JP2000002596A - Method for producing heat-sensitive color generation element and apparatus for producing heat-sensitive color generation element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable continuous mass-production by providing a process in which a raw material solution of a heat-sensitive color generation material is printed to a base body or by the like manner, thereby forming a heat-sensitive color generation material layer on a front face, a process in which a surface protection sheet or the like is set to the heat-sensitive color generation material layer, etc. SOLUTION: In order to produce a heat-sensitive color generation element which is used to manage a cold insulation system, etc., and utilizes a surface plasmon absorption of metallic fine particles, for instance, a heat-sensitive color generation material layer is formed on a front face of a base body 5 of a polypropyrene sheet or the like with the use of a printing or applying apparatus 1 and a drying apparatus 2, and a surface protection sheet of cellophane or the like or a tape 6 is further bonded or pressure applied. A heat-sensitive color generation material protected at the front face is kept at a low temperature in a freezer 4 or the like after an ultraviolet ray is irradiated with the use of a light irradiation apparatus 3, etc. A continuous tape-shaped heat-sensitive color generation element thus produced in continuous processes is cut appropriately to a desired size, etc. An arrangement whereby the heat-sensitive color generation material layer is held on a carrier body of a filter paper or the like and kept on the base body after cut, etc., is also adoptable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for manufacturing a thermosensitive coloring element, which utilizes a surface plasmon absorption due to the growth of metal fine particles and is used for temperature control during storage or distribution of a refrigerated or frozen food. Things.

[0002]

2. Description of the Related Art Conventionally, as a thermosensitive coloring element and a method of manufacturing the same, there is one disclosed in, for example, WO 97/28228. The thermosensitive coloring element is a plate-like element in which metal fine particles are dispersed in a matrix, or is supported on a filter paper or the like, and utilizes surface plasmon absorption due to the growth of the metal fine particles with an increase in temperature. Also,
The production method includes a step of preparing a mixed solution of a thermosensitive coloring material material and a step of irradiating the mixture with ultraviolet rays.

[0003]

However, in the conventional method for manufacturing a thermosensitive coloring device as described in the above-mentioned document,
In the case of mass production, it is difficult to obtain a thermosensitive coloring device having uniform characteristics in all cases, and it is difficult to mass-produce continuously. A situation that cannot keep up with demand will occur.

[0004]

According to the present invention, there is provided a thermosensitive coloring material comprising fine metal fine particles and a matrix material composed of glass or resin, wherein the size of the fine metal fine particles is irreversibly increased by a rise in temperature. This is an apparatus for continuously mass-producing thermosensitive coloring devices in a form held on a substrate. This thermosensitive coloring device is colorless and transparent at a relatively low temperature (〜１０10 ° C.), but irreversibly and efficiently develops color at a temperature close to room temperature. An apparatus capable of mass-producing such a thermosensitive coloring device. The purpose is to provide.

[0005] In order to solve this problem, the first aspect of the present invention.
The method and apparatus for producing a thermosensitive coloring element include a device for printing or applying a thermosensitive coloring material raw material solution on at least a part of a substrate and drying to form a thermosensitive coloring material layer on the substrate surface. It is equipped with a device for installing a surface protection sheet or tape.

The second method and apparatus for manufacturing a thermosensitive coloring element according to the present invention are to print or apply a thermosensitive coloring material raw material solution on at least a part of a substrate and to dry the same to form a thermosensitive coloring material layer on the substrate surface. The apparatus includes a device for forming, a device for placing a surface protective sheet or tape on the thermosensitive coloring material layer, and a light irradiation device for irradiating the thermosensitive coloring material with light from the surface protective sheet or tape side.

In a third method and apparatus for manufacturing a thermosensitive coloring element according to the present invention, a thermosensitive coloring material raw material solution is printed or applied to at least a part of a substrate and dried to form a thermosensitive coloring material layer on the substrate surface. A forming device, a device for forming a surface protective sheet or tape on the thermosensitive coloring material layer, a light irradiating device for irradiating the thermosensitive coloring material with light from the surface protecting sheet or tape side, and a thermosensitive coloring material after the light irradiation Provided with a refrigerating device for maintaining the temperature of the refrigeration at low temperature.

A fourth method and apparatus for manufacturing a thermosensitive coloring element according to the present invention provide a method for coating or impregnating a raw material solution of a thermosensitive coloring material, drying and supporting the same on a carrier, and cutting or punching into a predetermined size. And a device for sandwiching and fixing the carrier supporting the thermosensitive coloring material raw material solution between the substrate and the surface protection sheet or tape.

In a fifth aspect of the present invention, a method and apparatus for manufacturing a thermosensitive coloring element comprises applying or impregnating a raw material solution of a thermosensitive coloring material to a carrier, drying the carrier, supporting the carrier, and cutting or punching the carrier into a predetermined size. And a device for sandwiching and fixing the carrier carrying the thermosensitive coloring material raw material solution between the substrate and the surface protective sheet or tape, and light irradiation for irradiating the thermosensitive coloring material with light from the surface protective sheet or tape side It is equipped with a device.

In a sixth aspect of the present invention, there is provided a method and an apparatus for manufacturing a thermosensitive coloring element, wherein a raw material solution of a thermosensitive coloring material is applied to or impregnated on a carrier, dried, supported on the carrier, and cut or punched into a predetermined size. And a device for sandwiching and fixing the carrier carrying the thermosensitive coloring material raw material solution between the substrate and the surface protective sheet or tape, and light irradiation for irradiating the thermosensitive coloring material with light from the surface protective sheet or tape side A refrigerating device for holding the thermosensitive coloring material at a low temperature after the light irradiation.

A seventh method and apparatus for manufacturing a thermosensitive coloring element according to the present invention comprises applying or impregnating an inorganic substance or resin to a carrier, drying and supporting the carrier, and further applying a raw material solution of a thermosensitive coloring material to the carrier. Apparatus for coating or impregnating, drying and supporting on a carrier, cutting or punching into a predetermined size, and carrier supporting the inorganic substance or resin and a thermosensitive coloring material raw material solution between a substrate and a surface protection sheet or tape Is provided with a device for sandwiching and fixing.

An eighth method and apparatus for manufacturing a thermosensitive coloring element according to the present invention comprises applying or impregnating an inorganic substance or resin to a carrier, drying the carrier and supporting the carrier, and further applying a raw material solution of the thermosensitive coloring material to the carrier. Apparatus for coating or impregnating, drying and supporting on a carrier, cutting or punching into a predetermined size, and carrier supporting the inorganic substance or resin and a thermosensitive coloring material raw material solution between a substrate and a surface protection sheet or tape And a light irradiating device for irradiating the thermosensitive coloring material with light from the surface protective sheet or tape side.

A ninth method and apparatus for manufacturing a thermosensitive coloring element according to the present invention comprises coating or impregnating an inorganic substance or resin on a carrier, drying and supporting the carrier, and further applying a raw material solution of the thermosensitive coloring material to the carrier. Apparatus for coating or impregnating, drying and supporting on a carrier, cutting or punching into a predetermined size, and an apparatus for sandwiching and fixing the carrier carrying the thermosensitive coloring material solution between a substrate and a surface protection sheet or tape And a light irradiation device for irradiating the thermosensitive coloring material with light from the surface protective sheet or the tape side, and a refrigerating device for keeping the thermosensitive coloring material at a low temperature after the light irradiation.

Further, in the thermosensitive coloring device manufactured by the present invention, the thermosensitive coloring material has a smaller shape than the substrate, the surface protection sheet or the tape and is completely sealed, so that the reliability is improved.

Further, in the thermosensitive coloring device manufactured by the present invention, the fine metal particles are preferably at least one selected from gold, platinum, silver, copper, tin, rhodium, palladium and iridium. Further, the matrix is preferably at least one selected from silicon oxide, aluminum oxide, titanium oxide, fluororesin, polyvinyl alcohol, polyvinyl butyral, polystyrene, and acrylonitrile-styrene copolymer.

The substrate has a bonding function in which a waterproof cardboard, a sheet made of polyethylene, polypropylene, polyvinyl chloride, or polyvinylidene chloride, or an adhesive layer and a release liner are provided on the back of the cardboard or the sheet. It is preferably at least one selected from those described above.

The carrier is preferably at least one selected from filter paper, paper, cloth, and porous ceramic fiber sheet.

The sheet or tape may be cellophane,
It is preferably at least one selected from polyethylene, polypropylene, polyvinyl chloride, and polyvinylidene chloride. Further, it is preferable that the inorganic substance coated on the carrier is at least one selected from silicon oxide, aluminum oxide, and titanium oxide. The resin coated on the carrier is a fluororesin, polyvinyl alcohol, starch paste,
It is preferably at least one selected from polyvinyl butyral, polystyrene, and acrylonitrile-styrene copolymer.

