensitive layer solution (solution B), melting point was 4 ° C.
Use oleyl alcohol.

Example 3 (Preparation of Barrier Layer) As the barrier layer (X), a double-sided adhesive tape is used on a transparent polyester film (thickness: 25 μm) to prepare a transparent film having an adhesive layer on one side. In addition, as the barrier layer (Y), a transparent polyester film (thickness 50 μm
A double-sided adhesive tape is used for m) to prepare a transparent film having an adhesive layer on one side.

Example 4 (Production of Temperature History Display Using Liquid A) The intermediate product produced in Example 1 is recorded with a bar code by a thermal head. Thereafter, in a 5 ° C. environment, the temperature-sensitive layer coating liquid (solution A) described in Example 2 was heated to 13 ° C. and applied to the permeation layer surface at 10 g / m ² to form a temperature-sensitive layer. Then, a temperature history display is produced. Immediately after dropping, the liquid A is solidified by the influence of the environmental temperature and fixed on the surface of the permeation layer. This display is left in an environment of 15 ° C. and an environment of 5 ° C. 15
At ° C, the temperature-sensitive substance solidified on the surface of the permeation layer gradually melts, the melted liquid gradually moves from the permeation layer to the heat-sensitive layer, the bar code becomes gradually thin, and the bar code becomes unreadable. On the other hand, at 5 ° C, the temperature-sensitive substance remains solidified even after 1 week, and the barcode can be read.

Example 5 (Production of Temperature History Display Using Liquid B) The intermediate product produced in Example 1 is bar-coded with a thermal head. Then, in a 0 ° C. environment, the temperature-sensitive layer coating liquid (solution B) described in Example 2 was heated to 7 ° C. and applied to the permeation layer surface at 10 g / m ² to form a temperature-sensitive layer. Then, a temperature history display is produced. Immediately after dropping, the liquid B is solidified by the influence of the environmental temperature and fixed on the surface of the permeation layer. The resulting temperature history display is left in an environment of 7 ° C and 2 ° C. At 7 ° C, the temperature-sensitive substance solidified on the surface of the permeation layer gradually melts, and the melted liquid gradually moves from the permeation layer to the heat-sensitive layer, and the barcode becomes thinner, making it impossible to read the barcode. . On the other hand, at 2 ° C., the temperature-sensitive substance remains solidified even after 1 week, and the barcode can be read.

Example 6 (Temperature with Barrier Layer (X)
Manufacturing of degree history display) The intermediate product described in Example 1 was bar-coated with a thermal head.
Record the code. Then, in an environment of 0 ° C, it was heated to 7 ° C.
10g / m of the temperature-sensitive layer coating liquid (B liquid) on the permeation layer surface ^Twobecome
To form a temperature-sensitive layer, and subsequently described in Example 3.
Attach the placed barrier layer (X) with the adhesive layer facing down,
A temperature history display having a barrier layer is produced. This table
The indicator is left in an environment of 7 ° C and 2 ° C. At 7 ° C
The temperature-sensitive substance solidified on the surface of the permeation layer gradually melts and melts.
The dissolved solution gradually moves from the permeation layer to the heat-sensitive layer, and gradually
-The code becomes thin, making it impossible to read the barcode.
Become. On the other hand, at 5 ° C, the barcode can be read even after 1 week.
Is possible. Furthermore, to confirm the effect of the barrier layer
Therefore, touch the temperature history display with your finger for 1 second in an environment of 2 ° C.
And a nail rub test, both
However, no change is observed. On the other hand, it does not have a barrier layer.
Touch the temperature-sensitive layer surface of the temperature history display produced in Example 5 with a finger.
Then, the temperature sensitive substance adheres to the finger. Also, rub it with your nails
Some peeling occurs.

Example 7 (Temperature with Barrier Layer (Y)
Manufacturing of degree history display) The intermediate product described in Example 1 was bar-coated with a thermal head.
Record the code. Then, in an environment of 0 ° C, it was heated to 7 ° C.
10g / m of the temperature-sensitive layer coating liquid (B liquid) on the permeation layer surface ^Twobecome
To form a temperature-sensitive layer, and subsequently described in Example 3.
Stick the placed barrier layer (Y) with the adhesive layer facing down,
A temperature history display having a barrier layer is produced. This table
The indicator is left in an environment of 7 ° C and 2 ° C. At 7 ° C
The temperature-sensitive substance solidified on the surface of the permeation layer gradually melts and melts.
The dissolved solution gradually moves from the permeation layer to the heat-sensitive layer, and gradually
-The code becomes thin, making it impossible to read the barcode.
Become. On the other hand, at 5 ° C, the barcode can be read even after 1 week.
Is possible. Furthermore, to confirm the effect of the barrier layer
Therefore, touch the temperature history display with your finger for 1 second in an environment of 2 ° C.
Both the rubbed test and the nail rub test
No change is allowed.

