JP2919612B2 - Thermosensitive coloring material and thermosensitive element using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermosensitive coloring material and a thermosensitive element using the same, and more particularly, to a thermosensitive coloring material which develops a color at room temperature by surface plasmon absorption of metal fine particles and a thermosensitive coloring material. The present invention relates to a thermosensitive element used. The invention further relates to a method for their production.

BACKGROUND ART Conventionally, some thermosensitive coloring materials that develop color by applying heat, and thermosensitive elements using the same have been known. For example, Japanese Unexamined Patent Publication No. Hei 7-149057 discloses that an air layer 154 and an organic layer 15 are formed on a colored layer 155 as shown in FIG.
Disclosed is a thermosensitive element 150 sequentially provided with three. The organic layer 153 contains a material that reversibly changes light scattering depending on temperature. Specifically, such a material is composed of a resin (for example, a vinyl chloride resin) and an organic low-molecular substance dispersed therein. Examples of the organic low-molecular substance include a material that reversibly changes between a transparent state and a cloudy state depending on temperature. The organic low molecular weight substance is usually transparent at room temperature and becomes cloudy at a temperature of about 70 ° C. to about 80 ° C. or higher. Therefore, in the thermosensitive element 150, when the organic layer 153 shows a transparent state at a predetermined temperature, the color of the colored layer 155 transmitted through the organic layer 153 can be confirmed. Further, when the organic layer 153 shows a cloudy state at another temperature, the color of the coloring layer 155 is blocked by the organic layer 153, and as a result, it cannot be confirmed through the organic layer 153. The heat-sensitive element having such a structure can be used as a display element that changes a color tone according to a change in temperature by using a mechanism of transmitting or blocking a color of the colored layer 155 by the organic material layer 153.

However, since the heat-sensitive element 150 utilizes the change in the transparent state and the cloudy state of the organic material layer 153 depending on the temperature, it is extremely difficult to color the entire heat-sensitive element in various colors, and necessarily. It is necessary to provide a coloring layer. Further, in the thermosensitive element 150, the transparent / opaque state of the organic low-molecular substance used reversibly changes depending on the temperature, and thus is suitable for, for example, a display element whose color tone changes in accordance with a change in temperature. However, it cannot be used as an element for displaying a temperature history, which indicates that the temperature once increased to a temperature indicating a cloudy state and then decreased to a temperature indicating a transparent state. Furthermore, in the thermosensitive element 150, since the temperature at which the white turbidity starts is relatively high, the temperature is usually relatively low (for example, about −20 ° C. to about 4
When the product which needs to be stored at (° C.) is exposed to a temperature near room temperature, a change in the temperature cannot be confirmed.

JP-A-61-110585 discloses a thermosensitive element in which a thermosensitive coloring layer and a protective layer are sequentially provided on a support. The thermosensitive coloring layer contains a leuco dye, a color developer, and a zirconium compound, and reversibly develops a color at a temperature of about 50 ° C. or more. Similarly to the above, this heat-sensitive element cannot be used as an element for displaying a temperature history indicating that the temperature once rises to a colorless state and then drops to a color development state.

Japanese Patent Application Laid-Open No. Sho 60-171191 discloses a packaging material having a heat-sensitive portion which can be printed by heat at the stage of shipping or distribution of a packaged product. This packaging material is produced by applying, printing, or adhering a thermochromic material as a thermosensitive portion to the surface of a packaging film (for example, polypropylene).

However, the thermochromic material only changes color when exposed to very high temperatures (eg, about 200 ° C.)
When a product that needs to be stored at a relatively low temperature, such as frozen food and medicine, is exposed to a temperature near room temperature, the change in the temperature cannot be confirmed.

DISCLOSURE OF THE INVENTION The thermosensitive coloring material of the present invention contains gold,
Formed by at least one selected from the group consisting of platinum, silver, copper, tin, rhodium, palladium, and iridium, and (1) at least one inorganic alkoxide containing silicon, aluminum, or titanium as a matrix material (2) at least one complex-forming inorganic component formed of at least one complex-forming inorganic component and at least one complex-forming organic component, wherein the complex-forming inorganic component contains silicon, aluminum, or titanium; (3) the inorganic alkoxide, and wherein the complex-forming organic component is an inorganic / organic complex selected from polyacrylic acid, polyacrylate, and polyethylene oxide;
Polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-styrene copolymer, and a resin selected from the group consisting of resins selected from the group consisting of fluororesins and at least one selected from those described in the above three groups. Are irreversibly increased due to aggregation with each other due to the temperature rise from low temperature to room temperature.

In the method for producing a thermosensitive coloring material of the present invention, the metal ion may be at least one selected from the group consisting of gold ion, platinum ion, silver ion, copper ion, tin ion, rhodium ion, palladium ion, and iridium ion.
And a group consisting of (1) an inorganic substance formed of at least one inorganic alkoxide containing silicon, aluminum, or titanium as a matrix-forming material and (2) at least one complex The complex-forming inorganic component is at least one silicon-, aluminum-, or titanium-containing inorganic alkoxide formed by the complex-forming inorganic component and at least one complex-forming organic component; A group consisting of an inorganic / organic composite selected from acrylic acid, polyacrylate, and polyethylene oxide; or (3) a tree selected from polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-styrene copolymer, and fluororesin Preparing a mixture comprising at least one selected from those described in the three groups of the group consisting of; and the step of irradiating ultraviolet rays to the mixture;
Is included.

In a preferred embodiment, the α-hydrogen-containing alcohol is a dihydric alcohol selected from the group consisting of ethylene glycol and propylene glycol.

The first thermosensitive element of the present invention includes a base and a thermochromic material held on the base, and the thermochromic material includes, as metal fine particles, gold, platinum, silver, copper, tin, rhodium, and palladium. And at least one selected from the group consisting of iridium, and (1) silicon,
A group consisting of an inorganic substance formed by at least one inorganic alkoxide containing aluminum or titanium, or (2) a composite formed by at least one composite-forming inorganic component and at least one composite-forming organic component; The forming inorganic component is at least one inorganic alkoxide containing silicon, aluminum, or titanium, and the complex forming organic component is an inorganic / organic composite selected from polyacrylic acid, polyacrylate, and polyethylene oxide Or (3) at least one selected from those described in the above-described three groups of the group consisting of polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-styrene copolymer, and a resin selected from fluororesins. Contains The size of the fine metal particles irreversibly increases in aggregate with each other due to a temperature rise to room temperature from a low temperature.

In a preferred embodiment, the metal fine particles and the matrix material are the same as those used for the thermosensitive coloring material of the present invention.

In a preferred embodiment, the thermosensitive coloring material is disposed directly on the substrate as a coloring layer, or is disposed on the substrate as a coloring layer via an adhesive layer.

In a further preferred embodiment, the substrate is a sheet or plate made of at least one material selected from the group consisting of a metal film, a plastic film, a fabric, paper, and glass.

In a preferred embodiment, the thermochromic material is impregnated in the substrate.

In a further preferred embodiment, the substrate is a sheet made of cloth and paper, and at least one material selected from the group consisting of a metal film and a plastic film having a large number of pores.

In a preferred embodiment, the thermosensitive coloring material is held in each of a plurality of regions in the substrate to form a coloring region, and the coloring region contains the metal fine particles at different concentrations.

