JP3468101B2 - Method for producing thermosensitive coloring element and apparatus for producing thermosensitive coloring element - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive color-developing element manufacturing method and manufacturing apparatus which utilize surface plasmon absorption due to the growth of fine metal particles and are used for temperature control during cold storage, refrigeration, and during storage or distribution of frozen food. It is a thing.

[0002]

2. Description of the Related Art Conventionally, as a thermosensitive color-developing element and a manufacturing method thereof, there is one disclosed in, for example, WO97 / 28228. This thermosensitive color-developing element is a plate-shaped element in which metal fine particles are dispersed in a matrix, or is carried on a filter paper or the like, and utilizes surface plasmon absorption due to the growth of the metal fine particles as the temperature rises. Also,
The manufacturing method thereof includes a step of preparing a mixed solution of a raw material for thermosensitive coloring material and a step of irradiating the mixture with ultraviolet rays.

[0003]

However, in the conventional method for manufacturing a thermosensitive color-developing element as described in the above literature,
Although it is good for small-scale production, when it is mass-produced, it is difficult to obtain a thermosensitive color developing element having uniform properties in all, and it is difficult to continuously mass-produce it. There will be a situation where the demand cannot be kept up.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a thermosensitive coloring material comprising fine metal fine particles and a matrix material composed of glass or resin, in which the size of the fine metal fine particles irreversibly increases with an increase in temperature. This is an apparatus for continuously producing a large amount of thermosensitive color-developing elements held on a substrate. This thermosensitive color-developing element is colorless and transparent at a relatively low temperature (-10 ° C), but it irreversibly and efficiently develops color at a temperature near room temperature, and an apparatus capable of mass-producing such thermosensitive color-developing element. The purpose is to provide.

In order to solve this problem, the first aspect of the present invention
The method and apparatus for manufacturing a thermosensitive color-developing element comprises: an apparatus for printing or coating a thermosensitive color-developing material raw material solution on at least a part of a substrate and drying the solution to form a thermosensitive color-developing material layer on the surface of the substrate; It is equipped with a device for installing a surface protection sheet or tape.

In the second method and apparatus for manufacturing a thermosensitive color-developing element of the present invention, the thermosensitive color-developing material raw material solution is printed or applied on at least a part of the substrate and dried to form a thermosensitive color-developing material layer on the surface of the substrate. An apparatus for forming, a device for installing a surface protective sheet or tape on the thermosensitive color developing material layer, and a light irradiation device for irradiating the thermosensitive color developing material with light from the surface protective sheet or tape side.

In the third method and apparatus for manufacturing a thermosensitive color developing element of the present invention, the thermosensitive color developing material raw material solution is printed or applied on at least a part of the substrate and dried to form a thermosensitive color developing material layer on the surface of the substrate. Apparatus for forming, a device for forming 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, and further the thermosensitive coloring material after the light irradiation. Is equipped with a refrigerating device for maintaining the temperature at low temperature.

Further, the fourth method and apparatus for manufacturing a thermosensitive color-developing element of the present invention comprises coating or impregnating a carrier with a raw material solution of a thermosensitive color-developing material, drying it, and supporting it on the carrier, and cutting or punching it 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.

Further, the fifth method and apparatus for manufacturing a thermosensitive color-developing element of the present invention comprises coating or impregnating a carrier with a raw material solution of a thermosensitive color-developing material, drying and supporting the solution on the carrier, and cutting or punching into a predetermined size. For 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 the sixth method and apparatus for manufacturing a thermosensitive color-developing element of the present invention, a thermosensitive color-developing material raw material solution is applied to or impregnated into a carrier, dried and supported on the carrier, and cut or punched into a predetermined size. For 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. The apparatus further comprises a refrigerating apparatus for holding the thermosensitive coloring material at a low temperature after the light irradiation.

In a seventh method and apparatus for manufacturing a thermosensitive color-developing element of the present invention, a carrier is coated with or impregnated with an inorganic substance or a resin, dried and supported on the carrier, and a raw material solution for thermosensitive color-developing material is applied to the carrier. An apparatus for coating, impregnating, and drying, supporting on a carrier, and cutting or punching to a predetermined size, and a carrier carrying the inorganic substance or resin and a thermosensitive coloring material raw material solution between the substrate and the surface protection sheet or tape. It is provided with a device for sandwiching and fixing.

In the eighth method and apparatus for manufacturing a thermosensitive color-developing element of the present invention, a carrier is coated with or impregnated with an inorganic substance or resin, dried and supported on the carrier, and a raw material solution for thermosensitive color-developing material is applied to the carrier. An apparatus for coating, impregnating, and drying, supporting on a carrier, and cutting or punching to a predetermined size, and a carrier carrying the inorganic substance or resin and a thermosensitive coloring material raw material solution between the substrate and the 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.

In a ninth method and apparatus for manufacturing a thermosensitive color-developing element of the present invention, a carrier is coated with or impregnated with an inorganic substance or resin, dried and supported on the carrier. A device for applying or impregnating and drying, supporting on a carrier, and cutting or punching to a predetermined size, and a device for sandwiching and fixing the carrier carrying the above-mentioned raw material solution for thermosensitive coloring material between a substrate and a surface protective 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 refrigeration device for holding the thermosensitive coloring material at a low temperature after the irradiation with light.

Further, in the thermosensitive color-developing element manufactured by the present invention, the thermosensitive color-developing material has a smaller shape than the substrate, the surface protective sheet or the tape and is completely sealed, so that the reliability is high.

Further, in the thermosensitive coloring element produced by the present invention, it is preferable that the fine metal fine particles are at least one selected from gold, platinum, silver, copper, tin, rhodium, palladium or iridium. 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.

Further, the substrate has a function of adhering a waterproof cardboard, a sheet made of polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, or an adhesive layer and a release liner provided on the back surface of the cardboard or sheet. At least one selected from the above is preferable.

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

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

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings.

(Embodiment 1) FIG. 1 shows a schematic structure of an apparatus for manufacturing a thermosensitive color-developing element. The printing device 1 is provided on a part of the substrate 5.
Alternatively, the thermosensitive coloring material raw material solution is printed or applied on at least a part of the substrate by using the coating device 1, and is passed through the dryer 2 to dry the thermosensitive coloring material raw material to form a thermosensitive coloring material layer on the substrate surface. To do. Further, the surface protection sheet 6 or the tape 6 is placed by adhesion or pressure bonding, and light (ultraviolet rays) is irradiated from the surface protection sheet 6 or the tape 6 side to the thermosensitive coloring material using the light irradiation device 3. After the light irradiation The heat-sensitive color-developing material is immediately sent to the freezer 4 and is kept at a low temperature, so that a large number of heat-sensitive color-developing elements can be produced. In actual use, the thermosensitive color-developing element continuous in the form of a tape is appropriately cut into a desired size.