[0019]

Embodiments of the present invention will be described below with reference to the drawings.

(Embodiment 1) FIG. 1 shows a schematic configuration of an apparatus for manufacturing a thermosensitive coloring element. Printing device 1 on part of base 5
Alternatively, the thermosensitive coloring material solution is printed or coated on at least a part of the substrate by using the coating device 1 and passed through a drier 2 to dry the thermosensitive coloring material and form a thermosensitive coloring material layer on the surface of the base. I do. Further, the surface protection sheet 6 or the tape 6 is attached by bonding or pressure bonding, and the thermosensitive coloring material is irradiated with light (ultraviolet light) from the side of the surface protection sheet 6 or the tape 6 using the light irradiation device 3. The thermosensitive coloring material is immediately sent to the freezer 4 and kept at a low temperature so that a large number of thermosensitive coloring elements can be produced in a continuous process. When actually used, the continuous thermosensitive coloring element in a tape shape is appropriately cut into a desired size.

In FIG. 1, the thermosensitive coloring material has a configuration in which metal ions are dispersed in a matrix until the thermosensitive coloring material is held on a substrate and a surface protection sheet or tape is provided. However, when the heat-sensitive coloring material is irradiated with light (ultraviolet light) from the surface protection sheet or the tape side, the metal ions are reduced by the light and gradually become fine metal particles. When the thermosensitive coloring element is held in the freezer (〜0 ° C.) at such a stage, the size of the fine metal particles hardly changes. On the other hand, once the thermosensitive coloring element is exposed to a temperature near room temperature, the fine metal particles begin to grow by obtaining thermal energy, and color development based on remarkable surface plasmon absorption by the metal fine particles is observed. Therefore, the manufactured thermosensitive coloring device must be used immediately or stored in a refrigerator or a refrigerator as shown in FIG. When a thermosensitive coloring element is used, it is appropriately cut from a tape-like form into a desired size.

In the heat-sensitive coloring element of the present invention, the amount of the heat-sensitive coloring material to be printed, applied, or carried on the substrate is not particularly limited, but 0.1 g / m ^{2 to} 100 g in which the coloring is remarkable. / range of m ² are preferred, especially good adhesion is 2 g / m ² to 50 g / m ² obtained with the substrate more preferable.

Further, the metal fine particles are made of gold, platinum, silver, copper,
According to a preferred embodiment of the present invention, which is at least one selected from tin, rhodium, palladium, and iridium, these metals exhibit a coloration based on surface plasmon absorption, and exhibit oxygen and other impurities as compared with other metals. And is capable of precipitating relatively pure metal fine particles, so that a material exhibiting excellent thermosensitive coloring characteristics can be realized.

The dispersion amount of the metal fine particles in the matrix is not particularly limited, but the particle size can be easily controlled, and the fine particles are hardly agglomerated.
wt%, preferably about 0.05 to 10 wt%. When agglomeration occurs, only a part of the material develops a deep color, and it cannot be confirmed whether or not the temperature has definitely changed.

The average particle diameter of the grown metal fine particles is as follows:
Although it varies depending on the type, for example, a range of 1 nm to 50 nm is usually preferable, and a range of 3 nm to 30 nm is more preferable particularly for reducing the particle size distribution and uniform coloring.

In the present invention, the raw material solution of the thermosensitive coloring material may be a solution in which a metal salt that becomes fine metal fine particles by a photoreduction reaction is a lower alkoxy solution of a sol-like metal or a solution in which a resin is dissolved in water or an organic solvent. Use the one dissolved in

The metal salts include HAuCl ₄ , N
aAuCl ₄ , H ₂ PtCl ₆ , AgClO ₄ , CuC
Preferred are l ₂ , SnCl ₂ , IrCl ₃ , RhCl ₃ and PdCl ₂ .

As a glass material for coating a matrix or a carrier surface prepared by the sol-gel method, silica gel, alumina gel, or titania gel which is chemically stable and optically transparent over a wide wavelength range is preferable. The sol-gel method is a method of obtaining glass or ceramics by hydrolyzing a lower alkoxide of a metal in a sol, gelling and heating. Specific examples of typical metal alkoxides include lower alkoxides of silicon such as methoxide and ethoxide of silicon, lower alkoxides of aluminum such as methoxide and ethoxide of aluminum, and lower alkoxides of titanium such as methoxide and ethoxide of titanium. Kind. As a dispersion medium of the sol, water and / or methanol, ethanol, propanol or dihydric alcohols such as ethylene glycol and propylene glycol are used, and hydrochloric acid or ammonia is usually added as a catalyst for hydrolysis. Furthermore, the amount of glass coating the substrate surface is 0.5
g / m ² to 100 g / range m ² is preferably, in particular in order to obtain the adhesion of good glass prevents the adverse effects of chemical substances from the substrate completely covers the substrate surface, 2 g /
coverage of m ² ~30g / m ² is more preferable.

The resin for coating the matrix and the surface of the carrier is chemically stable, can contain alcohol and water, and can uniformly cover a large area with polyvinyl alcohol and polyvinyl butyral.
It is preferable to use polystyrene, polyacrylic acid, acrylonitrile / styrene copolymer, or fluororesin. Further, the amount of the resin coating the substrate surface is 0.1
g / m ² range to 150 g / m ² is preferably, in particular in order to prevent the adverse effects of chemical substances from the substrate completely covers the substrate surface, more the coverage of 1g / m ² ~40g / m ² preferable.

Preferably, the sheet or tape uses cellophane, polyethylene, polypropylene, polyvinyl chloride, or polyvinylidene chloride having excellent moisture resistance.

A dryer for drying the thermosensitive coloring material comprises:
It is preferable to use a type that blows hot air or a far-infrared lamp with a surface temperature of 120 ° C. or less without deteriorating the substrate or carrier.

It is preferable to use a xenon lamp, a halogen lamp, a high-pressure mercury lamp, or a low-pressure mercury lamp as a light source for irradiating ultraviolet rays. Further, it is more preferable to use a tunnel-shaped light irradiation device in which a plurality of light sources are arranged vertically or horizontally because light can be efficiently irradiated in a short time.

Further, the freezer or refrigerator for storing the produced thermosensitive coloring device at a low temperature is preferably at 0 ° C. or lower, and more preferably, one which can be stored while winding the thermosensitive coloring device without taking up space.

(Embodiment 2) FIG. 2 shows a schematic configuration of another apparatus for manufacturing a thermosensitive coloring element. Using a printing device 1 or a coating device 1 on a part of the carrier 5, a thermosensitive coloring material material solution is printed or coated on at least a portion of the carrier, and passed through a dryer 2 to dry the thermosensitive coloring material material. A thermosensitive coloring material layer. Further, after the thermosensitive coloring material is formed into a predetermined size and shape by the cutting device 8 or the punching device 8, the thermosensitive coloring material is placed between the surface protection sheet 6 or the tape 6 and the base 7, and is adhered or pressed and sealed.
Further, light (ultraviolet light) is irradiated to the thermosensitive coloring material from the surface protective sheet 6 or the tape 6 side by using the light irradiation device 3. The thermosensitive coloring material after the light irradiation is immediately sent to the freezer 4 and kept at a low temperature. It is configured to be able to mass-produce thermosensitive coloring devices in a continuous process.

(Embodiment 3) FIG. 3 shows a schematic configuration of another apparatus for manufacturing a thermosensitive coloring element. Using a printing device 9 or a coating device 9 on a part of the carrier 5, an inorganic substance or a resin solution is supported on at least a part of the carrier, passed through a drier 10, and the carrier is dried to form an inorganic substance or resin on the carrier. Carry. Further, the printing apparatus 1 is continuously applied to a part of the base 5.
Alternatively, using a coating device 1, a thermosensitive coloring material solution is printed or applied to at least a part of the carrier and carried, and then passed through a dryer 2, the thermosensitive coloring material is dried, and the carrier is loaded with the thermosensitive coloring material. I do. Further, after the thermosensitive coloring material is formed into a predetermined size and shape by the cutting device 8 or the punching device 8, the thermosensitive coloring material is placed between the surface protection sheet 6 or the tape 6 and the base 7, and is adhered or pressed and sealed. Further, light (ultraviolet light) is applied to the thermosensitive coloring material from the surface protection sheet 6 or the tape 6 side using the light irradiation device 3.
The heat-sensitive coloring material after light irradiation is immediately
, And can be mass-produced in a continuous process of maintaining the temperature at a low temperature.

[0036]

EXAMPLES Specific examples of the present invention will be described below.