In a preferred embodiment, the thermosensitive coloring material is held in each of a plurality of regions in the substrate to form a coloring region, and the coloring region contains the fine metal particles having different average particle diameters.

In a preferred embodiment, the thermochromic material is retained in a plurality of regions in the substrate to form color regions, and each of the thermochromic materials is formed by different drying conditions. It contains a substance and the metal fine particles.

In a preferred embodiment, the first heat-sensitive element of the present invention includes a light-shielding layer for preventing the heat-generating coloring material from being colored by light.

The method for producing a first thermosensitive element of the present invention is characterized in that the metal ions are at least selected from the group consisting of gold ions, platinum ions, silver ions, copper ions, tin ions, rhodium ions, palladium ions, and iridium ions. A group consisting of one and an α-hydrogen-containing alcohol and, as a matrix-forming material, (1) an inorganic substance formed by at least one inorganic alkoxide containing silicon, aluminum, or titanium; or (2)
At least one complex-forming inorganic component and at least one complex-forming organic component, wherein the complex-forming inorganic component is at least one inorganic alkoxide containing silicon, aluminum, or titanium; and The organic component is selected from the group consisting of an inorganic / organic composite selected from polyacrylic acid, polyacrylate, and polyethylene oxide; or (3) polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-styrene copolymer, and fluororesin. Preparing a mixture comprising at least one selected from the group consisting of the resins selected from the above three groups; holding the mixture on the substrate; and applying ultraviolet light to the mixture held on the substrate. To irradiate the thermosensitive coloring material. Including; step of forming.

In a preferred embodiment, the metal ion, the α-hydrogen-containing alcohol, and the matrix forming material are the same as those used in the method for producing a thermosensitive coloring material of the present invention.

In a preferred embodiment, the substrate is a sheet or plate made of at least one material selected from the group consisting of a metal film, a plastic film, a fabric, paper, and glass.

In a preferred embodiment, the holding of the mixture on the substrate is performed by a coating method, a spin coating method, or a dipping method.

In a preferred embodiment, the method further includes a step of disposing a light-shielding layer to prevent the thermosensitive coloring material from being colored by light.

The second heat-sensitive element of the present invention includes gold,
A substrate containing at least one selected from platinum, silver, copper, tin, rhodium, palladium, and iridium, wherein the size of the metal fine particles is irreversible by aggregating with each other due to a temperature rise from a low temperature to room temperature; To increase.

In a preferred embodiment, the metal fine particles are gold, platinum,
It is at least one metal selected from the group consisting of silver, copper, tin, rhodium, palladium, and iridium.

In a preferred embodiment, the substrate is a sheet made of at least one material selected from the group consisting of paper, fabric, and porous material.

The second method for producing a thermosensitive element of the present invention is characterized in that, as the metal ion, at least one selected from gold ion, platinum ion, silver ion, copper ion, tin ion, rhodium ion, palladium ion, and iridium ion;
And preparing a mixture containing α-hydrogen-containing alcohol; and impregnating the mixture with the substrate; and irradiating the mixture impregnated with the substrate with ultraviolet rays to form the metal fine particles.

In a preferred embodiment, the metal ion and the α-
The hydrogen-containing alcohol is the same as that used in the method for producing a thermosensitive coloring material of the present invention.

In a preferred embodiment, the substrate is a sheet or plate made of at least one material selected from the group consisting of paper, fabric, and porous material.

Thus, the present invention may provide the following advantages: (1) Products that need to be stored at relatively low temperatures (e.g., about -20C to about 4C), such as frozen foods and pharmaceuticals, once at room temperature. To provide a thermosensitive coloring material capable of confirming a change in temperature when exposed to a nearby temperature and a thermosensitive element using the same; (2) By irreversibly developing color depending on temperature,
To provide a thermosensitive coloring material capable of confirming a temperature history and a thermosensitive element using the same; (3) Before coloring, it is physically and chemically stable and optically transparent over a wide wavelength range. (4) To provide a thermosensitive coloring material having a higher contrast and a thermosensitive element using the same; and (4) To provide a thermosensitive element which is flexible and can be formed into various shapes without separately providing a coloring layer. thing.

These and other advantages of the present invention may become apparent to those of ordinary skill in the art upon reading and understanding the following detailed description with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a surface plasmon absorption spectrum of metal fine particles when gold is used as a material of the metal fine particles used in the present invention.

FIG. 2 is a surface plasmon absorption spectrum of the metal fine particles when silver is used as a material of the metal fine particles used in the present invention.

FIG. 3 is a surface plasmon absorption spectrum of metal fine particles when copper is used as a material of the metal fine particles used in the present invention.

FIGS.4A and 4B are schematic diagrams for explaining a mechanism in which the thermosensitive coloring material of the present invention aggregates and develops the metal fine particles therein by the application of heat, and FIG. FIG. 4B is a schematic diagram of the thermosensitive coloring material of the present invention when stored in a dark place at a relatively low temperature (for example, 0 ° C. or lower), and FIG. 4B is a thermosensitive coloring material of the present invention in which metal fine particles aggregate after application of heat. It is a schematic diagram of a sexual coloring material.

FIG. 5 is a schematic diagram showing an example of the first heat-sensitive element of the present invention, which includes a plurality of coloring regions each containing a different concentration of metal fine particles.

FIG. 6 is a schematic diagram showing an example of the first heat-sensitive element of the present invention, which includes a plurality of coloring regions each containing metal fine particles with different average particle diameters.

FIG. 7 is a partial cross-sectional view showing an example of the first heat-sensitive element of the present invention provided with a light-shielding layer.

8A and 8B are perspective views showing an example of a thermosensitive element of the present invention having a thermosensitive coloring material containing metal fine particles on a substrate and a coloring reference, and FIG. 8A shows a comparative example before heat application. FIG. 8B shows an example of the thermosensitive element of the present invention when stored in a dark place at a low temperature (for example, 0 ° C. or lower), and FIG. 8B shows an example of the thermosensitive element of the present invention in which metal fine particles aggregate after application of heat. .

FIG. 9 is a graph showing the relationship between the time and the color tone change rate obtained when the thermosensitive coloring material used to manufacture the thermosensitive element of the present invention was placed in a dark place at a predetermined temperature.

FIG. 10 is a perspective view showing an example of the thermosensitive element of the present invention having a thermosensitive coloring material containing metal fine particles on a base and a plurality of coloring references.

11A and 11B are perspective views showing an example of a thermosensitive element of the present invention in which a thermosensitive coloring material having different thermosensitive properties is provided on a substrate. FIG. 11A shows a comparatively low temperature (for example, , 0 ° C. or lower) shows an example of the thermosensitive element of the present invention when stored in a dark place, and FIG. 11B shows an example of the thermosensitive element of the present invention in which color was formed by aggregation of metal fine particles after application of heat. Show.

12A, 12B, and 12C are schematic diagrams illustrating a sequence of steps for manufacturing the thermosensitive element of the present invention shown in FIGS. 11A and 11B, and FIG. FIG. 12B shows a step of applying the mixture to obtain a laminate, FIG. 12B shows a step of irradiating the laminate with light (hν), and FIG. 12C shows a step of FIG. 12A and FIG. Represents the thermosensitive element of the present invention obtained by the above method.