In FIG. 1, the thermosensitive coloring material has a structure in which metal ions are dispersed in a matrix until it is held on a substrate and a surface protective sheet or tape is installed. However, when the thermosensitive coloring material is irradiated with light (ultraviolet rays) from the surface protective sheet or the tape side, the metal ions are reduced by the light and gradually become fine metal fine particles. If the thermosensitive coloring element is held in the freezer (up to 0 ° C.) at such a stage, the size of the fine metal fine particles hardly changes. On the other hand, even if the thermosensitive color-developing element is exposed to a temperature near room temperature even once, the fine metal fine particles start to grow by obtaining heat energy, and the coloration based on the remarkable surface plasmon absorption by the fine metal particles comes to be observed. Therefore, the manufactured thermosensitive coloring element must be used immediately or stored in a freezer or a refrigerator as shown in FIG. When using a thermosensitive color-developing element, the tape-shaped form is appropriately cut into a desired size.

Further, in the thermosensitive color-developing element of the present invention, the amount of the thermosensitive color-developing 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 color development can be noticeably observed. / 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.

The fine metal particles are gold, platinum, silver, copper,
According to a preferred example of the present invention, which is at least one selected from tin, rhodium, palladium or iridium, these metals exhibit coloration based on surface plasmon absorption, and oxygen and other impurities are compared with other metals. Since it is difficult to be affected by the above, and relatively pure metal fine particles can be deposited, it is possible to realize a material exhibiting excellent thermosensitive coloring characteristics.

The amount of the fine metal particles dispersed in the matrix is not particularly limited, but the particle size can be easily controlled, and the fine particles do not easily agglomerate.
About wt%, preferably about 0.05 to 10 wt% is good. When agglomeration occurs, only a part of the material is deeply colored, and it is not possible to confirm whether or not the temperature change is sure.

The average particle size of the fine metal particles after growth is
Although it varies depending on the type, for example, the range of 1 nm to 50 nm is usually preferable, and the range of 3 nm to 30 nm is more preferable for uniform color distribution with a narrow particle size distribution.

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

Further, as the metal salt, HAuCl ₄ , N
aAuCl ₄ , H ₂ PtCl ₆ , AgClO ₄ , CuC
L ₂ , SnCl ₂ , IrCl ₃ , RhCl ₃ and PdCl ₂ are preferred.

Further, as the glass material for coating the matrix or the carrier surface produced by the sol-gel method, silica gel, alumina gel and titania gel which are chemically stable and transparent in an optically wide wavelength range are preferable. The sol-gel method is a method in which a lower alkoxide of a sol-like metal is hydrolyzed, gelled, and heated to obtain glass or ceramics. 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 of things. Water and / or methanol, ethanol, propanol or dihydric alcohol ethylene glycol or propylene glycol is used as a dispersion medium for the sol, and hydrochloric acid or ammonia is usually added as a catalyst for hydrolysis. Further, 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 /
A coating amount of m ^{2 to} 30 g / m ² is more preferable.

Further, the resin coating the matrix or the carrier surface is chemically stable, can contain alcohol and water, and can cover a large area uniformly, such as polyvinyl alcohol, polyvinyl butyral,
It is preferable to use polystyrene, polyacrylic acid, acrylonitrile / styrene copolymer, or fluororesin. Further, the amount of 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.

Further, it is preferable to use cellophane, polyethylene, polypropylene, polyvinyl chloride or polyvinylidene chloride whose sheet or tape has excellent moisture resistance.

Further, the dryer for drying the thermosensitive coloring material is
It is preferable to use a type that blows hot air or a far-infrared lamp that has a surface temperature of 120 ° C. or less without degrading the substrate or the carrier.

Further, 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.

The freezer or refrigerator for storing the produced thermosensitive color-developing element at a low temperature is preferably 0 ° C. or lower, and more preferably, it can be stored while winding the thermosensitive color-developing element because it does not take up space.

(Embodiment 2) FIG. 2 shows a schematic structure of another manufacturing apparatus for a thermosensitive color-developing element. The printing device 1 or the coating device 1 is used on a part of the carrier 5 to print or apply the heat-sensitive coloring material raw material solution on at least a part of the carrier, and the drier 2 is passed through to dry the heat-sensitive coloring material raw material. A heat-sensitive coloring material layer is carried on. Further, after the thermosensitive coloring material is molded 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 tape 6 and the substrate 7, and is adhered or pressure-bonded for encapsulation.
Furthermore, the surface protective sheet 6 or the tape 6 is used to irradiate the thermosensitive coloring material with light (ultraviolet rays) 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 consists of a large number of thermosensitive coloring elements that can be produced in a continuous process.

(Embodiment 3) FIG. 3 shows a schematic structure of another manufacturing apparatus for a thermosensitive color-developing 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 carried on at least a part of the carrier, and is passed through a drier 10 to dry the carrier, and the inorganic substance or the resin is applied to the carrier. Carry. Further, the printing device 1 is continuously attached to a part of the substrate 5.
Alternatively, by using the coating device 1, the thermosensitive color-developing material raw material solution is printed or applied on at least a part of the carrier to carry it, and is passed through the dryer 2 to dry the thermosensitive color-developing material raw material to carry the thermosensitive color-developing material on the carrier. To do. Further, after the thermosensitive coloring material is molded 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 tape 6 and the substrate 7, and is adhered or pressure-bonded for encapsulation. Further, light (ultraviolet rays) is applied to the thermosensitive coloring material from the surface protection sheet 6 or the tape 6 side by using the light irradiation device 3.
The thermosensitive coloring material after the light irradiation is immediately stored in the freezer 4.
The heat-sensitive color-developing element can be mass-produced in a continuous process of feeding it to and keeping it at a low temperature.

[0036]

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

Example 1 Using the manufacturing apparatus shown in FIG. 1, a large number of thermosensitive coloring elements were manufactured. In the sol solution shown in (Table 1), HAuCl ₄ was added to SiO ₂ with 1 w of Au.
A raw material solution was prepared by adding the solution to t% and then stirring.
This raw material solution is coated with an adhesive layer and a release liner on the back surface by the coating apparatus shown in FIG.
It was applied to a part of a substrate 5 made of a polypropylene sheet of 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 pressure-bonded to form a surface protection tape 6.

[0038]

[Table 1]

The thermosensitive color-developing element thus produced was pale yellow. Each of the thermosensitive color-developing elements manufactured in the above process is applied with a width 1
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 side by side, and the element changed from yellow to colorless. Then, this device was immediately stored in a freezer at 0 ° C. In this state, it is colorless even if stored in an atmosphere of 0 ° C for 2 months,
It did not develop color. However, when this thermosensitive color developing element was taken out from a 0 ° C. freezer into a room at 25 ° C., it developed a reddish purple color within 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 color-developing 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 could not be used in actual use. Further, the average particle size of Au fine particles generated at room temperature is 5n.
It was found that the particle size was m and the particle size distribution was small. Even when the same thermosensitive color-developing element was stored in an atmosphere of 10 ° C. for 1 month, it was colorless and did not develop color. However, when this composite was taken out of the refrigerator at 10 ° C. into a room at 25 ° C., it again developed a reddish purple color within a few minutes.