[0044]

The heat-sensitive layer, permeation layer, and
When the temperature history display medium formed with the temperature sensitive layer is exposed to a predetermined temperature, it causes an irreversible change such as a change so that the information recorded on the heat sensitive layer becomes legible, so that the temperature above the predetermined temperature is exceeded. The history of exposure to can be displayed irreversibly. Further, it is possible to control the time required for the temperature-sensitive substance to reach the heat-sensitive layer by changing the thickness of the permeation layer. Furthermore, by forming a barrier layer on the outermost surface, it is possible to prevent physical damage to the temperature-sensitive layer and prevent deterioration due to the external environment. Also, the time with respect to the environmental temperature can be controlled by changing the thickness of the barrier layer. This temperature history display medium can be easily manufactured by forming the temperature history display medium up to the permeation layer in advance and forming the temperature sensitive layer in an atmosphere having a temperature not higher than the melting point of the temperature sensitive agent.

[Brief description of drawings]

FIG. 1 shows a layered structure of a cross section of a temperature history display of the present invention.

FIG. 2 shows a layer structure of a cross section of the temperature history display of the invention having a barrier layer.

FIG. 3 is a temperature history display of the present invention having a barrier layer, and shows a layer structure of a cross section when the barrier layer and the support have an adhesive layer to which the support can be attached.

[Explanation of symbols]

1 support 2 heat sensitive layer 3 Penetration layer 4 temperature sensitive layer 5 barrier layers 6 Adhesive layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tadahiro Ishii             1-11-1 Isehara Town, Kawagoe City, Saitama Prefecture (72) Inventor Katsunori Tsunoda             84 Maison Blanche, Akagi Town, Shinjuku-ku, Tokyo             U 410 (72) Inventor Mitsui Kamai             1-26 Kandasudacho Stock Exchange, Chiyoda-ku, Tokyo             In company chromic (72) Inventor Yoko Asakawa             1-26 Kandasudacho Stock Exchange, Chiyoda-ku, Tokyo             In company chromic (72) Inventor Akira Masuda             Mitsubishi 3-4-2 Marunouchi, Chiyoda-ku, Tokyo             Paper Manufacturing Co., Ltd. (72) Inventor Shigetoshi Hiraishi             Mitsubishi 3-4-2 Marunouchi, Chiyoda-ku, Tokyo             Paper Manufacturing Co., Ltd.

Claims (11)

[Claims] 1. A heat-sensitive layer containing a dye precursor and a color developer that develops the dye precursor, a permeation layer, and a temperature-sensitive layer containing a temperature-sensitive substance having a melting point at a specific temperature are sequentially formed on a support. A temperature history display characterized by being performed. 2. When the ambient temperature exceeds the melting point of the temperature-sensitive substance,
The temperature history display according to claim 1, wherein the temperature-sensitive substance causes an irreversible change in the heat-sensitive layer. 3. The temperature history display according to claim 1 or 2, wherein the temperature sensitive substance has a characteristic of changing recorded information on the heat sensitive layer. 4. The temperature history display body according to claim 1, wherein a barrier layer is formed on the temperature sensitive layer of the temperature history display body. 5. The pressure-sensitive adhesive layer is formed on the side of the support of the temperature history display opposite to the heat-sensitive layer.
The temperature history display according to any one of 4 above. 6. An intermediate product in which a heat-sensitive layer and a permeation layer are sequentially formed on a support, and a temperature-sensitive layer or a temperature-sensitive layer and a barrier layer are formed when the intermediate product is attached to an object. The method for manufacturing a temperature history display body according to claim 1, wherein 7. The method for producing a temperature history indicator according to claim 6, wherein the temperature-sensitive layer or the temperature-sensitive layer and the barrier layer are formed after heat-sensitive recording is performed on the intermediate product. 8. An information recording medium having, on a support, a heat sensitive layer containing a dye precursor and a color developer that develops the dye precursor, and a permeation layer. 9. The information recording medium according to claim 8, wherein the permeation layer is a layer for permeating a temperature-sensitive substance having a melting point at a specific temperature. 10. The information recording medium according to claim 8, wherein the support is paper. 11. The information recording medium according to claim 8, which is used for the temperature history display according to any one of claims 1 to 5.