Example 1 A large number of thermosensitive coloring devices were manufactured using the manufacturing apparatus shown in FIG. The sol solution shown in Table 1, the Au of HAuCl ₄ with respect to SiO ₂ 1 w
After the addition, the mixture was stirred so that the concentration became t% to prepare a raw material solution.
This raw material solution was applied to the backside with an adhesive layer and a release liner by a coating apparatus shown in FIG.
It was applied to a part of a substrate 5 made of a polypropylene sheet having a thickness of 2 mm, sent to a drier 2 and dried with hot air at 80 ° C. for 3 minutes to form a thermosensitive coloring material layer on the surface of the substrate. further,
A cellophane tape was pressed onto the substrate and pressed to form a surface protection tape 6.

[0038]

[Table 1]

The thermosensitive coloring device thus produced was pale yellow. Each of the heat-sensitive coloring elements manufactured in the above steps was placed at a position where no heat-sensitive coloring element was formed.
After cutting to 0 mm and a length of 20 mm, light irradiation was performed at room temperature for 30 seconds using a light irradiation device in which five 20 W low-pressure mercury lamps were arranged, and the element changed from yellow to colorless. Then, the device was immediately stored in a freezer at 0 ° C. In this state, it is colorless even when stored for 2 months in an atmosphere of 0 ° C.
Did not develop color. However, when the thermosensitive coloring device was taken out of the freezer at 0 ° C. into the room at 25 ° C., the device developed reddish purple in a few minutes. This is because the surface plasmon absorption of the fine particles became clear due to the growth of the Au fine particles at room temperature. Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. It was found that such a photoreduction reaction of HAuCl ₄ was extremely slow in the absence of ethylene glycol and was not used for practical use. The average particle size of the Au fine particles generated at room temperature is 5n.
m and the particle size distribution was found to be small. Even when the same thermosensitive coloring device was stored in an atmosphere at 10 ° C. for one month, it was colorless and did not develop color. However, when the complex was taken out of the refrigerator at 10 ° C. into the room at 25 ° C., the complex again developed a purple-red color within a few minutes.

Further, such a thermosensitive coloring device can be used one at a time.
It was found that they had almost the same characteristics when manufactured 100 times 10 times.

A similar thermosensitive coloring device could be produced by using NaAuCl ₄ instead of HAuCl _{4 in} the above process.

In the sol solution of (Table 1), Si (O
A similar thermosensitive coloring element could be produced when C ₂ H ₅ ) ₄ was changed to Al (OC ₂ H ₅ ) ₃ or Ti (OC ₂ H ₅ ) ₄ .

In the sol solution of (Table 1), the sol of Table 1 was used.
HAuCl in aqueous solution_FourInstead of H_TwoPtCl₆,
AgCLO_Four, CuCl_Two, SnCl_Two, IrCl_Three, Rh
Cl _Three, PdCl_TwoCan be used to create a thermosensitive coloring element.
Could be manufactured.

In this embodiment, a 0.2 mm-thick polypropylene sheet having an adhesive layer and a release liner on the back surface of the substrate is used. However, waterproof cardboard, polyethylene, polyvinyl chloride, Similar effects could be obtained by using a sheet made of polyvinylidene chloride, or a cardboard or sheet having an adhesive function provided with an adhesive layer and a release liner on the back surface of the sheet.

Example 2 In the same manner as in Example 1, a large number of thermosensitive coloring devices were manufactured using the manufacturing apparatus shown in FIG. HAuCl ₄ was added to the sol solution shown in Example 1 (Table 1).
After adding Au so as to be 1 wt% with respect to iO ₂ , the mixture was stirred to prepare a raw material solution. This raw material solution is applied to a part of a base member 5 made of a 0.2 mm thick polypropylene sheet having an adhesive layer and a release liner on the back surface by a coating apparatus shown in FIG. Send to 2,
It was dried with hot air at 80 ° C. for 3 minutes to form a thermosensitive coloring material layer on the substrate surface. Further, a cellophane tape was pressed onto the substrate and pressed to form a surface protection tape 6. Thereafter, when light irradiation was performed at room temperature for 10 seconds using a tunnel-shaped light irradiation device 3 in which five 20 W low-pressure mercury lamps were continuously arranged, the element changed from yellow to colorless. Then, the heat-sensitive coloring devices produced in the above steps were immediately cut into a width of 10 mm and a length of 20 mm at portions where no heat-sensitive coloring devices were formed, and then stored in a freezer at -20 ° C.
In this state, it was colorless even after storage for 2 months, and did not develop color. However, the thermosensitive coloring device was placed in a freezer at 25 ° C.
When it was taken out of the room, it grew reddish purple in a few minutes. This is because the surface plasmon absorption of the fine particles became clear due to the growth of the Au fine particles at room temperature. Also,
The color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. It was found that such a photoreduction reaction of HAuCl ₄ was extremely slow in the absence of ethylene glycol and was not used for practical use. The average particle size of the Au fine particles generated at room temperature was 5 nm, and the particle size distribution was found to be small. Even when the same thermosensitive coloring device was stored in an atmosphere at 10 ° C. for one month, it was colorless and did not develop color. However, this complex was placed in a refrigerator at
When it was taken out of the room, it turned reddish purple in a few minutes.

Further, such a thermosensitive coloring device can be used one at a time.
It was found that they had almost the same characteristics when manufactured 100 times 10 times.

In this embodiment, a 0.2 mm-thick polypropylene sheet having an adhesive layer and a release liner on the back surface of the substrate is used. However, waterproof cardboard, polyethylene, polyvinyl chloride, Similar effects could be obtained by using a sheet made of polyvinylidene chloride, or a cardboard or sheet having an adhesive function provided with an adhesive layer and a release liner on the back surface of the sheet.

Example 3 In the same manner as in Example 1, a large number of thermosensitive coloring devices were manufactured using the manufacturing apparatus shown in FIG. HAuCl ₄ was added to the sol solution shown in Example 1 (Table 1).
After adding Au so as to be 1 wt% with respect to iO ₂ , the mixture was stirred to prepare a raw material solution. This raw material solution is applied to a part of a base member 5 made of a 0.2 mm thick polypropylene sheet having an adhesive layer and a release liner on the back surface by a coating apparatus shown in FIG. Send to 2,
It was dried with hot air at 80 ° C. for 3 minutes to form a thermosensitive coloring material layer on the substrate surface. Further, a cellophane tape was pressed onto the substrate and pressed to form a surface protection tape 6. Thereafter, when light irradiation was performed at room temperature for 10 seconds using a tunnel-shaped light irradiation device 3 in which five 20 W low-pressure mercury lamps were continuously arranged, the element changed from yellow to colorless. Immediately after the light irradiation, the thermosensitive coloring device was stored while being wound up in a freezer 4 at -20 ° C. In this state, it was colorless even after storage for one month, and did not develop color. Then, each of the portions where the thermosensitive coloring element was not formed was cut into a width of 10 mm and a length of 20 mm, and was taken out of the freezer into a room at 25 ° C., and a reddish purple color was formed in a few minutes. This is because the surface plasmon absorption of the fine particles became clear due to the growth of the Au fine particles at room temperature. Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. When 100 such thermosensitive coloring devices were manufactured 10 times at a time, it was found that they had almost the same characteristics.

In this embodiment, a 0.2 mm thick polypropylene sheet having an adhesive layer and a release liner on the back surface is used for the substrate. However, waterproof cardboard, polyethylene, polyvinyl chloride, Similar effects could be obtained by using a sheet made of polyvinylidene chloride, or a cardboard or sheet having an adhesive function provided with an adhesive layer and a release liner on the back surface of the sheet.

Example 4 In the same manner as in Example 1, a large number of thermosensitive coloring devices were manufactured using the manufacturing apparatus shown in FIG. Polyvinyl alcohol (PVA) with an average degree of polymerization of 1000 and ethylene glycol (20% by weight based on PVA)
The Au respect PVA in PVA aqueous solution prepared by dissolving in hot water is stirred after the addition of HAuCl ₄ so as to 1 wt%, to prepare a raw material solution. This raw material solution is
Is applied to a part of a base member 5 made of a 0.2 mm-thick polypropylene sheet having an adhesive layer and a release liner on the back surface, and sent to the dryer 2 at 80 ° C. After drying with hot air for a minute, a thermosensitive coloring material layer was formed on the substrate surface. Further, a cellophane tape was pressed onto the substrate and pressed to form a surface protection tape 6. Thereafter, when light irradiation was performed at room temperature for 20 seconds using a tunnel-shaped light irradiation device 3 in which five 20 W low-pressure mercury lamps were continuously arranged, the element changed from yellow to colorless. Immediately after the light irradiation, the thermosensitive coloring device was stored while being wound up in a freezer 4 at -20 ° C. In this state, it was colorless even after storage for one month, and did not develop color. Each of the portions where the thermosensitive coloring element is not formed has a width of 10 mm and a length of 20 mm.
After being cut into a freezer, it was taken out of the freezer into a room at 25 ° C., and in a few minutes, a purple-red color developed. This is because the surface plasmon absorption of the fine particles became clear due to the growth of the Au fine particles at room temperature. Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. When 100 such thermosensitive coloring devices were manufactured 10 times at a time, it was found that they had almost the same characteristics.