In addition, such a thermosensitive color-developing element is used one at a time.
It was found that when 00 pieces were manufactured 10 times, they had almost the same characteristics.

A similar thermosensitive color-developing element could be produced by using NaAuCl ₄ instead of HAuCl _{4 in} the above process.

In the sol solution of (Table 1), Si (O 2
Even when the C ₂ H _{5) 4} was Al (OC ₂ H _{5) 3} and _{Ti (OC 2 H 5) 4} , could be produced similar thermosensitive coloring elements.

In addition, in the sol solution of (Table 1),
Solution in HAuCl_FourInstead of H₂PtCl₆,
AgClO_Four, CuCl₂, SnCl₂, IrCl₃, Rh
Cl ₃, PdCl₂Even if you use the
Could be manufactured.

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

(Example 2) As in Example 1, a large amount of thermosensitive color-developing elements were manufactured using the manufacturing apparatus shown in FIG. HAuCl ₄ was added to the sol solution shown in Actual Example 1 (Table 1) in an amount of S
A raw material solution was prepared by adding Au so as to be 1 wt% with respect to iO ₂ and then stirring. This raw material solution is applied to a part of a base 5 made of a polypropylene sheet having a thickness of 0.2 mm, which has an adhesive layer and a release liner on the back surface thereof, by the application device 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 surface of the substrate. Further, a cellophane tape was pressed onto the substrate and pressure-bonded to form a surface protection tape 6. After that, when light was irradiated for 10 seconds at room temperature 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 color-developing element produced in the above steps was immediately cut into a width of 10 mm and a length of 20 mm at a location where no thermosensitive color-developing element was formed, and then stored in a freezer at -20 ° C.
In this state, it was colorless even when stored for 2 months, and no color was developed. However, this thermosensitive coloring element was removed from the freezer at 25 ° C.
When I took it out to my room, it turned red 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 that was 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 could not be used in actual use. It was also found that the average particle size of the Au fine particles generated at room temperature was 5 nm and the particle size distribution was small. Even when the same thermosensitive color-developing element was stored in an atmosphere of 10 ° C. for 1 month, it was colorless and did not develop color. However, this composite was removed from the refrigerator at 10 ° C at 25 ° C.
When I took it out to my room, it turned red purple in a few minutes.

In addition, such a thermosensitive color-developing element is used one at a time.
It was found that when 00 pieces were manufactured 10 times, they had almost the same characteristics.

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

(Example 3) Similar to the actual example 1, a large amount of thermosensitive color-developing elements were manufactured using the manufacturing apparatus shown in FIG. HAuCl ₄ was added to the sol solution shown in Actual Example 1 (Table 1) in an amount of S
A raw material solution was prepared by adding Au so as to be 1 wt% with respect to iO ₂ and then stirring. This raw material solution is applied to a part of a base 5 made of a polypropylene sheet having a thickness of 0.2 mm, which has an adhesive layer and a release liner on the back surface thereof, by the application device 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 surface of the substrate. Further, a cellophane tape was pressed onto the substrate and pressure-bonded to form a surface protection tape 6. After that, when light was irradiated for 10 seconds at room temperature 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 irradiation with light, the thermosensitive color developing element was stored while being wound in the freezer 4 at -20 ° C. In this state, it was colorless even after storage for 1 month and did not develop color. Then, after cutting to a width of 10 mm and a length of 20 mm at the portions where the thermosensitive color-developing elements were not formed, when they were taken out of the freezer into a room at 25 ° C., a reddish purple color was developed 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 color-developing element once colored did not disappear even when the temperature was lowered again. Further, when 100 such thermosensitive color-developing elements were manufactured 10 times at a time, it was found that they had substantially the same characteristics.

In this embodiment, a polypropylene sheet having a thickness of 0.2 mm, which has 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 a sheet having an adhesive function in which an adhesive layer and a release liner are provided on the back surface of the sheet.

(Example 4) Similar to Example 1, a large amount of thermosensitive color-developing elements 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 relative to PVA)
Was added to hot water to prepare a PVA aqueous solution, and HAuCl ₄ was added so that Au was 1 wt% with respect to PVA, followed by stirring to prepare a raw material solution. This raw material solution is designated as 1 in FIG.
With the printing device shown in FIG. 2, the adhesive layer and the release liner are provided on the back surface of the base material, which is applied to a part of a base 5 made of a polypropylene sheet having a thickness of 0.2 mm, which is then sent to a dryer 2 and heated at 80 ° C. for 3 It was dried with hot air for a minute to form a thermosensitive coloring material layer on the surface of the substrate. Further, a cellophane tape was pressed onto the substrate and pressure-bonded to form a surface protection tape 6. After that, when light irradiation was continuously performed for 20 seconds at room temperature using a tunnel-shaped light irradiation device 3 in which five 20 W low-pressure mercury lamps were lined up, the element changed from yellow to colorless. Immediately after irradiation with light, the thermosensitive color developing element was stored while being wound in the freezer 4 at -20 ° C. In this state, it was colorless even after storage for 1 month and did not develop color. Then, at a location where the thermosensitive coloring element is not formed, a width of 10 mm and a length of 20 mm
After cutting into pieces, the pieces were taken out of the freezer into a room at 25 ° C. and developed a reddish purple color within 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 color-developing element once colored did not disappear even when the temperature was lowered again. Further, when 100 such thermosensitive color-developing elements were manufactured 10 times at a time, it was found that they had substantially the same characteristics.

In this embodiment, a polypropylene sheet having a thickness of 0.2 mm, which has 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 a sheet having an adhesive function in which an adhesive layer and a release liner are provided on the back surface of the sheet.

Example 5 Using the manufacturing apparatus shown in FIG. 2, a large number of thermosensitive color developing elements were manufactured. Actual example 1 (Table 1)
The sol solution shown in, A and HAuCl ₄ with respect to SiO ₂
A raw material solution was prepared by adding and stirring so that u was 1 wt%. This raw material solution was coated on the filter paper carrier 5 for ion exchange by the coating device 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 color developing material. The supported amount was 16 g / m ² . This carrier is cut by a cutting device 8 to have a width of 10 mm and a length of 30 mm, and then the carrier is placed on a substrate 7 made of a polypropylene sheet having a thickness of 0.2 mm, which has an adhesive layer and a release liner on its back surface. A cellophane tape was pressed from above and pressure-bonded, and enclosed between the substrate 7 and the surface protection tape 6.