13A, 13B, and 13C are schematic diagrams illustrating an example of a procedure for manufacturing the thermosensitive element of the present invention shown in FIGS. 11A and 11B, and FIG. 13A illustrates metal ions on a base. FIG. 13B illustrates a step of applying a mixture to obtain a laminate, FIG. 13B illustrates a step of performing different light irradiation (hν and hν ′) on the laminate, and FIG.
13B shows the thermosensitive element of the present invention obtained by the process shown in FIG. 13B.

14A, 14B, and 14C are schematic diagrams illustrating an example of a procedure for manufacturing the thermosensitive element of the present invention shown in FIGS. 11A and 11B, and FIG. 14A shows metal ions on a base. FIG. 14B shows a step of applying the mixture containing and then drying under different conditions, FIG. 14B shows a step of performing light irradiation (hν) on the laminate, and FIG. 14B shows a thermosensitive element of the present invention obtained by the process shown in FIG. 14B.

FIG. 15 is a schematic sectional view showing an example of a conventional thermosensitive element.

BEST MODE FOR CARRYING OUT THE INVENTION <Thermosensitive Coloring Material> The following describes the thermosensitive coloring material of the present invention.

The thermosensitive coloring material of the present invention contains metal fine particles and a matrix substance. Here, the term “coloring” used in the present specification includes changing the color tone of a material from colorless to a predetermined color, and changing from a predetermined color to another predetermined color.

The metal fine particles used in the present invention exhibit color development based on surface plasmon absorption, and are less susceptible to oxidation or reduction by oxygen and other impurities, with an irreversible size increase due to aggregation described below. Fine particles composed of a metal having a relatively high purity. Typically,
The metal fine particles are composed of at least one metal selected from the group consisting of gold, platinum, silver, tin, rhodium, palladium, and iridium.

As shown in FIG. 1, the metal fine particles composed of gold have a steep peak at about 530 nm based on surface plasmon absorption due to aggregation, so the thermosensitive coloring material of the present invention containing gold fine particles is It shows a vivid color tone between purple and red when colored. As shown in FIG. 2, the metal fine particles composed of silver are aggregated to about 400 nm, as shown in FIG.
Has a peak based on surface plasmon absorption, so that the thermosensitive coloring material of the present invention containing silver fine particles shows a brown color tone when coloring. Since the metal fine particles composed of copper have a peak based on surface plasmon absorption at about 590 nm due to aggregation as shown in FIG. 3, the thermosensitive coloring material of the present invention containing copper fine particles has a light green color when developed. Shows the color tone. Therefore, the metal constituting the metal fine particles used in the present invention is preferably gold because the color tone of the thermosensitive coloring material obtained at the time of aggregation of the metal fine particles is more easily observed.
Gold is also known to be chemically more stable alone than the above metals.

The content of the metal fine particles varies depending on the type of the metal used, but is preferably about 0.01% by weight to about 20% by weight, more preferably about 0.1% by weight, based on the weight of the entire thermosensitive coloring material.
It is contained at a ratio of from 05% by weight to about 10% by weight. By such a content, the particle diameter can be easily controlled, and aggregation of the metal fine particles which can occur independently of application of heat can be prevented. When the content of the metal fine particles is less than 0.01% by weight, even if heat is applied to the thermosensitive coloring material at a temperature described below, the fine particles may not aggregate to a colorable (that is, visible) temperature. is there. When the content of the metal fine particles exceeds 20% by weight, the metal fine particles are easily aggregated irrespective of the application of heat, and as a result, the color may be partially formed in the thermosensitive coloring material.

In the present invention, the metal fine particles aggregate at room temperature and irreversibly increase their size. As used herein, the term "room temperature" refers to any temperature in the range from about 10C to about 40C. Such metal fine particles generally begin to irreversibly increase in size at temperatures above about -100 ° C. However, in fact, the color development of the thermosensitive coloring material of the present invention accompanying the increase in the size of the metal fine particles is preferably about 5 ° C. or higher, more preferably about 5 ° C. or more, although it changes depending on the time of applying the heat at that temperature. Occurs at temperatures above room temperature.

The matrix material used in the present invention is a material that can uniformly disperse the metal fine particles therein, is physically and chemically stable, and is optically transparent over a wide wavelength range. Such matrix materials include inorganic materials, inorganic / organic composites, and resins.

The inorganic material used as the matrix material is formed from at least one inorganic alkoxide containing silicon, aluminum, or titanium. Such an inorganic substance contains at least one gel selected from the group consisting of silica gel, alumina gel, and titania gel.

The inorganic / organic composite is formed from a composite forming material containing at least one composite forming inorganic component and at least one composite forming organic component. Examples of the complex-forming inorganic component include an inorganic alkoxide containing silicon, aluminum, or titanium. Examples of complex forming organic components include polyacrylic acid, polyacrylates, and polyethylene oxide. It is considered that the inorganic / organic composite used as the matrix material has a form in which the organic component forming the composite is adsorbed on the gel formed by hydrolysis of the inorganic component forming the composite (K. Nakanishi, "Organic-Inorganic Composite System"). Gelation ”, Abstracts of 2nd Izumi Forum Workshop, 15 and 16
P. 1992).

The resin is formed of a matrix forming resin selected from the group consisting of polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-styrene copolymer, and fluororesin. Fluororesins are preferred because the resulting matrix material is transparent and has excellent mechanical strength. When a resin is used as the matrix material, the thermosensitive coloring material may preferably contain a stabilizer for protecting metal ions forming the metal fine particles. Examples of such stabilizers include polyvinylpyrrolidone. The stabilizer is preferably contained in a proportion of about 0.01% by weight to about 3% by weight based on the weight of gold of the thermosensitive coloring material.

As the matrix substance used in the present invention, among the above-mentioned inorganic substances, inorganic / organic composites, and resins,
Silica gel that is physically and chemically stable and easy to prepare is preferred.

Generally, as shown in FIG. 4A, in the thermosensitive coloring material 40 of the present invention, in a dark place at a relatively low temperature (for example, 0 ° C. or lower), metal fine particles are too small to be actually measured. Exists in diameter. In this state, when heat near room temperature is applied to the thermosensitive coloring material of the present invention, for example, in a dark place, as shown in FIG.4B, the metal fine particles aggregate with each other and the size thereof is irreversible. Increase. The average particle diameter of the increased metal fine particles 41 'is preferably about 1 nm to about 50 n.
m, more preferably in the range of about 3 nm to about 30 nm. If the particle size distribution of the irreversibly increased metal fine particles is small and the average particle size is particularly in the range of about 3 nm to about 30 nm, the coloring of the thermosensitive coloring material can be further uniform. In addition, the particle diameter of these metal fine particles can be measured using a transmission electron microscope. However, the average particle diameter of the metal fine particles after heat application in actual use varies depending on, for example, the type of metal used and the temperature (heat-sensitive temperature) and time (heat-sensitive time) at which the metal particles are applied. It is not limited to.

<Production method of thermosensitive coloring material> The production method of the thermosensitive coloring material of the present invention will be described below.

First, a mixture containing a metal ion, an α-hydrogen-containing alcohol, and a matrix-forming material is prepared.

Examples of metal ions include gold, platinum, silver, copper, tin, rhodium, palladium, and iridium ions.
The metal ion is provided from a metal compound that can be dispersed in a sol-like matrix forming material described below. Examples of such metal compounds include AuHCl ₄ , AuNaCl ₄ , H ₂ PtCl ₆ , AgCl
AuHCl ₄ is particularly preferred, including O ₄ , CuCl ₂ , SnCl ₂ , IrCl ₃ , RhCl ₃ , and PdCl ₂ . The metal compound is added in an amount that can satisfy the content of the metal fine particles in the thermochromic material of the present invention.