In this embodiment, a 0.2 mm-thick polypropylene sheet having an adhesive layer and a release liner on the back surface of the substrate is used. However, waterproof paperboard, polyethylene, polyvinyl chloride, Similar effects could be obtained by using a sheet made of polyvinylidene chloride, or a cardboard or sheet having an adhesive function provided with an adhesive layer and a release liner on the back surface of the sheet.

Example 5 A large number of thermosensitive coloring devices were manufactured using the manufacturing apparatus shown in FIG. Actual example 1 (Table 1)
The sol solution shown in, A and HAuCl ₄ with respect to SiO ₂
After adding so that u becomes 1 wt%, the mixture was stirred to prepare a raw material solution. This raw material solution was applied to the filter paper carrier 5 for ion exchange by the coating apparatus shown in 1 of FIG. 2, sent to the dryer 2, and dried with hot air at 90 ° C. for 3 minutes to carry the thermosensitive coloring material. The carried amount was 16 g / m ² . The carrier is cut into a width of 10 mm and a length of 30 mm by a cutting device 8 and then placed on a substrate 7 made of a 0.2 mm thick polypropylene sheet having an adhesive layer and a release liner on the back surface. A cellophane tape was pressed and pressed from above and sealed between the substrate 7 and the surface protection tape 6.

The thermosensitive coloring device thus manufactured was pale yellow. When the thermosensitive coloring device manufactured in the above process was irradiated with light at room temperature for 30 seconds using a light irradiation device in which five 20 W low-pressure mercury lamps were arranged, the device changed from yellow to colorless. Then, the device was immediately stored in a freezer at 0 ° C. In this state, even if stored in an atmosphere at 0 ° C. for 2 months, the color was colorless and no color was formed. However, when the thermosensitive coloring device was taken out of the freezer at 0 ° C. into the room at 25 ° C., the device developed reddish purple in a few minutes. This is because at room temperature Au
This is because the surface plasmon absorption of the fine particles became clear by the growth of the fine particles. Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. It was found that such a photoreduction reaction of HAuCl ₄ was extremely slow in the absence of ethylene glycol and was not used for practical use. The average particle size of the Au fine particles generated at room temperature was 5 nm, and the particle size distribution was found to be small. Even when the same thermosensitive coloring device was stored in an atmosphere at 10 ° C. for one month, it was colorless and did not develop color. However, when the complex was taken out of the refrigerator at 10 ° C. into the room at 25 ° C., the complex again developed a purple-red color within a few minutes.

Further, such a thermosensitive coloring device can be used one at a time.
It was found that they had almost the same characteristics when manufactured 100 times 10 times.

Further, in this example, filter paper for ion exchange was used as a carrier, but qualitative filter paper, quantitative filter paper, glass fiber filter paper,
Similar effects could be obtained by using silica fiber filter paper, paper made from Manila hemp, or cotton cloth.

Example 6 A large number of thermosensitive coloring devices were manufactured using the manufacturing apparatus shown in FIG. Average degree of polymerization 100
Polyvinyl alcohol (PVA) and ethylene glycol (20% by weight based on PVA) were dissolved in boiling water. This raw material solution was applied to the filter paper carrier 5 for ion exchange by the coating apparatus shown in 1 of FIG. 2, sent to the dryer 2, and dried with hot air at 80 ° C. for 3 minutes to carry the thermosensitive coloring material. The supported amount was 18 g / m ² . The carrier is cut into a width of 10 mm and a length of 30 mm by a cutting device 8 and then placed on a substrate 7 made of a 0.2 mm thick polypropylene sheet having an adhesive layer and a release liner on the back surface. A cellophane tape was pressed and pressed from above and sealed between the substrate 7 and the surface protection tape 6.

The thermosensitive coloring device thus produced was pale yellow. When the thermosensitive coloring device manufactured in the above process was irradiated with light at room temperature for 30 seconds using a light irradiation device in which five 20 W low-pressure mercury lamps were arranged, the device changed from yellow to colorless. Then, the device was immediately stored in a freezer at 0 ° C. In this state, even if stored in an atmosphere at 0 ° C. for 2 months, the color was colorless and no color was formed. However, when the thermosensitive coloring device was taken out of the freezer at 0 ° C. into the room at 25 ° C., the device developed reddish purple in a few minutes. This is because at room temperature Au
This is because the surface plasmon absorption of the fine particles became clear by the growth of the fine particles. Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. It was found that such a photoreduction reaction of HAuCl ₄ was extremely slow in the absence of ethylene glycol and was not used for practical use. The average particle size of the Au fine particles generated at room temperature was 5 nm, and the particle size distribution was found to be small. Even when the same thermosensitive coloring device was stored in an atmosphere at 10 ° C. for one month, it was colorless and did not develop color. However, when the complex was taken out of the refrigerator at 10 ° C. into the room at 25 ° C., the complex again developed a purple-red color within a few minutes.

Further, such a thermosensitive coloring device can be used one at a time.
It was found that they had almost the same characteristics when manufactured 100 times 10 times.

Further, in this embodiment, filter paper for ion exchange was used as the carrier, but qualitative filter paper, quantitative filter paper, glass fiber filter paper,
Similar effects could be obtained by using silica fiber filter paper, paper made from Manila hemp, or cotton cloth.

Example 7 A large number of thermosensitive coloring devices were manufactured using the manufacturing apparatus shown in FIG. Average degree of polymerization 100
Polyvinyl alcohol (PVA) and ethylene glycol (20% by weight based on PVA) were dissolved in boiling water. This raw material solution was applied to the filter paper carrier 5 for ion exchange by the coating apparatus shown in 1 of FIG. 2, sent to the dryer 2, and dried with hot air at 80 ° C. for 3 minutes to carry the thermosensitive coloring material. The supported amount was 18 g / m ² . The carrier is cut into a width of 10 mm and a length of 30 mm by a cutting device 8 and then placed on a substrate 7 made of a 0.2 mm thick polypropylene sheet having an adhesive layer and a release liner on the back surface. A cellophane tape was pressed and pressed from above and sealed between the substrate 7 and the surface protection tape 6. Thereafter, when light irradiation was performed at room temperature for 10 seconds using a tunnel-shaped light irradiation device 3 in which five 20 W low-pressure mercury lamps were continuously arranged, the element changed from yellow to colorless. Then, the thermosensitive coloring device produced in the above steps was immediately stored in a freezer at −20 ° C. In this state, it was colorless even after storage for 2 months, and did not develop color. However, when the thermosensitive coloring device was taken out of the freezer into a room at 25 ° C., the device developed a reddish purple color in a few minutes. This is because the surface plasmon absorption of the fine particles became clear due to the growth of the Au fine particles at room temperature. Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. It was found that such a photoreduction reaction of HAuCl ₄ was extremely slow in the absence of ethylene glycol and was not used for practical use. The average particle size of the Au fine particles generated at room temperature is 5n.
m and the particle size distribution was found to be small. Even when the same thermosensitive coloring device was stored in an atmosphere at 10 ° C. for one month, it was colorless and did not develop color. However, when the complex was taken out of the refrigerator at 10 ° C. into the room at 25 ° C., the complex again developed a purple-red color within a few minutes.

Further, such a thermosensitive coloring device can be used one at a time.
It was found that they had almost the same characteristics when manufactured 100 times 10 times.

Further, in this embodiment, the filter paper for ion exchange was used as the carrier, but qualitative filter paper, quantitative filter paper, glass fiber filter paper,
Similar effects could be obtained by using silica fiber filter paper, paper made from Manila hemp, or cotton cloth.