The thermosensitive color-developing element thus produced was pale yellow. When the thermosensitive coloring element produced in the above process was irradiated with light for 30 seconds at room temperature using a light irradiation device in which five 20 W low-pressure mercury lamps were arranged, the element changed from yellow to colorless. Then, this device was immediately stored in a freezer at 0 ° C. In this state, even if it was stored in an atmosphere of 0 ° C. for 2 months, it was colorless and did not develop color. However, when this thermosensitive color developing element was taken out from a 0 ° C. freezer into a room at 25 ° C., it developed a reddish purple color within a few minutes. This is Au at room temperature
This is because the surface plasmon absorption of the fine particles became clear due to the growth of the fine particles. Further, the color of the thermosensitive color-developing 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 could not be used in actual use. It was also found that the average particle size of the Au fine particles generated at room temperature was 5 nm and the particle size distribution was small. Even when the same thermosensitive color-developing element was stored in an atmosphere of 10 ° C. for 1 month, it was colorless and did not develop color. However, when this composite was taken out of the refrigerator at 10 ° C. into a room at 25 ° C., it again developed a reddish purple color within a few minutes.

In addition, such a thermosensitive color-developing element is used one at a time.
It was found that when 00 pieces were manufactured 10 times, they had almost the same characteristics.

Further, in this embodiment, the ion exchange filter paper 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 as raw material, or cotton cloth.

(Example 6) A large amount of thermosensitive color-developing elements were manufactured using the manufacturing apparatus shown in FIG. Average degree of polymerization 100
It was prepared by dissolving 0 polyvinyl alcohol (PVA) and ethylene glycol (20% by weight relative to PVA) in hot water. This raw material solution was applied to the filter paper carrier 5 for ion exchange by the application device shown in 1 of FIG. 2, sent to the dryer 2 and dried in hot air at 80 ° C. for 3 minutes to carry the thermosensitive color developing material. The supported amount was 18 g / m ² . This carrier is cut by a cutting device 8 to have a width of 10 mm and a length of 30 mm, and then the carrier is placed on a substrate 7 made of a polypropylene sheet having a thickness of 0.2 mm, which has an adhesive layer and a release liner on its back surface. A cellophane tape was pressed from above and pressure-bonded, and enclosed between the substrate 7 and the surface protection tape 6.

The thermosensitive color-developing element thus produced was pale yellow. When the thermosensitive coloring element produced in the above process was irradiated with light for 30 seconds at room temperature using a light irradiation device in which five 20 W low-pressure mercury lamps were arranged, the element changed from yellow to colorless. Then, this device was immediately stored in a freezer at 0 ° C. In this state, even if it was stored in an atmosphere of 0 ° C. for 2 months, it was colorless and did not develop color. However, when this thermosensitive color developing element was taken out from a 0 ° C. freezer into a room at 25 ° C., it developed a reddish purple color within a few minutes. This is Au at room temperature
This is because the surface plasmon absorption of the fine particles became clear due to the growth of the fine particles. Further, the color of the thermosensitive color-developing 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 could not be used in actual use. It was also found that the average particle size of the Au fine particles generated at room temperature was 5 nm and the particle size distribution was small. Even when the same thermosensitive color-developing element was stored in an atmosphere of 10 ° C. for 1 month, it was colorless and did not develop color. However, when this composite was taken out of the refrigerator at 10 ° C. into a room at 25 ° C., it again developed a reddish purple color within a few minutes.

In addition, such a thermosensitive color-developing element is used one at a time.
It was found that when 00 pieces were manufactured 10 times, they had almost the same characteristics.

Further, in this embodiment, the ion exchange filter paper 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 as raw material, or cotton cloth.

(Embodiment 7) A large amount of thermosensitive color-developing elements were manufactured using the manufacturing apparatus shown in FIG. Average degree of polymerization 100
It was prepared by dissolving 0 polyvinyl alcohol (PVA) and ethylene glycol (20% by weight relative to PVA) in hot water. This raw material solution was applied to the filter paper carrier 5 for ion exchange by the application device shown in 1 of FIG. 2, sent to the dryer 2 and dried in hot air at 80 ° C. for 3 minutes to carry the thermosensitive color developing material. The supported amount was 18 g / m ² . This carrier is cut by a cutting device 8 to have a width of 10 mm and a length of 30 mm, and then the carrier is placed on a substrate 7 made of a polypropylene sheet having a thickness of 0.2 mm, which has an adhesive layer and a release liner on its back surface. A cellophane tape was pressed from above and pressure-bonded, and enclosed between the substrate 7 and the surface protection tape 6. After that, when light was irradiated for 10 seconds at room temperature 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 color-developing element produced in the above process was immediately stored in a freezer at -20 ° C. In this state, it was colorless even when stored for 2 months, and no color was developed. However, when this thermosensitive coloring element was taken out of the freezer into a room at 25 ° C., it developed a reddish purple color within 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 color-developing 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 could not be used in actual use. Further, the average particle size of Au fine particles generated at room temperature is 5n.
It was found that the particle size was m and the particle size distribution was small. Even when the same thermosensitive color-developing element was stored in an atmosphere of 10 ° C. for 1 month, it was colorless and did not develop color. However, when this composite was taken out of the refrigerator at 10 ° C. into a room at 25 ° C., it again developed a reddish purple color within a few minutes.

In addition, such a thermosensitive color-developing element is used one at a time.
It was found that when 00 pieces were manufactured 10 times, they had almost the same characteristics.

In this embodiment, ion exchange filter paper is 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 as raw material, or cotton cloth.

Example 8 Using the manufacturing apparatus shown in FIG. 2, a large number of thermosensitive color developing elements were manufactured. Average degree of polymerization 100
It was prepared by dissolving 0 polyvinyl alcohol (PVA) and ethylene glycol (20% by weight relative to PVA) in hot water. This raw material solution was applied to the filter paper carrier 5 for ion exchange by the application device shown in 1 of FIG. 2, sent to the dryer 2 and dried in hot air at 80 ° C. for 3 minutes to carry the thermosensitive color developing material. The supported amount was 18 g / m ² . This carrier is cut by a cutting device 8 to have a width of 10 mm and a length of 30 mm, and then the carrier is placed on a substrate 7 made of a polypropylene sheet having a thickness of 0.2 mm, which has an adhesive layer and a release liner on its back surface. A cellophane tape was pressed from above and pressure-bonded, and enclosed between the substrate 7 and the surface protection tape 6. After that, when light was irradiated for 10 seconds at room temperature 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 irradiation with light, the thermosensitive color developing element was stored while being wound in the freezer 4 at -20 ° C. In this state, it was colorless even after storage for 1 month and did not develop color. Then, after cutting to a width of 10 mm and a length of 20 mm at the portions where the thermosensitive color-developing elements were not formed, when they were taken out of the freezer into a room at 25 ° C., a reddish purple color was developed 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 color-developing element once colored did not disappear even when the temperature was lowered again. Further, when 100 such thermosensitive color-developing elements were manufactured 10 times at a time, it was found that they had substantially the same characteristics.

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 as raw material, or cotton cloth.