The α-hydrogen-containing alcohol used in the present invention is α-hydrogen-containing alcohol.
Dihydric alcohols having hydrogen are preferred, and representative examples include ethylene glycol and propylene glycol. The α-hydrogen-containing alcohol is contained in the prepared mixture at a ratio of preferably 0.5 mol to 1.5 mol, more preferably 1.0 mol to 1.2 mol, per 1 mol of the metal ion.

Examples of matrix forming materials include (1) at least one inorganic alkoxide; (2) a composite forming material; and (3) a matrix forming resin.

The inorganic alkoxide (1) used as the matrix forming material may contain silicon, aluminum, or titanium. Representative examples of such inorganic alkoxides include silicon-containing lower alkoxides such as methyl silicate and ethyl silicate, aluminum-containing lower alkoxides such as aluminum methoxide and aluminum ethoxide, and titanium methoxide and titanium ethoxide. Such titanium-containing lower alkoxides are mentioned. Inexpensive methyl silicate and ethyl silicate are particularly preferred.

When an inorganic alkoxide is used as a matrix forming material, for example, water and methanol, ethanol, and / or propanol are added as a dispersing solvent to the prepared mixture, and hydrochloric acid or ammonia is further added as a catalyst at a predetermined ratio. Is added. In the presence of such a dispersion solvent and a catalyst, the inorganic alkoxide is hydrolyzed to gel (polycondensation), and further dried (that is, a sol-gel method is performed), whereby a glass or ceramic matrix is formed. A substance is formed.

The composite forming material (2) used as the matrix forming material contains at least one kind of complex forming inorganic component and at least one kind of complex forming organic component. Examples of the complex forming inorganic component include the above-mentioned inorganic alkoxides containing silicon, aluminum, or titanium. Examples of the complex-forming organic component include the above-mentioned polyacrylic acid, polyacrylate, and polyethylene oxide.

When a complex-forming material is used as the matrix-forming material, the mixture to be prepared is added with, for example, water and methanol, ethanol, and / or propanol as a dispersing solvent, and hydrochloric acid or ammonia is added as a catalyst to a predetermined mixture. It is added in proportions. In the presence of such a dispersion solvent and a catalyst, the inorganic alkoxide of the complex-forming material is hydrolyzed and polycondensed to gel the whole, and further dried (that is, a sol-gel method is performed). , A glass or ceramic matrix material is formed.

Examples of the matrix forming resin (3) used as the matrix forming material include the above-mentioned polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-styrene copolymer, and fluororesin.

When a matrix-forming resin is used as the matrix-forming material, polyvinyl pyrrolidone may preferably be added to the prepared mixture at a predetermined ratio as a stabilizer. A dispersion solvent may be added to the mixture, if necessary. Examples of the dispersion solvent include water and / or
Or methanol, ethanol, and propanol.

In the mixture containing the metal ion, the α-hydrogen-containing alcohol, and the matrix-forming material, formamide or dimethylformamide is further used as a drying inhibitor to prevent cracking or foaming in the obtained matrix material. It can be added. The amount of the dry transfer agent to be added can be appropriately determined by those skilled in the art as needed.

The prepared mixture is preferably dried at a temperature of about 50 ° C. to about 110 ° C. for a predetermined time (eg, about 0.5 hour to about 100 hours).

 The mixture is then irradiated with ultraviolet light.

The irradiation conditions of the ultraviolet ray differ depending on the kind and the amount of the metal ion used, and can be arbitrarily selected by those skilled in the art. By such irradiation with ultraviolet rays, the metal ions in the mixture are reduced by the α-arbitrarily containing alcohol, and as a result, metal fine particles composed of a simple metal are dispersed and formed in the matrix material. UV light is applied until the color of the metal ions in the mixture (eg, when gold ions are used, the mixture shows a pale yellow color) and the resulting exothermic chromogenic material is colorless and transparent. Is preferred.
This is because, when the ultraviolet rays are excessively irradiated, the metal fine particles aggregate regardless of the application of heat, and as a result, color is generated.

Thus, the thermosensitive coloring material of the present invention is formed. Since the thermosensitive coloring material develops color at room temperature and under irradiation of ultraviolet rays, it can be formed at a relatively low temperature (for example, about-
(20 ° C to about 4 ° C) in a dark place.

<First Thermal Element> The first thermal element of the present invention will be described below.

The first thermosensitive element of the present invention includes a base and a thermosensitive coloring material held on the base.

In the first thermosensitive element of the present invention, the thermosensitive coloring material used is the same as described above. The thermosensitive coloring material is held on a substrate, and more specifically, is disposed directly on the substrate; or on the substrate via an adhesive layer (for example, an adhesive layer made of an epoxy-based adhesive). Located; or impregnated in the substrate. The amount of the thermosensitive coloring material held on the substrate is not particularly limited, but may be 1 cm ^{2 of} the substrate.
Preferably about 0.1 mg to about 100 mg, more preferably about 1 mg to about 10 mg.

When the thermosensitive coloring material is disposed directly on the substrate or is disposed on the substrate via an adhesive layer,
Examples of the substrate used in the present invention include a metal film,
Examples include a sheet or plate made of at least one material selected from the group consisting of plastic films, fabrics, papers, and glass. Further, when the thermosensitive coloring material is impregnated in the substrate, examples of the substrate used in the present invention are selected from the group consisting of cloth and paper, and metal film and plastic film having a large number of pores. Examples include a sheet made of at least one material. The size of the pores in the metal film and the plastic film is not particularly limited.

Examples of metal films include aluminum foil, and films and sheets made of stainless steel. Examples of the plastic film include a sheet made of an ethylene-vinyl acetate copolymer, a polyethylene sheet, and a polypropylene sheet. Examples of fabrics include any woven, knitted and nonwoven fabric made from rayon, cotton, glass fibers, silica fibers, alumina fibers, and the like. Examples of paper include:
Filter paper, kraft paper, and Kent paper. The substrate may also be a laminate of the above sheets, such as a three-layer sheet in which an ethylene-vinyl acetate copolymer sheet, an aluminum foil, and a polyethylene sheet are sequentially laminated. The glass used as the substrate includes a glass plate made of transparent glass or frosted glass.
As the substrate based on the present invention, filter paper is particularly preferable. The substrate used in the present invention can also preferably be the packaging material itself. The thickness of the substrate is not particularly limited.

The first heat-sensitive element of the present invention is a special heat-sensitive element in which heat at a predetermined temperature (for example, room temperature) is applied for a certain period of time in a dark place by changing the concentration of metal fine particles contained in the heat-sensitive coloring material. Under different conditions, different shades can be obtained. For example, when the first thermosensitive element of the present invention has a concentration of gold (Au) fine particles of about 0.05 mg per 1 cm ² of the substrate, and exposing the thermosensitive element to a temperature of about 25 ° C. in a dark place for about 10 minutes, The thermosensitive element shows a purple color tone. In contrast, a thermosensitive element having a concentration of gold particles of about 0.5 mg / cm ² of the substrate shows a brown color upon application of the same heat as described above.