Example 8 Using the manufacturing apparatus shown in FIG. 2, a large number of thermosensitive coloring devices were manufactured. Average degree of polymerization 100
Polyvinyl alcohol (PVA) and ethylene glycol (20% by weight based on PVA) were dissolved in boiling water. This raw material solution was applied to the filter paper carrier 5 for ion exchange by the coating apparatus shown in 1 of FIG. 2, sent to the dryer 2, and dried with hot air at 80 ° C. for 3 minutes to carry the thermosensitive coloring material. The supported amount was 18 g / m ² . The carrier is cut into a width of 10 mm and a length of 30 mm by a cutting device 8 and then placed on a substrate 7 made of a 0.2 mm thick polypropylene sheet having an adhesive layer and a release liner on the back surface. A cellophane tape was pressed and pressed from above and sealed between the substrate 7 and the surface protection tape 6. Thereafter, when light irradiation was performed at room temperature for 10 seconds using a tunnel-shaped light irradiation device 3 in which five 20 W low-pressure mercury lamps were continuously arranged, the element changed from yellow to colorless. Immediately after the light irradiation, the thermosensitive coloring device was stored while being wound up in a freezer 4 at -20 ° C. In this state, it was colorless even after storage for one month, and did not develop color. Then, each of the portions where the thermosensitive coloring element was not formed was cut into a width of 10 mm and a length of 20 mm, and was taken out of the freezer into a room at 25 ° C., and a reddish purple color was formed in a few minutes. This is because the surface plasmon absorption of the fine particles became clear due to the growth of the Au fine particles at room temperature. Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. When 100 such thermosensitive coloring devices were manufactured 10 times at a time, it was found that they had almost the same characteristics.

Further, in this example, filter paper for ion exchange was used as a carrier, but qualitative filter paper, quantitative filter paper, glass fiber filter paper,
Similar effects could be obtained by using silica fiber filter paper, paper made from Manila hemp, or cotton cloth.

Example 9 A large number of thermosensitive coloring devices were manufactured using the manufacturing apparatus shown in FIG. Average degree of polymerization 100
The polyvinyl alcohol (PVA) aqueous solution prepared by dissolving polyvinyl alcohol (PVA) in hot water is applied to the filter paper carrier 5 for ion exchange by the application device shown in FIG. 9 and sent to the drier 10 at 80 ° C. for 3 minutes. It was dried by hot air and solidified, and the surface of the filter paper was covered with PVA and supported. 10 g of PVA coated
/ m ² . Further, HAuCl ₄ was added to the raw materials shown in Table 1 (Example 1) so that Au was 1 wt% with respect to SiO ₂ , and then stirred to prepare a sol solution similar to that of Example 1. The raw material solution was applied to the filter paper carrier 5 for ion exchange coated with PVA by the coating apparatus shown in 1 of FIG. 3, sent to the dryer 2, and dried with hot air at 80 ° C. for 3 minutes.
A heat-sensitive coloring material was supported. The loading amount was 19 g / m ² . The carrier prepared in this manner is formed into a circle having a diameter of 10 mm by a punching device 8 and then placed on a substrate 7 made of a 0.2 mm thick polypropylene sheet having an adhesive layer and a release liner on the back surface. Then, a cellophane tape was pressed and pressed thereon, and sealed between the base 7 and the surface protection tape 6.

The thermosensitive coloring device thus manufactured was pale yellow. When the thermosensitive coloring device manufactured in the above process was irradiated with light at room temperature for 30 seconds using a light irradiation device in which five 20 W low-pressure mercury lamps were arranged, the device changed from yellow to colorless. Then, the device was immediately stored in a freezer at 0 ° C. In this state, even if stored in an atmosphere at 0 ° C. for 2 months, the color was colorless and no color was formed. However, when the thermosensitive coloring device was taken out of the freezer at 0 ° C. into the room at 25 ° C., the device developed reddish purple in a few minutes. This is because at room temperature Au
This is because the surface plasmon absorption of the fine particles became clear by the growth of the fine particles. Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. It was found that such a photoreduction reaction of HAuCl ₄ was extremely slow in the absence of ethylene glycol and was not used for practical use. The average particle size of the Au fine particles generated at room temperature was 5 nm, and the particle size distribution was found to be small. Even when the same thermosensitive coloring device was stored in an atmosphere at 10 ° C. for one month, it was colorless and did not develop color. However, when the complex was taken out of the refrigerator at 10 ° C. into the room at 25 ° C., the complex again developed a purple-red color within a few minutes.

Further, such a thermosensitive coloring device can be used one at a time.
It was found that they had almost the same characteristics when manufactured 100 times 10 times.

Similar effects could be obtained by using polyvinyl butyral, polystyrene, polyacrylic acid, acrylonitrile / styrene copolymer, or fluororesin instead of the PVA resin coated on the carrier surface.

As a comparative example, when a thermosensitive coloring element similar to the above was prepared without coating the filter paper with a resin, color nonuniformity and variation in coloring start time due to a temperature change were compared with the example. It was observed. This is considered to be due to the non-uniformity of the surface shape of the filter paper and the influence of impurities contained or moisture.

In this example, a filter paper for ion exchange was used as the carrier. However, qualitative filter paper, quantitative filter paper, glass fiber filter paper, silica fiber filter paper, paper made from Manila hemp as a raw material, or cotton cloth was used. Also obtained the same effect.

(Example 10) Using the manufacturing apparatus shown in FIG. 3, a large number of thermosensitive coloring devices were manufactured. Table 1 (Example 1)
A sol solution similar to that shown in was prepared. This sol solution is applied to the filter paper carrier 5 for ion exchange by the application device shown in 9 of FIG. 3, sent to the drier 10, and solidified by drying with hot air at 80 ° C. for 3 minutes, and the surface of the filter paper is made of SiO ₂ . Coated and loaded. The amount of coated SiO ₂ was 11 g / m ² . Next, it was prepared by dissolving polyvinyl alcohol (PVA) having an average degree of polymerization of 1000 and ethylene glycol (20% by weight based on PVA) in boiling water. This raw material solution is applied to the filter paper carrier 5 for ion exchange coated with SiO ₂ by the coating apparatus shown in FIG.
It was dried with hot air at 80 ° C. for 3 minutes to carry the thermosensitive coloring material. The supported amount was 18 g / m ² . The carrier prepared in this manner is formed into a circle having a diameter of 10 mm by a punching device 8 and then placed on a substrate 7 made of a 0.2 mm thick polypropylene sheet having an adhesive layer and a release liner on the back surface. Then, a cellophane tape was pressed and pressed thereon, and sealed between the base 7 and the surface protection tape 6.

The thermosensitive coloring device thus produced was pale yellow. When the thermosensitive coloring device manufactured in the above process was irradiated with light at room temperature for 30 seconds using a light irradiation device in which five 20 W low-pressure mercury lamps were arranged, the device changed from yellow to colorless. Then, the device was immediately stored in a freezer at 0 ° C. In this state, even if stored in an atmosphere at 0 ° C. for 2 months, the color was colorless and no color was formed. However, when the thermosensitive coloring device was taken out of the freezer at 0 ° C. into the room at 25 ° C., the device developed reddish purple in a few minutes. This is because at room temperature Au
This is because the surface plasmon absorption of the fine particles became clear by the growth of the fine particles. Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. It was found that such a photoreduction reaction of HAuCl ₄ was extremely slow in the absence of ethylene glycol and was not used for practical use. The average particle size of the Au fine particles generated at room temperature was 5 nm, and the particle size distribution was found to be small. Even when the same thermosensitive coloring device was stored in an atmosphere at 10 ° C. for one month, it was colorless and did not develop color. However, when the complex was taken out of the refrigerator at 10 ° C. into the room at 25 ° C., the complex again developed a purple-red color within a few minutes.

Further, such a thermosensitive coloring device can be used one at a time.
It was found that they had almost the same characteristics when manufactured 100 times 10 times.

The same effect as SiO ₂ could be obtained by using Al ₂ O ₅ or TiO ₂ instead of SiO ₂ covering the substrate surface.

Further, it is possible to obtain a thermosensitive coloring element having the same effect as the PVA resin by using polyvinyl butyral, polystyrene, polyacrylic acid, acrylonitrile / styrene copolymer or fluororesin instead of the PVA resin serving as the matrix. Was completed.

As a comparative example, a thermosensitive coloring element similar to the above was produced without coating the filter paper with a resin. As compared with the example, the coloring was non-uniform, and the variation in the coloring start time due to a temperature change. It was observed. This is considered to be due to the non-uniformity of the surface shape of the filter paper and the influence of impurities contained or moisture.

In this embodiment, a filter paper for ion exchange was used as the carrier. However, qualitative filter paper, quantitative filter paper, glass fiber filter paper, silica fiber filter paper, paper made from Manila hemp, or cotton cloth was used. Also obtained the same effect.