(Example 9) A large amount of thermosensitive color-developing elements were manufactured using the manufacturing apparatus shown in FIG. Average degree of polymerization 100
An aqueous PVA solution prepared by dissolving 0 polyvinyl alcohol (PVA) in hot water was coated on the ion exchange filter paper carrier 5 by the coating device shown in FIG. 9 and sent to the dryer 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. The amount of PVA coated is 10g
It was / 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 the mixture was stirred to prepare a sol solution similar to that in Example 1. This raw material solution is applied to the ion exchange filter paper carrier 5 coated with PVA by the coating device shown in 1 of FIG. 3, sent to the dryer 2 and dried with hot air at 80 ° C. for 3 minutes,
The thermosensitive coloring material was supported. The supported amount was 19 g / m ² . The carrier thus produced is made into a circular shape having a diameter of 10 mm by a punching device 8 and then placed on a base 7 made of a polypropylene sheet having a thickness of 0.2 mm and having an adhesive layer and a release liner on the back surface. Then, a cellophane tape was pressed against it and pressure-bonded, and it was sealed between the substrate 7 and the surface protection tape 6.

The thermosensitive color-developing element thus produced was pale yellow. When the thermosensitive coloring element produced in the above process was irradiated with light for 30 seconds at room temperature using a light irradiation device in which five 20 W low-pressure mercury lamps were arranged, the element changed from yellow to colorless. Then, this device was immediately stored in a freezer at 0 ° C. In this state, even if it was stored in an atmosphere of 0 ° C. for 2 months, it was colorless and did not develop color. However, when this thermosensitive color developing element was taken out from a 0 ° C. freezer into a room at 25 ° C., it developed a reddish purple color within a few minutes. This is Au at room temperature
This is because the surface plasmon absorption of the fine particles became clear due to the growth of the fine particles. Further, the color of the thermosensitive color-developing 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 could not be used in actual use. It was also found that the average particle size of the Au fine particles generated at room temperature was 5 nm and the particle size distribution was small. Even when the same thermosensitive color-developing element was stored in an atmosphere of 10 ° C. for 1 month, it was colorless and did not develop color. However, when this composite was taken out of the refrigerator at 10 ° C. into a room at 25 ° C., it again developed a reddish purple color within a few minutes.

In addition, such a thermosensitive color-developing element is used one at a time.
It was found that when 00 pieces were manufactured 10 times, they had almost the same characteristics.

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 surface of the carrier.

As a comparative example, the same thermosensitive color-developing element as described above was prepared without covering the filter paper with the resin. As a result, the color-developing unevenness and variation in the color-starting time due to temperature change were compared with those of the examples. It was observed. It is considered that this is due to the non-uniformity of the surface shape of the filter paper and the influence of impurities or water content.

In this example, the carrier used was an ion exchange filter paper, but a qualitative filter paper, a quantitative filter paper, a glass fiber filter paper, a silica fiber filter paper, a paper made from Manila hemp as a raw material, or a cotton cloth was used. Was able to obtain a similar effect.

(Example 10) Using the manufacturing apparatus shown in FIG. 3, a large number of thermosensitive coloring elements were manufactured. Table 1 (Example 1)
A sol solution similar to that shown in was prepared. This sol solution was applied to the filter paper carrier 5 for ion exchange by the coating device shown in 9 of FIG. 3, sent to the dryer 10 and dried by hot air at 80 ° C. for 3 minutes to solidify, and the filter paper surface was made of SiO ₂ . Coated and supported. The amount of SiO ₂ coated was 11 g / m ² . Next, polyvinyl alcohol (PVA) having an average degree of polymerization of 1000 and ethylene glycol (20% by weight relative to PVA) were dissolved in hot water to prepare. This raw material solution is applied to the ion exchange filter paper carrier 5 coated with SiO ₂ by the coating device 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 thus produced is made into a circular shape having a diameter of 10 mm by a punching device 8 and then placed on a base 7 made of a polypropylene sheet having a thickness of 0.2 mm and having an adhesive layer and a release liner on the back surface. Then, a cellophane tape was pressed against it and pressure-bonded, and it was sealed between the substrate 7 and the surface protection tape 6.

The thermosensitive color-developing element thus produced was pale yellow. When the thermosensitive coloring element produced in the above process was irradiated with light for 30 seconds at room temperature using a light irradiation device in which five 20 W low-pressure mercury lamps were arranged, the element changed from yellow to colorless. Then, this device was immediately stored in a freezer at 0 ° C. In this state, even if it was stored in an atmosphere of 0 ° C. for 2 months, it was colorless and did not develop color. However, when this thermosensitive color developing element was taken out from a 0 ° C. freezer into a room at 25 ° C., it developed a reddish purple color within a few minutes. This is Au at room temperature
This is because the surface plasmon absorption of the fine particles became clear due to the growth of the fine particles. Further, the color of the thermosensitive color-developing 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 could not be used in actual use. It was also found that the average particle size of the Au fine particles generated at room temperature was 5 nm and the particle size distribution was small. Even when the same thermosensitive color-developing element was stored in an atmosphere of 10 ° C. for 1 month, it was colorless and did not develop color. However, when this composite was taken out of the refrigerator at 10 ° C. into a room at 25 ° C., it again developed a reddish purple color within a few minutes.

In addition, such a thermosensitive color-developing element is used one at a time.
It was found that when 00 pieces were manufactured 10 times, they had almost the same characteristics.

Even if Al ₂ O ₅ or TiO ₂ was used instead of SiO ₂ coating the surface of the substrate, the same effect as that of SiO ₂ could be obtained.

Further, in place of the PVA resin as the matrix, polyvinyl butyral, polystyrene, polyacrylic acid, acrylonitrile / styrene copolymer, or fluororesin can be used to obtain a thermosensitive coloring element having the same effect as the PVA resin. I was able to.

Further, as a comparative example, a thermosensitive color-developing element similar to the above was prepared without covering the filter paper with the resin, and as compared with the examples, the nonuniformity of the color development and the variation in the color-starting time due to the temperature change were observed. It was observed. It is considered that this is due to the non-uniformity of the surface shape of the filter paper and the influence of impurities or water content.

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, silica fiber filter paper, paper made from Manila hemp, or cotton cloth was used. Was able to obtain a similar effect.

(Embodiment 11) A large number of thermosensitive color-developing elements were manufactured using the manufacturing apparatus shown in FIG. Table 1 (Example 1)
A sol solution similar to that shown in was prepared. This sol solution was applied to the filter paper carrier 5 for ion exchange by the coating device shown in 9 of FIG. 3, sent to the dryer 10 and dried by hot air at 80 ° C. for 3 minutes to solidify, and the filter paper surface was made of SiO ₂ . Coated and supported. The amount of SiO ₂ coated was 11 g / m ² . Next, polyvinyl alcohol (PVA) having an average degree of polymerization of 1000 and ethylene glycol (20% by weight relative to PVA) were dissolved in hot water to prepare. This raw material solution is applied to the ion exchange filter paper carrier 5 coated with SiO ₂ by the coating device 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 thus produced is made into a circular shape having a diameter of 10 mm by a punching device 8 and then placed on a base 7 made of a polypropylene sheet having a thickness of 0.2 mm and having an adhesive layer and a release liner on the back surface. Then, a cellophane tape was pressed against it and pressure-bonded, and it was sealed between the substrate 7 and the surface protection tape 6. After that, when light was irradiated for 10 seconds at room temperature 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 element produced in the above steps is immediately
Stored in 0 ° C freezer. In this state, it was colorless even when stored for 2 months, and no color was developed. However, when this thermosensitive coloring element was taken out of the freezer into a room at 25 ° C., it developed a reddish purple color within 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 color-developing element once colored did not disappear even when the temperature was lowered again. HAu like this
It was found that the photoreduction reaction of Cl ₄ was extremely slow in the absence of ethylene glycol and could not be used in practice. It was also found that the average particle size of the Au fine particles generated at room temperature was 5 nm and the particle size distribution was small. Even when the same thermosensitive color-developing element was stored in an atmosphere of 10 ° C. for 1 month, it was colorless and did not develop color. However, this complex
When it was taken out of the refrigerator at 0 ° C into a room at 25 ° C, it turned red purple in a few minutes.