The first heat-sensitive element of the present invention can also obtain a different color tone under special conditions in which the temperature applied for a certain period of time in a dark place is different even when the concentration of the contained metal fine particles is constant. . This is because the rate at which the size of the metal fine particles irreversibly increases differs depending on the concentration of the metal fine particles in the thermosensitive coloring material. For example, when the first thermosensitive element of the present invention has a concentration of gold (Au) fine particles of about 0.05 mg per 1 cm ² of the substrate, when the thermosensitive element is exposed to a temperature of about 25 ° C. in a dark place for 10 minutes, the thermosensitive element becomes The element shows a purple color tone.
In contrast, this thermosensitive element was heated to about 60 ° C in a dark place.
Upon exposure for 10 minutes, the thermosensitive element exhibits a brown color.

In the first thermosensitive element of the present invention, the exothermic coloring material is held in each of the plurality of regions of the substrate to form coloring regions, and these coloring regions may contain metal fine particles at different concentrations.

For example, when a thermosensitive coloring material is directly disposed on a substrate, as shown in FIG. 5, the first thermosensitive element 50 of the present invention is used.
Are thermosensitive coloring materials 53 containing metal fine particles 54 at different concentrations as coloring regions 52a, 52b, and 52c, respectively.
a, 53b, and 53c may be held on the substrate 51 in the form of a bar code. By arranging a plurality of coloring regions in the form of a barcode, in the first thermosensitive element of the present invention, only the region that has developed color by the application of heat can be read using a known barcode reading device. It is possible to confirm the temperature that has contributed to color development.

When the thermosensitive coloring material used in the present invention is held on the substrate as a plurality of coloring regions, these coloring regions may further contain the fine metal particles having different average particle diameters. For example, as shown in FIG. 6, a first thermosensitive element 60 according to the present invention in which a thermosensitive coloring material is directly disposed on a substrate, is provided in the coloring areas 62a, 62b and 62c with metal particles having different average particle sizes. Microparticles 64a, 64b, and 64c may be included, respectively. Since the metal fine particles 64a, 64b, and 64c in such a thermosensitive element 60 have different sizes that increase reversibly depending on the temperature given for a certain period of time in a dark place, the coloring regions 62a, 62b , And 62c each show a different color tone. Therefore, the heat sensitive element 60
Can check the temperature history when a specific temperature is applied for a certain period of time in a dark place. The fine metal particles having different average particle diameters can be obtained, for example, by changing the amount of ultraviolet light to be irradiated when producing the thermosensitive coloring material. The amount of such ultraviolet light can be appropriately selected by those skilled in the art.

When the thermosensitive coloring material used in the present invention is held on the substrate as a plurality of coloring areas, the coloring areas further include a matrix material and metal fine particles formed under different drying conditions. It can be composed of materials. In a thermosensitive coloring material containing a matrix substance and metal fine particles formed under different drying conditions, the degree of freedom of the metal fine particles contained therein is different. Thus, the rate of increase of the metal fine particles in each of the coloring regions when heat is applied is different, so that each of the coloring regions has a different color tone. Such drying conditions can be appropriately selected by those skilled in the art.

The first thermosensitive element of the present invention may further include a coloring sample for confirming the temperature when the thermosensitive coloring material develops a color at a predetermined temperature. The color tone of the thermosensitive coloring material obtained when heat of a predetermined temperature is applied for a certain period of time in a dark place is printed on the coloring sample in advance. The coloring sample may be printed directly on the substrate, or may be a sheet or plate made of a material such as a metal film, a plastic film, a cloth, paper, or glass printed with a predetermined color tone. It can be attached. One or more colored samples may be provided in the thermosensitive element.
As described above, by printing a color tone obtained by applying heat of various temperatures to a color sample in a dark place for a certain period of time, the temperature of the color-developed thermosensitive element can be adjusted to any temperature in a dark place for a certain period of time. It is possible to visually confirm whether or not the exposure has been made.

In the present invention, the first thermosensitive element may also be provided with a light-shielding layer for preventing the thermosensitive coloring material from being colored by light (especially ultraviolet rays), for example, so that it can be used in direct sunlight. . FIG. 7 shows an example of the first thermal element 70 of the present invention provided with a light shielding layer. Thermal element 70 shown in FIG.
A thermosensitive coloring material 72 is provided on a base 73, and a light shielding layer 74 is provided so as to cover the thermosensitive coloring material 72. As a material used for such a light shielding layer,
Examples thereof include a metal tape such as an aluminum foil tape, a glass tape, and a paper tape, and are not particularly limited as long as the material can protect the thermosensitive coloring material from light. The shape of the light-shielding layer is also not particularly limited. The thickness of the light-shielding layer is not particularly limited, but is usually about 1 μm to about 30 μm.

<Method of Manufacturing First Thermal Element> A method of manufacturing the first thermal element of the present invention will be described below.

First, a mixture containing a metal ion, an α-hydrogen-containing alcohol, and a matrix-forming material is prepared. The method for preparing this mixture is the same as that for the thermosensitive coloring material of the present invention.

This mixture is then held on a substrate. As such a holding method, any of a coating method, a spin coating method, and a dipping method can be adopted. The means used for these retention methods are known to those skilled in the art. In the first thermosensitive element of the present invention, when the thermosensitive coloring material is provided on the base via the adhesive layer, the adhesive (for example, epoxy-based adhesive) is provided on the surface of the base for holding the mixture. )
Must be applied beforehand.

Next, the mixture held on the substrate is irradiated with ultraviolet rays to form a thermosensitive coloring material. The conditions used for the irradiation of the ultraviolet rays are the same as those of the thermosensitive coloring material. Furthermore, if necessary, a light-shielding layer may be provided on the thermosensitive coloring material formed by irradiation with ultraviolet rays.

Thus, the first thermosensitive element of the present invention is manufactured. Since the first thermosensitive element of the present invention develops color at room temperature and under irradiation of ultraviolet rays, it can be stored in a dark place at a relatively low temperature (for example, about −20 ° C. to about 4 ° C.) immediately after production. preferable.

<Second Thermal Element> The second thermal element of the present invention will be described below.

A second thermosensitive element of the present invention includes a base containing fine metal particles.

The type of metal fine particles used in the second thermosensitive element of the present invention is the same as described above.

The content of the metal fine particles varies depending on the type of the metal used, but is an amount that can easily control the particle diameter and prevents the metal fine particles from aggregating regardless of the application of heat.
The content of the metal fine particles is preferably about 0.01% by weight to about 20% by weight, more preferably about 0.05% by weight to about 10% by weight, based on the total weight of the thermosensitive coloring material. When the content of the metal fine particles is less than 0.01% by weight, even if heat is applied to the thermosensitive coloring material at a temperature described below, the coloring is possible (that is,
Fine particles may not aggregate to a size that is (visible). When the content of the metal fine particles exceeds 20% by weight, the metal fine particles may easily aggregate regardless of the application of heat, and may partially color in the second heat-sensitive element of the present invention.

The metal fine particles aggregate at room temperature and increase their size irreversibly. In the second thermosensitive element of the present invention,
The average particle diameter of the metal fine particles before heat is applied and the temperature at which the metal fine particles start increasing are also the first values of the present invention.
This is the same as that of the thermal element.

The metal fine particles used in the second thermosensitive element of the present invention are:
Impregnated in the substrate. The amount of the fine metal particles contained in the substrate is not particularly limited, the substrate 1 cm ² per preferably about 0.001mg~ about 1.0 mg, more preferably from about 0.01mg~ about 0.
1 mg.