Example 11 Using the manufacturing apparatus shown in FIG. 3, a large number of thermosensitive coloring devices were manufactured. Table 1 (Example 1)
A sol solution similar to that shown in was prepared. This sol solution is applied to the filter paper carrier 5 for ion exchange by the application device shown in 9 of FIG. 3, sent to the drier 10 and solidified by drying with hot air at 80 ° C. for 3 minutes, and the filter paper surface is made of SiO ₂ . Coated and loaded. The amount of coated SiO ₂ was 11 g / m ² . Next, it was prepared by dissolving polyvinyl alcohol (PVA) having an average degree of polymerization of 1000 and ethylene glycol (20% by weight based on PVA) in boiling water. This raw material solution is applied to the filter paper carrier 5 for ion exchange coated with SiO ₂ by the coating apparatus shown in FIG.
It was dried with hot air at 80 ° C. for 3 minutes to carry the thermosensitive coloring material. The supported amount was 18 g / m ² . The carrier prepared in this manner is formed into a circle having a diameter of 10 mm by a punching device 8 and then placed on a substrate 7 made of a 0.2 mm thick polypropylene sheet having an adhesive layer and a release liner on the back surface. Then, a cellophane tape was pressed and pressed thereon, and sealed between the base 7 and the surface protection tape 6. Thereafter, when light irradiation was performed at room temperature for 10 seconds using a tunnel-shaped light irradiation device 3 in which five 20 W low-pressure mercury lamps were continuously arranged, the element changed from yellow to colorless. Then, the thermosensitive coloring device produced in the above steps is immediately replaced by -2.
Stored in a 0 ° C. freezer. In this state, it was colorless even after storage for 2 months, and did not develop color. However, when the thermosensitive coloring device was taken out of the freezer into a room at 25 ° C., the device developed a reddish purple color in a few minutes. This is because the surface plasmon absorption of the fine particles became clear due to the growth of the Au fine particles at room temperature. Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. Such HAu
It was found that the photoreduction reaction of Cl ₄ was extremely slow in the absence of ethylene glycol and was not used for practical use. The average particle size of the Au fine particles generated at room temperature was 5 nm, and the particle size distribution was found to be small. Even when the same thermosensitive coloring device was stored in an atmosphere at 10 ° C. for one month, it was colorless and did not develop color. However, this complex
When it was taken out of the refrigerator at 0 ° C. to the room at 25 ° C., the color of the sample turned reddish purple in a few minutes.

Further, such a thermosensitive coloring device can be used one at a time.
It was found that they had almost the same characteristics when manufactured 100 times 10 times.

The same effect as SiO ₂ could be obtained by using Al ₂ O ₅ or TiO ₂ instead of SiO ₂ covering the substrate surface.

Further, it is possible to obtain a thermosensitive coloring element having the same effect as the PVA resin by using polyvinyl butyral, polystyrene, polyacrylic acid, acrylonitrile / styrene copolymer, or fluororesin instead of the PVA resin serving as a matrix. Was completed.

As a comparative example, a thermosensitive coloring element similar to that described above was produced without coating the filter paper with a resin. As compared with the embodiment, nonuniform coloring and variation in coloring start time due to temperature change were compared. It was observed. This is considered to be due to the non-uniformity of the surface shape of the filter paper and the influence of impurities contained or moisture.

In this example, a filter paper for ion exchange was used as the carrier. However, qualitative filter paper, quantitative filter paper, glass fiber filter paper, silica fiber filter paper, paper made from Manila hemp, or cotton cloth was used. Also obtained the same effect.

(Example 12) Using the manufacturing apparatus shown in FIG. 3, a large number of thermosensitive coloring devices were manufactured. Table 1 (Example 1)
A sol solution similar to that shown in was prepared. This sol solution is applied to the filter paper carrier 5 for ion exchange by the application device shown in 9 of FIG. 3, sent to the drier 10, and solidified by drying with hot air at 80 ° C. for 3 minutes, and the surface of the filter paper is made of SiO ₂ . Coated and loaded. The amount of coated SiO ₂ was 11 g / m ² . Next, it was prepared by dissolving polyvinyl alcohol (PVA) having an average degree of polymerization of 1000 and ethylene glycol (20% by weight based on PVA) in boiling water. This raw material solution is applied to the filter paper carrier 5 for ion exchange coated with SiO ₂ by the coating apparatus shown in FIG.
It was dried with hot air at 80 ° C. for 3 minutes to carry the thermosensitive coloring material. The supported amount was 18 g / m ² . The carrier prepared in this manner is formed into a circle having a diameter of 10 mm by a punching device 8 and then placed on a substrate 7 made of a 0.2 mm thick polypropylene sheet having an adhesive layer and a release liner on the back surface. Then, a cellophane tape was pressed and pressed thereon, and sealed between the base 7 and the surface protection tape 6. Thereafter, when light irradiation was performed at room temperature for 10 seconds using a tunnel-shaped light irradiation device 3 in which five 20 W low-pressure mercury lamps were continuously arranged, the element changed from yellow to colorless. Immediately after the light irradiation, the thermosensitive coloring device was stored while being wound up in a freezer 4 at -20 ° C. In this state, it was colorless even after storage for one month, and did not develop color. However, when the thermosensitive coloring device was taken out of the freezer into a room at 25 ° C., the device developed a reddish purple color in a few minutes. This is because the surface plasmon absorption of the fine particles became clear due to the growth of the Au fine particles at room temperature. Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. Such HAuC
photoreduction reaction of l ₄ is extremely slow when ethylene glycol is not present, the actual use was found not used. The average particle size of the Au fine particles generated at room temperature was 5 nm, and the particle size distribution was found to be small. Even when the same thermosensitive coloring device was stored in an atmosphere at 10 ° C. for one month, it was colorless and did not develop color. However, this complex was
When it was taken out of the refrigerator at 25 ° C. into the room at 25 ° C., it again developed a purple-red color in a few minutes.

Further, such a thermosensitive coloring device can be used one at a time.
It was found that they had almost the same characteristics when manufactured 100 times 10 times.

The same effect as SiO ₂ could be obtained by using Al ₂ O ₅ or TiO ₂ instead of SiO ₂ covering the substrate surface.

Further, it is possible to obtain a thermosensitive coloring element having the same effect as the PVA resin by using polyvinyl butyral, polystyrene, polyacrylic acid, acrylonitrile / styrene copolymer, or fluororesin instead of the PVA resin serving as a matrix. Was completed.

As a comparative example, a thermosensitive coloring element similar to that described above was prepared without coating the filter paper with resin. As compared with the example, non-uniform coloring and variation in coloring start time due to temperature change were observed. It was observed. This is considered to be due to the non-uniformity of the surface shape of the filter paper and the influence of impurities contained or moisture.

In this example, a filter paper for ion exchange was used as the carrier, but qualitative filter paper, quantitative filter paper, glass fiber filter paper, silica fiber filter paper, paper made from Manila hemp, or cotton cloth was used. Also obtained the same effect.

Example 13 Using the manufacturing apparatus shown in FIG. 3, a large number of thermosensitive coloring devices were manufactured. Average molecular weight 100
A polyacrylic acid (PAA) was dissolved in ion-exchanged water to prepare a PAA aqueous solution. This solution was applied to the filter paper carrier 5 for ion exchange by the application device shown in FIG. 3 and sent to the drier 10 where it was solidified by drying with hot air at 80 ° C. for 3 minutes, and the surface of the filter paper was coated with PAA. Carried. The amount of PAA coated was 14 g / m ² . Next, it was prepared by dissolving polyvinyl alcohol (PVA) having an average degree of polymerization of 1000 and ethylene glycol (20% by weight based on PVA) in boiling water. This raw material solution is applied to the ion-exchange filter paper carrier 5 coated with PAA by the coating apparatus shown in 1 of FIG. 3, sent to the dryer 2, and dried with hot air at 80 ° C. for 3 minutes to obtain a thermosensitive coloring material. Carried. 17g /
m ² . The carrier produced in this manner was formed into a circular shape having a diameter of 10 mm by the punching device 8, and then the adhesive layer and the release liner were provided on the back surface in a thickness of 0.2 mm.
Placed on a substrate 7 made of a polypropylene sheet of
A cellophane tape is pressed from above and press-bonded, and the substrate 7
And the surface protection tape 6. Thereafter, when light irradiation was performed at room temperature for 10 seconds using a tunnel-shaped light irradiation device 3 in which five 20 W low-pressure mercury lamps were continuously arranged, the element changed from yellow to colorless. Immediately after the light irradiation, the thermosensitive coloring device was stored while being wound up in a freezer 4 at -20 ° C. In this state, it was colorless even after storage for one month, and did not develop color. However, this thermosensitive coloring device was removed from the freezer by two.
After being taken out into a room at 5 ° C., it developed a purple-red color in a few minutes. This is because the surface plasmon absorption of the fine particles became clear due to the growth of the Au fine particles at room temperature.
Further, the color of the thermosensitive coloring element once colored did not disappear even when the temperature was lowered again. It was found that such a photoreduction reaction of HAuCl ₄ was extremely slow in the absence of ethylene glycol and was not used for practical use. Even when the same thermosensitive coloring device was stored in an atmosphere at 10 ° C. for one month, it was colorless and did not develop color. However, this complex was
When the product was taken out of the refrigerator into a room at 25 ° C., a reddish purple color was formed in a few minutes.