Further, such a thermosensitive color-developing element is used one at a time.
It was found that when 00 pieces were manufactured 10 times, they had almost the same characteristics.

Even if Al ₂ O ₅ or TiO ₂ was used instead of SiO ₂ coating the surface of the substrate, the same effect as that of SiO ₂ could be obtained.

Further, instead of the PVA resin as the matrix, polyvinyl butyral, polystyrene, polyacrylic acid, acrylonitrile / styrene copolymer, or fluororesin can be used to obtain a thermosensitive coloring element having the same effect as the PVA resin. I was able to.

Further, as a comparative example, a thermosensitive coloring element similar to the above was prepared without covering the filter paper with the resin. As a result, as compared with the examples, the unevenness of the coloring and the variation of the coloring start time due to the temperature change were observed. It was observed. It is considered that this is due to the non-uniformity of the surface shape of the filter paper and the influence of impurities or water content.

In this embodiment, ion exchange filter paper 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. Was able to obtain a similar effect.

(Example 12) A large amount of thermosensitive coloring elements were manufactured using the manufacturing apparatus shown in FIG. Table 1 (Example 1)
A sol solution similar to that shown in was prepared. This sol solution was applied to the filter paper carrier 5 for ion exchange by the coating device shown in 9 of FIG. 3, sent to the dryer 10 and dried by hot air at 80 ° C. for 3 minutes to solidify, and the filter paper surface was made of SiO ₂ . Coated and supported. The amount of SiO ₂ coated was 11 g / m ² . Next, polyvinyl alcohol (PVA) having an average degree of polymerization of 1000 and ethylene glycol (20% by weight relative to PVA) were dissolved in hot water to prepare. This raw material solution is applied to the ion exchange filter paper carrier 5 coated with SiO ₂ by the coating device 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 thus produced is made into a circular shape having a diameter of 10 mm by a punching device 8 and then placed on a base 7 made of a polypropylene sheet having a thickness of 0.2 mm and having an adhesive layer and a release liner on the back surface. Then, a cellophane tape was pressed against it and pressure-bonded, and it was sealed between the substrate 7 and the surface protection tape 6. After that, when light was irradiated for 10 seconds at room temperature 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 irradiation with light, the thermosensitive color developing element was stored while being wound in the freezer 4 at -20 ° C. In this state, it was colorless even after storage for 1 month and did not develop color. However, when this thermosensitive coloring element was taken out of the freezer into a room at 25 ° C., it developed a reddish purple color within 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 color-developing element once colored did not disappear even when the temperature was lowered again. HAuC like this
It was found that the photoreduction reaction of l ₄ was extremely slow in the absence of ethylene glycol and could not be used in practice. It was also found that the average particle size of the Au fine particles generated at room temperature was 5 nm and the particle size distribution was small. Even when the same thermosensitive color-developing element was stored in an atmosphere of 10 ° C. for 1 month, it was colorless and did not develop color. However, 10
When it was taken out of the refrigerator at 25 ° C into a room at 25 ° C, it turned reddish purple in a few minutes.

In addition, such a thermosensitive color-developing element is used one at a time.
It was found that when 00 pieces were manufactured 10 times, they had almost the same characteristics.

Even if Al ₂ O ₅ or TiO ₂ was used instead of SiO ₂ coating the surface of the substrate, the same effect as that of SiO ₂ could be obtained.

Further, instead of the PVA resin as the matrix, polyvinyl butyral, polystyrene, polyacrylic acid, an acrylonitrile / styrene copolymer, or a fluororesin can be used to obtain a thermosensitive coloring element having the same effect as the PVA resin. I was able to.

Further, as a comparative example, a thermosensitive color developing element similar to the above was prepared without covering the filter paper with the resin. As a result, as compared with the examples, the nonuniformity of the color development and the variation of the color development start time due to the temperature change were observed. It was observed. It is considered that this is due to the non-uniformity of the surface shape of the filter paper and the influence of impurities or water content.

In the present embodiment, the ion exchange filter paper 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 as raw material, or cotton cloth was used. Was able to obtain a similar effect.

Example 13 Using the manufacturing apparatus shown in FIG. 3, a large number of thermosensitive coloring elements were manufactured. Average molecular weight 100
A PAA aqueous solution prepared by dissolving 0 polyacrylic acid (PAA) in ion-exchanged water was prepared. This solution was applied to the filter paper carrier 5 for ion exchange by the coating device shown in 9 of FIG. 3, sent to the dryer 10 and dried by hot air at 80 ° C. for 3 minutes to solidify, and the filter paper surface was coated with PAA. Carried. The amount of PAA coated was 14 g / m ² . Next, polyvinyl alcohol (PVA) having an average degree of polymerization of 1000 and ethylene glycol (20% by weight relative to PVA) were dissolved in hot water to prepare. This raw material solution is applied to the ion exchange filter paper carrier 5 coated with PAA by the application device shown in FIG. 3 and sent to the dryer 2 and dried with hot air at 80 ° C. for 3 minutes to obtain a thermosensitive coloring material. Carried. Carrying capacity is 17g /
It was m ² . The carrier thus produced is made into a circle having a diameter of 10 mm by a punching device 8, and then an adhesive layer and a release liner are installed on the back surface to have a thickness of 0.2 mm.
Placed on a substrate 7 made of polypropylene sheet of
The cellophane tape is pressed from above and pressure-bonded, and the base 7
And the surface protection tape 6. After that, when light was irradiated for 10 seconds at room temperature 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 irradiation with light, the thermosensitive color developing element was stored while being wound in the freezer 4 at -20 ° C. In this state, it was colorless even after storage for 1 month and did not develop color. However, this thermosensitive coloring element can be removed from the freezer.
When taken out to a room at 5 ° C, a reddish purple color developed within 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 color-developing 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 could not be used in actual use. Even when the same thermosensitive color-developing element was stored in an atmosphere of 10 ° C. for 1 month, it was colorless and did not develop color. However, this composite was
When it was taken out from the refrigerator to a room at 25 ° C, it turned red purple in a few minutes.

Further, such a thermosensitive color-developing element is used one at a time.
It was found that when 00 pieces were manufactured 10 times, they had almost the same characteristics.