Examples of the substrate used in the second thermosensitive element of the present invention include a sheet or plate made of at least one material selected from the group consisting of paper, fabric, and porous material.

Examples of paper include filter paper, kraft paper, and Kent paper. Examples of fabrics include any woven, knitted and nonwoven fabric made from rayon, cotton, glass fibers, silica fibers, alumina fibers, and the like. Examples of porous materials include plates and granules made of gels such as zeolites and silica gel. As the substrate used in the second thermosensitive element of the present invention, a sheet or plate made of silica gel or porous glass is particularly preferable. The thickness of the substrate used in the present invention is not particularly limited.

In the second thermosensitive element of the present invention, a plurality of coloring regions and / or coloring samples can be provided as in the first thermosensitive element of the present invention.

<Method of Manufacturing Second Thermal Element> A method of manufacturing the second thermal element of the present invention will be described below.

First, a mixture containing a metal ion and an α-hydrogen-containing alcohol is prepared.

The types and amounts of the metal ion and the α-hydrogen-containing alcohol used in the second method for producing a thermosensitive element of the present invention are the same as those of the thermosensitive coloring material of the present invention. The amount of the metal ion that can be used is added in an amount that can satisfy the content of the metal fine particles in the thermosensitive coloring material of the present invention.

The mixture is then impregnated into a substrate. More specifically, the substrate is immersed in the mixture prepared above using means known to those skilled in the art.

Next, by irradiating the substrate with ultraviolet rays, metal fine particles are formed in the substrate. The conditions used for the irradiation of the ultraviolet rays are the same as those of the thermosensitive coloring material. Furthermore, a light-shielding layer may be provided on the base as needed.

Thus, the second thermosensitive element of the present invention is manufactured. Since the second thermosensitive element of the present invention develops color at room temperature and under irradiation of ultraviolet rays, it can be stored in a dark place at a relatively low temperature (for example, about −20 ° C. to about 4 ° C.) immediately after production. preferable.

Examples Examples of the present invention will be described below. Note that the present invention is not limited to these examples.

Example 1 A solution composed of the materials shown in Table 1 below was prepared.

To this solution, AuHCl ₄ · 4H ₂ O of 0.18g metal compound
Was added and the mixture was stirred at room temperature for 10 minutes.
Then, the mixture was cast on a flat plate and dried at room temperature for 5 days, followed by drying at 60 ° C. for 24 hours to obtain a transparent and pale yellow gel film having a thickness of 300 μm.

This film was irradiated with white light for 10 minutes at room temperature using a 500 W xenon lamp at an interval of 30 cm from the film to obtain a film made of a colorless material containing Au fine particles. The resulting film is immediately
Stored in a refrigerator (dark place) at 2 ° C. for 2 months.

The film did not develop color during this storage. Two months later, remove the film from the refrigerator and place it in a dark place at 25 ° C.
After 20 minutes, it developed color and became purple-red. The color-developed film has a small particle size distribution A having an average particle size of about 5 nm.
It contained u microparticles and had an absorption peak at 525 nm based on the surface plasmon absorption of the Au microparticles. Next, the color-developed film was placed again in a refrigerator at 0 ° C., but the color tone did not disappear, and the temperature history was confirmed. Table 2 shows the types of the metal compound, the α-hydrogen-containing alcohol, and the matrix forming material used in this example, and the evaluation results of the obtained films.

Examples 2 to 11 Films made of materials irradiated with a xenon lamp were prepared in the same manner as in Example 1 except that the metal compounds, α-hydrogen-containing alcohols, and matrix forming materials shown in Table 2 were used. , Was evaluated. Table 2 shows the results.

Comparative Example 1 A film made of a material irradiated with a xenon lamp was prepared and evaluated in the same manner as in Example 1, except that ethylene glycol (EG) was not used. Table 2 shows the results.

Before application of heat, the metal fine particles in the material prepared in Examples 1 to 11 were too small to measure the particle size, but after heat application, the fine particles increased, and the particle size increased. Measurement was possible.

As shown in Table 2, the materials prepared in Examples 1 to 11 are useful as heat-sensitive coloring materials that increase the particle diameter of metal fine particles by applying heat and develop color, and that can confirm the temperature history. You can see that there is. On the other hand, it can be seen that the material of Comparative Example 1 produced without using the α-hydrogen-containing alcohol did not develop color by application of heat, and could not be used as a thermosensitive coloring material.

Of the materials obtained in Example 1 and Examples 5 to 11,
The material obtained in Example 1 containing Au fine particles developed a clear color with the best contrast as a thermosensitive coloring material.

Examples 12 to 15 In the same manner as in Example 1, the solutions shown in Table 1 were prepared.
To this solution, the types and amounts of metal chemicals shown in Table 3 were added and stirred at room temperature to obtain a mixture. Next, this mixture was applied to an aluminum foil (base) having a thickness of 20 μm.
Coated on top and dried for 1 hour at room temperature followed by 1 hour at 60 ° C. This application and drying were repeated 10 times to obtain a laminate having a transparent, pale yellow, thin wound gel film having a thickness of 3 μm on the substrate. This laminate was irradiated with a xenon lamp for 3 minutes in the same manner as in Example 1 to obtain an element having a film made of a colorless material on a substrate. Using this element, the same temperature history evaluation as in Example 1 was performed.
Table 3 shows the results.

Comparative Example 2 An element having a film made of a material irradiated with a xenon lamp was produced and evaluated in the same manner as in Example 12, except that ethylene glycol (EG) was not used. Table 3 shows the results.

The metal fine particles in the element prepared in Examples 12 to 15 before applying heat were too small to measure the particle diameter, but after heat application, the fine particles increased, and the particle diameter was increased. Measurement was possible.

As shown in Table 3, the devices manufactured in Examples 12 to 15 were useful as heat-sensitive devices that increased the particle diameter of metal fine particles by applying heat, developed color, and allowed to confirm the temperature history. I understand. On the other hand, the device of Comparative Example 2 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

Example 16 A solution shown in Table 1 was prepared in the same manner as in Example 1,
To this solution was added AuHCl ₄ · 4H ₂ O in 0.18 g, and was obtained mixture was stirred at room temperature. Next, a 200-μm-thick polypropylene bag (substrate) is immersed in the mixed solution, taken out, dried at room temperature for 1 hour, and subsequently at 60 ° C.
For 1 hour. This immersion and drying were repeated three times to form a transparent and pale yellow thin gel film having a thickness of about 1 μm on the surface of the bag. The obtained bag was irradiated with a xenon lamp for 3 minutes in the same manner as in Example 1 to obtain a device having a film made of a colorless material on a substrate. Using this element, the same temperature history evaluation as in Example 1 was performed.
Table 4 shows the results.

Example 17 An element was prepared and evaluated in the same manner as in Example 16 except that a rayon-made cloth having a thickness of 500 µm was used instead of the polypropylene-made bag. Table 4 shows the results.

Comparative Example 3 An element having a film made of a material irradiated with a xenon lamp was prepared and evaluated in the same manner as in Example 16 except that ethylene glycol (EG) was not used. Table 4 shows the results.

The metal fine particles in the element prepared in Examples 16 and 17 before applying heat were too small to produce a particle diameter, but after heat application, the fine particles increased, and the particle diameter increased. Measurement was possible.