Further, such a thermosensitive coloring device can be used one at a time.
It was found that they had almost the same characteristics when manufactured 100 times 10 times.

Further, a thermosensitive coloring element having the same effect as the PAA resin can be obtained by using polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile / styrene copolymer, or fluororesin instead of the PAA resin coating the filter paper. Was completed.

Further, it is possible to obtain a thermosensitive coloring element having the same effect as the PVA resin by using polyvinyl butyral, polystyrene, polyacrylic acid, acrylonitrile / styrene copolymer, or fluororesin instead of the PVA resin serving as the matrix. Was completed.

As a comparative example, a thermosensitive coloring element similar to that described above was produced without coating the filter paper with a resin. As compared with the example, non-uniform coloring and variation in coloring start time due to temperature change were compared. It was observed. This is considered to be due to the non-uniformity of the surface shape of the filter paper and the influence of impurities contained or moisture.

In this example, a filter paper for ion exchange was used as the carrier. However, qualitative filter paper, quantitative filter paper, glass fiber filter paper, silica fiber filter paper, paper made from Manila hemp, or cotton cloth was used. Also obtained the same effect.

[0096]

As described above, according to the apparatus for manufacturing a thermosensitive coloring element of the present invention, the apparatus is composed of fine metal fine particles and a matrix material composed of glass or resin, and the size of the fine metal fine particles increases with increasing temperature. Accordingly, it is possible to continuously provide a large number of thermosensitive coloring elements in a form in which a thermosensitive coloring material that increases irreversibly is held on a substrate.

Further, in the apparatus for manufacturing a thermosensitive coloring element of the present invention, an apparatus for forming a thermosensitive coloring material layer on the surface of a substrate by printing or applying and drying a thermosensitive coloring material raw material solution on at least a part of a substrate; Since a device for installing a surface protection sheet or a tape on the coloring material layer is provided, a large number of uniform thermosensitive coloring devices having uniform characteristics can be provided.

Further, in the apparatus for manufacturing a thermosensitive coloring element of the present invention, an apparatus for forming or printing a thermosensitive coloring material layer on the surface of a substrate by printing or applying and drying a thermosensitive coloring material raw material solution on at least a part of the substrate; A device for installing a surface protective sheet or tape on the color forming material layer, and a light irradiating device for irradiating the thermosensitive coloring material with light from the surface protective sheet or tape side, so that a uniform thermosensitive coloring element with uniform characteristics is provided. Can be provided in large quantities.

Further, in the apparatus for producing a thermosensitive coloring element of the present invention, an apparatus for printing or coating a thermosensitive coloring material raw material solution on at least a part of a substrate and drying to form a thermosensitive coloring material layer on the surface of the substrate; A device for forming a surface protective sheet or tape on the color forming material layer, a light irradiating device for irradiating the thermosensitive coloring material with light from the surface protecting sheet or tape side, and a refrigeration for keeping the thermosensitive coloring material at a low temperature after the light irradiation Since the apparatus is provided, a large number of uniform thermosensitive coloring elements having uniform characteristics can be provided.

Further, in the apparatus for manufacturing a thermosensitive coloring element of the present invention, an apparatus for coating or impregnating a carrier with a thermosensitive coloring material material solution, drying and supporting the carrier, and cutting or punching into a predetermined size; Since there is provided an apparatus for sandwiching and fixing the carrier carrying the thermosensitive coloring material raw material solution between the surface protecting sheet and the tape, a large number of uniform thermosensitive coloring elements having uniform characteristics can be provided.

Further, in the apparatus for manufacturing a thermosensitive coloring element of the present invention, an apparatus for coating or impregnating a carrier with a thermosensitive coloring material raw material solution, drying and supporting the carrier, and cutting or punching into a predetermined size; Since a device that holds the carrier carrying the thermosensitive coloring material solution between the surface protecting sheet or the tape is fixed, and a light irradiation device that irradiates the thermosensitive coloring material with light from the surface protecting sheet or the tape side is provided. In addition, a large number of uniform thermosensitive coloring elements having uniform characteristics can be provided.

Further, in the apparatus for manufacturing a thermosensitive coloring element of the present invention, an apparatus for coating or impregnating a carrier for a thermosensitive coloring material raw material, drying and supporting the carrier, and cutting or punching the carrier into a predetermined size; An apparatus for sandwiching and fixing the carrier supporting the thermosensitive coloring material raw material solution between the surface protecting sheet or the tape, a light irradiating apparatus for irradiating the thermosensitive coloring material with light from the surface protecting sheet or the tape side, and the light irradiation Since a refrigerating device for keeping the thermosensitive coloring material at a low temperature is provided later, a large number of uniform thermosensitive coloring devices having uniform characteristics can be provided. It is a thing.

Further, in the apparatus for manufacturing a thermosensitive coloring element of the present invention, an inorganic substance or a resin is coated or impregnated on a carrier, dried and supported on the carrier, and a raw material solution of a thermosensitive coloring material is applied or impregnated on the carrier and dried. Supported on a carrier,
Since it has a device for cutting or punching to a predetermined size and a device for sandwiching and fixing the carrier carrying the inorganic substance or resin and the raw material solution of the thermosensitive coloring material between the substrate and the surface protection sheet or tape, Can provide a large amount of uniform thermosensitive coloring devices with uniformity.

Further, in the apparatus for manufacturing a thermosensitive coloring device of the present invention, an inorganic substance or a resin is coated or impregnated on a carrier, dried and supported on the carrier, and a thermosensitive coloring material raw material solution is coated or impregnated on the carrier and dried. Supported on a carrier,
A device for cutting or punching to a predetermined size, a device for sandwiching and fixing a carrier carrying the inorganic substance or resin and the thermosensitive coloring material raw material solution between a substrate and a surface protection sheet or tape, and the surface protection sheet or Since the light irradiating device for irradiating the thermosensitive coloring material with light from the tape side is provided, a large number of uniform thermosensitive coloring elements having uniform characteristics can be provided.

Further, the apparatus for producing a thermosensitive coloring device of the present invention is characterized in that an inorganic substance or a resin is coated or impregnated on a carrier, dried and supported on the carrier, and a raw material solution of a thermosensitive coloring material is coated or impregnated on the carrier and dried. And a device for cutting or punching the carrier into a predetermined size, a device for sandwiching and fixing the carrier carrying the thermosensitive coloring material material solution between a substrate and a surface protection sheet or tape, and the surface protection sheet Alternatively, a large number of uniform heat-sensitive coloring elements with uniform characteristics are provided because of the provision of a light irradiation device for irradiating light to the heat-sensitive coloring material from the tape side and a refrigerating device for keeping the heat-sensitive coloring material at a low temperature after the light irradiation. can do.

Further, in the thermosensitive coloring element manufactured in the present invention, the thermosensitive coloring material portion is smaller in shape than the substrate, the surface protection sheet or the tape, and is completely sealed by both, so that the reliability and the characteristics are high. It is possible to provide a large number of uniform thermosensitive coloring elements.

Further, a dryer for drying the thermosensitive coloring material comprises:
A hot-air blowing type or a far-infrared lamp having a surface temperature of 120 ° C. or less can provide a large amount of uniform thermosensitive coloring elements with uniform characteristics without deteriorating the base or carrier.

When a xenon lamp, a halogen lamp, a high-pressure mercury lamp, or a low-pressure mercury lamp is used as a light source for irradiating ultraviolet rays, a large number of uniform thermosensitive coloring devices having uniform characteristics can be provided. Furthermore, if a tunnel-shaped light irradiating device is used in which a plurality of light sources are arranged vertically and horizontally, it is possible to efficiently irradiate light in a short time and to provide a large number of uniform thermosensitive coloring devices with more uniform characteristics. Can be.

A freezer or refrigerator that stores the produced thermosensitive coloring device at a low temperature of 0 ° C. or less can provide a large number of uniform thermosensitive coloring devices having uniform characteristics. In addition, it is possible to provide a large amount of uniform thermosensitive coloring devices having uniform characteristics without taking up space for a device that can be stored while winding the thermosensitive coloring devices.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of a manufacturing apparatus of a thermosensitive coloring element according to an embodiment of the present invention.

FIG. 2 is a configuration diagram of a manufacturing apparatus for a thermosensitive coloring element according to an embodiment of the present invention.