Further, instead of the PAA resin coating the filter paper, polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile / styrene copolymer, or fluororesin can be used to obtain a thermosensitive coloring element having the same effect as the PAA resin. I was able to.

Further, in place of the PVA resin as the matrix, polyvinyl butyral, polystyrene, polyacrylic acid, acrylonitrile / styrene copolymer, or fluororesin can be used to obtain a thermosensitive coloring element having the same effect as the PVA resin. I was able to.

Further, as a comparative example, a thermosensitive coloring element similar to the above was prepared without covering the filter paper with the resin. As a result, the nonuniformity of the coloring and the variation of the coloring start time due to the temperature change were compared with the examples. It was observed. It is considered that this is due to the non-uniformity of the surface shape of the filter paper and the influence of impurities or water content.

In this embodiment, ion-exchange filter paper is 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 is used. Was able to obtain a similar effect.

[0096]

As described above, according to the apparatus for producing a thermosensitive color-developing element of the present invention, it is composed of fine metal fine particles and a matrix material made of glass or resin, and the size of the fine metal fine particles increases in temperature. This makes it possible to continuously provide a large amount of thermosensitive color-developing elements in a form in which the thermosensitive color-developing material, which increases irreversibly, is held on the substrate.

In the apparatus for producing a thermosensitive color-developing element of the present invention, a thermosensitive color-developing material material solution is printed or applied on at least a part of the substrate and dried to form a thermosensitive color-developing material layer on the surface of the substrate, and a thermosensitive color-developing material layer. Since a device for installing a surface protective sheet or tape on the color-forming material layer is provided, a large amount of uniform thermosensitive color-developing elements having uniform characteristics can be provided.

Further, in the apparatus for producing a thermosensitive color-developing element of the present invention, an apparatus for forming or forming a thermosensitive color-developing material layer on the surface of the substrate by printing or coating the raw material solution of the thermosensitive color-developing material on at least a part of the substrate and drying the solution. Since a device for installing a surface protective sheet or tape on the coloring material layer and a light irradiation device for irradiating the thermosensitive coloring material with light from the surface protective sheet or tape side are provided, a uniform thermosensitive coloring element with uniform characteristics can be provided. It can be provided in large quantities.

Further, in the apparatus for producing a thermosensitive color-developing element of the present invention, an apparatus for forming a thermosensitive color-developing material layer on the surface of the substrate by printing or coating the thermosensitive color-developing material raw material solution on at least a part of the substrate, and drying the solution. A device for forming a surface protective sheet or tape on the color-developing material layer, and a light irradiation device for irradiating the thermosensitive color-developing material with light from the surface-protective sheet or tape side, and further a freezing device for holding the thermosensitive color-developing material at a low temperature after the light irradiation. Since the apparatus is provided, it is possible to provide a large amount of uniform thermosensitive coloring elements having uniform characteristics.

Further, in the thermosensitive color-developing element manufacturing apparatus of the present invention, an apparatus for coating or impregnating a thermosensitive color-developing material raw material solution on a carrier, carrying the solution on the carrier, and cutting or punching to a predetermined size, and a substrate. Since a device for holding and fixing the carrier carrying the thermosensitive coloring material raw material solution between the surface protective sheet or tape is provided, a large amount of uniform thermosensitive coloring elements having uniform characteristics can be provided.

Further, in the thermosensitive color-developing element manufacturing apparatus of the present invention, the thermosensitive color-developing material raw material solution is applied to or impregnated into a carrier, dried, and then carried on the carrier, and cut or punched into a predetermined size; A surface protection sheet or tape is provided with a device for sandwiching and fixing the carrier carrying the thermosensitive coloring material raw material solution, and a light irradiation device for irradiating the thermosensitive coloring material with light from the surface protection sheet or tape side. It is possible to provide a large amount of uniform thermosensitive coloring elements having uniform characteristics.

Further, in the thermosensitive color-developing element manufacturing apparatus of the present invention, a thermosensitive color-developing material raw material solution is applied to or impregnated into a carrier, dried, supported on the carrier, and cut or punched into a predetermined size; A device for sandwiching and fixing a carrier carrying the thermosensitive coloring material raw material solution between a surface protective sheet or a tape, and a light irradiation device for irradiating the thermosensitive coloring material with light from the surface protective sheet or tape side, and further for the light irradiation. Since a refrigerating device for holding the thermosensitive coloring material at a low temperature is provided later, a large amount of uniform thermosensitive coloring elements having uniform characteristics can be provided. It is a thing.

In the apparatus for producing a thermosensitive color-developing element of the present invention, an inorganic substance or resin is applied or impregnated on a carrier and dried to be carried on the carrier, and further a raw material solution for thermosensitive color-developing material is applied or impregnated on the carrier and dried. Supported on a carrier,
Since it is equipped with 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 for the thermosensitive coloring material between the substrate and the surface protection sheet or tape, the characteristic It is possible to provide a large amount of uniform thermosensitive color-developing elements with uniform colors.

In the apparatus for producing a thermosensitive color-developing element of the present invention, an inorganic substance or resin is applied or impregnated on a carrier and dried to be carried on the carrier. Further, a raw material solution for thermosensitive color-developing material is applied 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 the carrier carrying the inorganic substance or resin and the thermosensitive coloring material raw material solution between the substrate and the surface protection sheet or tape, and the surface protection sheet or Since a light irradiation device for irradiating the thermosensitive coloring material from the tape side is provided, a large amount of uniform thermosensitive coloring elements having uniform characteristics can be provided.

Further, in the apparatus for producing a thermosensitive color-developing element of the present invention, an inorganic substance or resin is applied to or impregnated into a carrier, dried and supported on the carrier, and further, a thermosensitive color-developing material raw material solution is applied or impregnated into the carrier and dried. And a device for cutting or punching to a predetermined size, a device for sandwiching and fixing the carrier carrying the raw material solution for the thermosensitive coloring material between the substrate and the surface protective sheet or tape, and the surface protective sheet. Alternatively, since it is equipped with a light irradiation device that irradiates the thermosensitive coloring material from the tape side and a refrigeration device that keeps the thermosensitive coloring material at a low temperature after the irradiation with light, a large amount of uniform thermosensitive coloring elements with uniform characteristics are provided. can do.

Further, in the thermosensitive color-developing element produced by the present invention, the thermosensitive color-developing material portion has a smaller shape than the substrate, the surface protective 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 amount of uniform and thermosensitive color-developing elements.

Further, the dryer for drying the thermosensitive coloring material is
It is possible to provide a large amount of uniform heat-sensitive color-developing elements having uniform characteristics without deteriorating the substrate or the carrier when the surface temperature is 120 ° C. or less using a type of blowing hot air or a far-infrared lamp.