As shown in Table 4, the devices manufactured in Examples 16 and 17 were useful as heat-sensitive devices that increased the particle diameter of the metal fine particles by applying heat, developed color, and confirmed the temperature history. I understand. On the other hand, the device of Comparative Example 3 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

Example 18 A solution shown in Table 1 was prepared in the same manner as in Example 1,
To this solution were added the types and amounts of metal compounds shown in Table 3 and stirred at room temperature to obtain a mixture. Next, this mixture was applied to kraft paper (substrate) having a thickness of 50 μm by a spin coating method, and dried at room temperature for 30 minutes.
Subsequently, it was dried at 60 ° C. for 30 minutes. Apply and dry this
This was repeated twice to obtain a laminate having a transparent and pale yellow thin gel film having a thickness of about 0.5 μm on the substrate. This laminate was irradiated with a xenon lamp for 3 minutes in the same manner as in Example 1 to obtain an element having a film made of a colorless material on a substrate. Using this element, the same temperature history evaluation as in Example 1 was performed. Table 5 shows the results.

Comparative Example 4 An element having a film made of a material was produced by irradiation with a xenon lamp in the same manner as in Example 18 except that ethylene glycol (EG) was not used, and its evaluation was performed. Table 5 shows the results.

The metal fine particles in the element prepared in Example 18 before applying heat were too small to measure the particle diameter,
After the application of heat, the fine particles increased, and their particle diameter could be measured.

As shown in Table 5, it was found that the element manufactured in Example 18 was useful as a heat-sensitive element that increased the particle diameter of the metal fine particles by applying heat, developed color, and confirmed the temperature history. . On the other hand, the element of Comparative Example 4 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive element.

Example 19 A solution composed of the materials shown in Table 6 below was prepared.

To this solution was added AuHCl ₄ · 4H ₂ O 0.2g of a metal compound, and the mixture was stirred for 1 hour at room temperature. Then, the mixture was cast on a flat plate and dried at room temperature for 3 days, followed by drying at 60 ° C. for 24 hours to obtain a transparent, pale yellow film having a thickness of 200 μm.

This film was irradiated with white light for 5 minutes at room temperature using a 500 W xenon lamp at an interval of 30 cm from the film to obtain a film made of a colorless material containing Au fine particles. The obtained film was immediately stored in a refrigerator (dark place) at 0 ° C. for 2 months. The film did not develop color during this storage. Two months later, the film was removed from the refrigerator and kept in a dark place at 25 ° C. for 10 minutes, and the color was developed to show reddish purple. The color-developed film contains Au fine particles having a small particle size distribution having an average particle size of 5 nm, and
It had an absorption peak at 525 nm based on the surface plasmon absorption of the fine particles. Next, the color-developed film was placed again in a refrigerator at 0 ° C., but the color tone did not disappear, and the temperature history was confirmed. Table 7 shows the types of the metal compound, the α-hydrogen-containing alcohol, and the matrix forming material used in this example, and the evaluation results of the obtained films.

Examples 20 to 24 Except that the metal compounds, α-hydrogen-containing alcohols, and matrix forming materials shown in Table 7 were used, films made of materials irradiated with a xenon lamp were prepared in the same manner as in Example 19. , Was evaluated. Table 7 shows the results.

Examples 25 to 31 Irradiation with a xenon lamp was performed in the same manner as in Example 19, except that the metal compounds, α-hydrogen-containing alcohols, and matrix forming materials shown in Table 7 were used, and irradiation was performed with a xenon lamp for 10 minutes. Films made of each material were produced and evaluated. Table 7 shows the results.

Comparative Example 5 A film made of a material irradiated with a xenon lamp was produced and evaluated in the same manner as in Example 19 except that ethylene glycol (EG) was not used. Table 7 shows the results
Shown in

The metal fine particles in the material before applying heat, which were prepared in Examples 19 to 31, were too small to measure the particle diameter, but after heat application, the fine particles increased, and the particles were increased. The diameter could be measured.

As shown in Table 7, the materials produced in Examples 19 to 31 are useful as heat-sensitive coloring materials that increase the particle diameter of the metal fine particles by applying heat and develop color, and that can confirm the temperature history. You can see that. On the other hand, the material of Comparative Example 5 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive coloring material.

Of the materials obtained in Example 19 and Examples 25 to 31,
The material obtained in Example 19 containing Au fine particles had the best contrast as a thermosensitive coloring material and was colored for explanation.

Example 32 Films A to C made of colorless materials were produced in the same manner as in Example 19, except that the amounts of AuHCl ₄ .4H ₂ O were 0.018 g, 0.54 g, and 1.8 g, respectively. The obtained film is
Stored in refrigerator at 0 ° C. for 2 months. None of the films developed color during this storage. Then, these films were taken out of the refrigerator and placed in a dark place at various temperatures for 10 minutes. As a result, film A developed reddish purple at a temperature of 28 ° C., and film B reddish at a temperature of 15 ° C. A purple color developed and Film C developed a reddish purple color at a temperature of 7 ° C.

From the above, it is understood that the material obtained in this example is useful as a thermosensitive coloring material. Furthermore, when these materials contain various concentrations of metal fine particles, and when heat is applied for a certain period of time in a dark place, the temperature for obtaining a specific color tone depends on the concentration of the metal fine particles. It can be seen that it changes.

Example 33 A film made of a colorless material was prepared in the same manner as in Example 19, and stored in a refrigerator at 0 ° C. for 2 months. The films were then removed from the refrigerator and placed in the dark for 10 minutes at a temperature of 25 ° C, 40 ° C, and 60 ° C, respectively. This film develops a purple-red color at 25 ° C,
Developed a brownish-purple color and a brown color at 60 ° C.

From the above, it can be seen that the material obtained in this example is useful as a thermosensitive coloring material. Further, when heat is applied to a film made of these materials in a dark place for a certain period of time, the color tone obtained by coloring changes depending on the temperature at that time.

Examples 34 to 41 Materials irradiated with a xenon lamp were prepared and evaluated in the same manner as in Examples 19 and 25 to 31, except that the temperature at the time of irradiation with the xenon lamp was set to 0 ° C.
The evaluation processes of the obtained materials were all the same as those of Example 19 and Examples 25 to 31, and it was found that they were useful as thermosensitive coloring materials.

Examples 42-54 Solutions composed of the materials shown in Table 8 below were prepared. Materials shown in Table 9 below were used as matrix forming materials.

To this solution were added the types and amounts of metal compounds shown in Table 9 and stirred at room temperature to obtain a mixture. Next, the mixture was cast on a flat plate and dried at 80 ° C. for 2 hours to obtain a transparent, pale yellow film having a thickness of 200 μm.

This film was irradiated with the same xenon lamp as in Example 19 to obtain a film made of a colorless material. This film was evaluated in the same manner as in Example 19. Table 9 shows the results.

Comparative Example 6 A film made of a material irradiated with a xenon lamp was prepared and evaluated in the same manner as in Example 42 except that ethylene glycol (EG) was not used. Table 9 shows the results.

The metal fine particles in the material before applying heat, which were produced in Examples 42 to 54, were too small to measure the particle diameter, but after heat application, the fine particles increased, and the particles were increased. The diameter could be measured.