FIG. 3 is a configuration diagram of a manufacturing apparatus for a thermosensitive coloring element according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Printing device or coating device 2, 10 Drying device 3 Light irradiation device 4 Refrigeration device 5, 7 Substrate 6 Surface protection sheet or surface protection tape 8 Cutting device or punching device 9 Printing device or coating device

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Naoki Ohara 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. F-term (reference) 2F056 VA01 VA05 VA10

Claims (20)

[Claims] 1. A step of printing or applying a heat-sensitive coloring material raw material solution on at least a part of a substrate to form a heat-sensitive coloring material layer on a surface of the substrate, and installing a surface protection sheet or a tape on the heat-sensitive coloring material layer. A method for producing a thermosensitive coloring element, comprising the steps of: 2. A step of printing or applying a heat-sensitive coloring material raw material solution on at least a part of the substrate to form a heat-sensitive coloring material layer on the surface of the substrate, and installing a surface protection sheet or tape on the heat-sensitive coloring material layer. And a step of irradiating the thermosensitive coloring material with light from the surface protective sheet or the tape side. 3. A step of printing or applying a heat-sensitive coloring material raw material solution on at least a part of the substrate to form a heat-sensitive coloring material layer on the surface of the base, and applying a surface protective sheet or tape to the heat-sensitive coloring material layer. A method for producing a thermosensitive coloring element, comprising: forming; irradiating the thermosensitive coloring material with light from the surface protection sheet or the tape side; and freezing the thermosensitive coloring material at a low temperature after the light irradiation. 4. A step of coating or impregnating the carrier with a thermosensitive coloring material raw material solution, drying and supporting the carrier, cutting or punching the carrier into a predetermined size, and placing the thermosensitive coloring material between the substrate and the surface protection sheet or tape. A method for manufacturing a thermosensitive coloring element, comprising a step of sandwiching and fixing a carrier supporting a coloring material material solution. 5. A step of coating or impregnating a carrier with a thermosensitive coloring material raw material solution, drying and supporting the carrier, cutting or punching the carrier into a predetermined size, and placing the thermosensitive coloring material between a substrate and a surface protection sheet or tape. A method for producing a thermosensitive coloring element, comprising: a step of sandwiching and fixing a carrier supporting a coloring material material solution; and a step of irradiating light to the thermosensitive coloring material from the surface protective sheet or tape side. 6. A step of coating or impregnating a carrier with a thermosensitive coloring material raw material solution, drying and supporting the carrier, cutting or punching the carrier into a predetermined size, and placing the thermosensitive coloring material between a substrate and a surface protection sheet or tape. A step of sandwiching and fixing a carrier supporting the color forming material solution, a light irradiation step of irradiating the thermosensitive coloring material with light from the surface protective sheet or the tape side, and a freezing step of maintaining the thermosensitive coloring material at a low temperature after the light irradiation A method for producing a thermosensitive coloring element comprising: 7. A step of coating or impregnating an inorganic substance or a resin on a carrier and drying and supporting the carrier, a step of applying or impregnating and drying a thermosensitive coloring material raw material solution on the carrier and supporting the carrier on the carrier, A thermosensitive coloring element comprising: a step of cutting or punching the substrate into a predetermined size; and a step of sandwiching and fixing the carrier carrying the inorganic substance or the resin and the thermosensitive coloring material raw material solution between the substrate and the surface protection sheet or tape. Manufacturing method. 8. A step of coating or impregnating an inorganic substance or a resin on a carrier and drying and supporting the carrier, applying or impregnating and drying a thermosensitive coloring material raw material solution on the carrier and supporting the carrier on the carrier. Cutting or punching into a predetermined size, sandwiching and fixing a carrier supporting the inorganic substance or resin and the thermosensitive coloring material raw material solution between a substrate and a surface protection sheet or tape, and fixing the surface protection sheet. Alternatively, a method for manufacturing a thermosensitive coloring element, comprising a step of irradiating the thermosensitive coloring material with light from the tape side. 9. A step of coating or impregnating an inorganic substance or a resin on a carrier and drying and supporting the carrier, a step of coating or impregnating and drying a thermosensitive coloring material raw material solution on the carrier and supporting the carrier on the carrier. Cutting or punching into a predetermined size, sandwiching and fixing a carrier carrying the thermosensitive coloring material material solution between a substrate and a surface protection sheet or tape, and heat-sensitive from the surface protection sheet or tape side. A method for producing a thermosensitive coloring element, comprising: irradiating the coloring material with light; and holding the thermosensitive coloring material at a low temperature after the light irradiation. 10. The method according to claim 4, wherein the carrier is smaller than the substrate or the surface protection sheet. 11. An apparatus for printing or applying a thermosensitive coloring material raw material solution on at least a part of a substrate and drying to form a thermosensitive coloring material layer on the surface of the base, and a surface protective sheet or tape provided on the thermosensitive coloring material layer. An apparatus for manufacturing a thermosensitive coloring element provided with an apparatus for performing the above. 12. An apparatus for printing or applying a thermosensitive coloring material raw material solution on at least a part of a substrate to form a thermosensitive coloring material layer on a substrate surface, and a surface protection sheet or tape provided on the thermosensitive coloring material layer. And a light irradiating device for irradiating the thermosensitive coloring material with light from the surface protection sheet or the tape side. 13. An apparatus for printing or applying a thermosensitive coloring material raw material solution on at least a part of a substrate to form a thermosensitive coloring material layer on the surface of a substrate, and a surface protective sheet or tape on the thermosensitive coloring material layer. An apparatus for producing a thermosensitive coloring element, comprising: a forming device; a light irradiating device for irradiating the thermosensitive coloring material with light from the surface protection sheet or the tape side; and a refrigerating device for keeping the thermosensitive coloring material at a low temperature after the light irradiation. 14. An apparatus for coating or impregnating a carrier with a thermosensitive coloring material raw material solution, drying and supporting the carrier, and cutting or punching the carrier into a predetermined size, and between the base and the surface protection sheet or tape. An apparatus for manufacturing a thermosensitive coloring element, comprising a device for sandwiching and fixing a carrier supporting a coloring material material solution. 15. An apparatus for coating or impregnating a carrier with a thermosensitive coloring material raw material solution, drying and supporting the carrier and cutting or punching the carrier into a predetermined size, and the thermosensitive material between a substrate and a surface protection sheet or tape. An apparatus for manufacturing a thermosensitive coloring element, comprising: a device for sandwiching and fixing a carrier carrying a coloring material raw material solution; and a light irradiating device for irradiating the thermosensitive coloring material with light from the surface protective sheet or tape side. 16. An apparatus for coating or impregnating a carrier with a thermosensitive coloring material raw material solution, drying and supporting the carrier, and cutting or punching the carrier into a predetermined size, and between the base and the surface protection sheet or tape. A device for sandwiching and fixing a carrier supporting a color forming material solution, a light irradiating device for irradiating the thermosensitive coloring material with light from the surface protective sheet or the tape side, and a refrigeration device for holding the thermosensitive coloring material at a low temperature after the light irradiation An apparatus for manufacturing a thermosensitive coloring device, comprising: 17. An inorganic substance or resin is coated or impregnated on a carrier, dried and supported on the carrier, and a thermosensitive coloring material raw material solution is coated or impregnated on the carrier, dried and supported on the carrier, and the carrier is fixed to a predetermined size. An apparatus for manufacturing a thermosensitive coloring element, comprising: a device for cutting or punching; and a device for sandwiching and fixing a carrier carrying the inorganic substance or resin and a raw material solution of a thermosensitive coloring material between a substrate and a surface protection sheet or tape. 18. An inorganic substance or a resin is coated or impregnated on a carrier, dried and supported on the carrier, and a thermosensitive coloring material raw material solution is coated or impregnated on the carrier, dried and supported on the carrier, and the carrier is fixed to a predetermined size. A device for cutting or punching, a device for sandwiching and fixing the carrier carrying the inorganic substance or resin and the thermosensitive coloring material raw material solution between the substrate and the surface protective sheet or tape, and a thermosensitive coloring from the surface protective sheet or tape side An apparatus for manufacturing a thermosensitive coloring device, comprising a light irradiation device for irradiating a material with light. 19. A carrier in which an inorganic substance or a resin is coated or impregnated, dried and supported on the carrier, and a thermosensitive coloring material raw material solution is coated or impregnated on the carrier, dried and supported on the carrier. A device for cutting or punching, a device for sandwiching and fixing a carrier carrying the thermosensitive coloring material material solution between a substrate and a surface protective sheet or tape, and irradiating light to the thermosensitive coloring material from the surface protective sheet or tape side And a refrigerating device that keeps the thermosensitive coloring material at a low temperature after the light irradiation. 20. The apparatus according to claim 14, wherein the carrier is smaller than the substrate or the surface protection sheet.