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 amount of uniform thermosensitive coloring elements having uniform characteristics can be provided. Further, by using a tunnel-shaped light irradiation device in which a plurality of light sources are arranged vertically or horizontally, it is possible to efficiently irradiate light in a short time and to provide a large amount of uniform thermosensitive coloring elements with more uniform characteristics. You can

Further, a freezer or a refrigerator for storing the manufactured thermosensitive color developing element at a low temperature of 0 ° C. or less can provide a large amount of uniform thermosensitive coloring element having uniform characteristics. Further, it is possible to provide a large amount of uniform thermosensitive color-developing elements having uniform characteristics, which can be stored while winding the thermosensitive color-developing element, without taking up space.

[Brief description of drawings]

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

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

FIG. 3 is a block diagram of a thermosensitive color-developing device manufacturing apparatus according to an embodiment of the present invention.

[Explanation of symbols]

1 Printing device or coating device 2,10 Dryer 3 Light irradiation device 4 Refrigerator 5,7 base 6 Surface protection sheet or surface protection tape 8 Cutting device or punching device 9 Printing device or coating device

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-6-48032 (JP, A) JP-A-60-33023 (JP, A) JP-A-6-79849 (JP, A) Actual development Sho-58- 136351 (JP, U) Actually open 60-150037 (JP, U) Actually open 6-87834 (JP, U) International publication 97/028228 (WO, A1) (58) Fields investigated (Int.Cl. ⁷⁾ , DB name) G01K 11/12 G01K 11/06

Claims (14)

(57) [Claims] 1. A process of coating or impregnating a carrier with a raw material solution for a thermosensitive color-developing material, supporting the carrier on the carrier by drying, cutting or punching into a predetermined size, and the heat-sensitive material between the substrate and the surface protective sheet or tape. A method for producing a thermosensitive color-developing element, comprising a step of sandwiching and fixing a carrier carrying a raw material solution for color-developing material. 2. A step of coating or impregnating a carrier with a raw material solution for a thermosensitive color-developing material, drying and supporting on a carrier, cutting or punching into a predetermined size, and the heat-sensitive material between the substrate and the surface protective sheet or tape. 1. A method for producing a thermosensitive color-developing element, comprising the steps of sandwiching and fixing a carrier carrying a color-developing material raw material solution, and irradiating the thermosensitive color-developing material with light from the surface protective sheet or tape side. 3. A process of coating or impregnating a carrier with a raw material solution for a thermosensitive color-developing material, supporting the carrier on the carrier by drying, cutting or punching into a predetermined size, and the heat-sensitive material between the substrate and the surface protective sheet or tape. A step of sandwiching and fixing a carrier carrying a coloring material raw 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 holding the thermosensitive coloring material at a low temperature after the light irradiation. A method for manufacturing a thermosensitive color developing element comprising: 4. A step of applying or impregnating an inorganic substance or a resin to a carrier to carry it on a carrier, and a step of applying or impregnating a carrier solution of a thermosensitive color developing material to a carrier to dry it, and carrying it on the carrier. A thermosensitive coloring element comprising a step of cutting or punching into a predetermined size, and a step of 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. Manufacturing method. 5. A step of applying or impregnating an inorganic substance or a resin on a carrier to carry it on the carrier, and a step of applying or impregnating a thermosensitive color-developing material raw material solution on the carrier to carry it on the carrier, said carrier A step of cutting or punching into a predetermined size, a step of 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 the surface protective sheet Alternatively, a method for manufacturing a thermosensitive coloring element, which comprises a step of irradiating the thermosensitive coloring material with light from the tape side. 6. A step of applying or impregnating an inorganic substance or a resin to a carrier to carry it on a carrier, and carrying it on a carrier, a step of applying or impregnating a carrier solution of a thermosensitive color developing material to a carrier and drying it to carry it on a carrier, Is cut or punched to a predetermined size, a step of sandwiching and fixing the carrier carrying the heat-sensitive coloring material raw material solution between the substrate and the surface protective sheet or tape, and heat-sensitive from the surface protective sheet or tape side. A method for producing a thermosensitive color-developing element, comprising: a step of irradiating the color-developing material with light; and a step of holding the thermosensitive color-developing material at a low temperature after the light irradiation. 7. The method for producing a heat-sensitive color-developing element according to claim 1 , wherein the carrier is smaller than the substrate and the surface protective sheet. 8. A heat-sensitive color-developing material raw material solution is applied or impregnated on a carrier, dried, carried on a carrier, and cut or punched into a predetermined size, and the heat-sensitive material is provided between the substrate and the surface protective sheet or tape. An apparatus for manufacturing a thermosensitive color-developing element, comprising a device for sandwiching and fixing a carrier carrying a raw material solution for color-forming material. 9. A thermosensitive coloring material raw material solution is applied or impregnated on a carrier, dried, carried on a carrier, and cut or punched into a predetermined size, and the thermosensitive material is provided between the substrate and the surface protective sheet or tape. An apparatus for producing a thermosensitive color-developing element, comprising: an apparatus for sandwiching and fixing a carrier carrying a color-developing material raw material solution; 10. A heat-sensitive color-developing material raw material solution is applied or impregnated on a carrier, dried, carried on a carrier, and cut or punched to a predetermined size, and the heat-sensitive material is provided between the substrate and the surface protective sheet or tape. A device for sandwiching and fixing a carrier carrying a color forming material raw material solution, a light irradiating device for irradiating the thermosensitive color developing material with light from the surface protective sheet or tape side, and a refrigerating device for holding the thermosensitive color developing material at a low temperature after the light irradiation. An apparatus for manufacturing a thermosensitive color-developing element. 11. An inorganic substance or resin is applied to or impregnated into a carrier and dried to be supported on the carrier, and a thermosensitive coloring material raw material solution is applied or impregnated onto the carrier and dried to be supported on the carrier to a predetermined size. An apparatus for producing a thermosensitive color-developing element, comprising a device for cutting or punching, and a device for sandwiching and fixing a carrier carrying a raw material solution for a thermosensitive color-developing material between a substrate and a surface protective sheet or tape. 12. An inorganic substance or resin is applied or impregnated on a carrier and dried to be supported on the carrier, and a thermosensitive coloring material raw material solution is applied or impregnated on the carrier and dried to be supported on the carrier 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 thermosensitive coloring from the surface protective sheet or tape side. An apparatus for manufacturing a thermosensitive color-developing element, comprising a light irradiation device for irradiating a material with light. 13. An inorganic substance or a resin is applied or impregnated on a carrier and dried to be supported on the carrier, and further, a raw material solution for a thermosensitive coloring material is applied or impregnated on the carrier and dried to be supported on the carrier to a predetermined size. A device for cutting or punching, a device for sandwiching and fixing the carrier carrying the raw material solution of the thermosensitive coloring material between the substrate and the surface protective sheet or tape, and irradiating the thermosensitive coloring material with light from the surface protective sheet or tape side. An apparatus for manufacturing a thermosensitive color-developing element, comprising: a light irradiating device for controlling the temperature; 14. The heat-sensitive color- developing device manufacturing apparatus according to claim 8 , wherein the carrier is smaller than the substrate and the surface protective sheet.