As shown in Table 9, the materials prepared in Examples 42 to 54 are useful as heat-sensitive color developing properties by increasing the particle diameter of the metal fine particles by applying heat to develop color and confirming the temperature history. You can see that. On the other hand, the material of Comparative Example 6 produced without using the α-hydrogen-containing alcohol was:
It turns out that it does not develop color by application of heat and cannot be used as a thermosensitive coloring material.

Of the materials obtained in Example 42 and Examples 44 to 47,
In particular, the material obtained in Example 47 using a fluororesin was transparent and had excellent mechanical strength. Furthermore, of the materials obtained in Example 42 and Examples 48 to 54, the material obtained in Example 42 containing Au fine particles had the best contrast as a thermosensitive coloring material and formed a clear color. .

Example 55 Films A to C made of colorless materials were produced in the same manner as in Example 42, except that the amounts of AuHCl ₄ .4H ₂ O were 0.018 g, 0.54 g, and 1.8 g, respectively. The obtained film is
Stored in refrigerator at 0 ° C. for 2 months. None of these films developed color during this storage. Then
When these films were taken out of the refrigerator and left in the dark for 30 minutes at various temperatures, film A developed reddish purple at a temperature of 29 ° C, and film B developed reddish purple at a temperature of 16 ° C. Film C developed a magenta color at a temperature of 7 ° C.

From the above, it can be seen that the material obtained in this example is useful as a thermosensitive coloring material. Furthermore, when these materials contain various concentrations of metal fine particles, and when heat is applied for a certain period of time in a dark place, the temperature for obtaining a specific color tone depends on the concentration of the metal fine particles. It can be seen that it changes.

Example 56 A film made of a colorless material was prepared in the same manner as in Example 42, and stored in a refrigerator at 0 ° C. for 2 months. The films were then removed from the refrigerator and placed in the dark for 20 minutes at temperatures of 25 ° C, 40 ° C, and 60 ° C, respectively. The films developed a reddish purple color at 25 ° C., a brownish purple color at 40 ° C., and a brown color at 60 ° C.

From the above, it can be seen that the materials obtained in this example are useful as thermosensitive coloring materials. Further, these materials are obtained by coloring when heat is applied for a certain period of time in a dark place. It can be seen that the color tone changes depending on the temperature at that time.

Example 57 A solution composed of the materials shown in Table 10 below was prepared.

To this solution was added AuHCl ₄ · 4H ₂ O in 0.05 g, and was obtained mixture was stirred at room temperature. Next, the mixture was cast on a flat plate and dried at 80 ° C. for 2 hours to obtain a transparent, pale yellow film having a thickness of 200 μm.

This film was irradiated with the same xenon lamp as in Example 19 to obtain a film made of a colorless material. The obtained film was evaluated in the same manner as in Example 19. Table 11 shows the results.

Comparative Example 7 A film made of a material irradiated with a xenon lamp was prepared and evaluated in the same manner as in Example 57 except that ethylene glycol (EG) was not used. Table 11 shows the results.

The metal fine particles in the material before applying heat prepared in Example 57 were too small to measure the particle diameter,
After the application of heat, the fine particles increased, and their particle diameter could be measured.

As shown in Table 11, the material prepared in Example 57 is useful as a thermosensitive coloring material that develops color by increasing the particle diameter of the metal fine particles by applying heat and that can confirm the temperature history. I understand. Further, the material prepared in Example 57 contained polyvinylpyrrolidone to further uniformly disperse metal fine particles. In contrast, the material of Comparative Example 7, which was produced without using the α-hydrogen-containing alcohol, did not develop color due to the application of heat, indicating that it cannot be used as a thermosensitive coloring material.

Example 58 A solution shown in Table 8 was prepared in the same manner as in Example 42,
To this solution was added AuHCl ₄ · 4H ₂ O of 0.1 g, and was obtained mixture was stirred at room temperature. Then, the mixture is 20 μm thick.
And coated on a polypropylene bag (substrate)
Dried at 60 ° C. for 30 minutes. This coating and drying were repeated twice to obtain a laminate having a transparent, pale yellow thin gel film having a thickness of about 1 μm on the substrate. This laminate was irradiated with a xenon lamp for 3 minutes in the same manner as in Example 19, to obtain an element having a film made of a colorless material on a substrate. Using this device, Example 19
The same evaluation of the temperature history was performed. Table 12 shows the results.

Comparative Example 8 An element having a film made of a material irradiated with a xenon lamp was prepared and evaluated in the same manner as in Example 58 except that ethylene glycol (EG) was not used. Table 12 shows the results.

The metal fine particles in the element prepared in Example 58 before applying heat were too small to measure the particle diameter,
After the application of heat, the fine particles increased, and their particle diameter could be measured.

As shown in Table 12, it can be seen that the device manufactured in Example 58 is useful as a heat-sensitive device capable of increasing the particle diameter of the metal fine particles by applying heat and developing color, and confirming the temperature history. . On the other hand, the device of Comparative Example 8 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

Example 59 A solution shown in Table 10 was prepared in the same manner as in Example 57,
To this solution was added AuHCl ₄ · 4H ₂ O of 0.1 g, and was obtained mixture was stirred at room temperature. Next, a bag (substrate) made of polypropylene having a thickness of 20 μm is immersed in a solution of the mixture, taken out, dried at room temperature for 10 minutes, and then dried at room temperature.
Dry at 20 ° C. for 20 minutes. This immersion and drying were repeated twice to form a transparent and pale yellow thin gel film having a thickness of about 1 μm on the surface of the bag.

The obtained bag was irradiated with a xenon lamp for 3 minutes in the same manner as in Example 19 to obtain an element having a film made of a colorless material. Using this device, the same temperature history evaluation as in Example 19 was performed. Table 13 shows the results.

Example 60 A device was prepared and evaluated in the same manner as in Example 59, except that a 200-μm-thick rayon fabric was used instead of the polypropylene bag. Table 13 shows the results.

Comparative Example 9 An element having a film made of a material irradiated with a xenon lamp was prepared and evaluated in the same manner as in Example 59 except that ethylene glycol (EG) was not used. Table 13 shows the results.

The metal fine particles in the element prepared in Examples 59 and 60 before applying heat were too small to measure the particle diameter, but after heat application, the fine particles increased, and the particles increased. The diameter could be measured.

As shown in Table 13, the devices fabricated in Examples 59 and 60 are useful as heat-sensitive devices that increase the particle diameter of metal particles by applying heat and develop color, and that can confirm the temperature history. I understand. On the other hand, the device of Comparative Example 9 manufactured without using the α-hydrogen-containing alcohol,
It turns out that it does not develop color by application of heat and cannot be used as a thermosensitive element.

Example 61 A solution shown in Table 6 was prepared in the same manner as in Example 19,
Was added AuHCl ₄ · 4H ₂ O of 0.2 g, and was obtained mixture was stirred at room temperature. Next, this mixture was applied to kraft paper (substrate) having a thickness of 50 μm by a spin coating method, dried at room temperature for 30 minutes, and then dried at 60 ° C. for 30 minutes. This coating and drying were repeated twice to obtain a laminate having a transparent, pale yellow thin gel film having a thickness of about 0.5 μm on the substrate. This laminate was irradiated with a xenon lamp for 3 minutes in the same manner as in Example 19 to obtain an element having a film made of a colorless material. Example using this element
Evaluation of the temperature history similar to 19 was performed. Table 14 shows the results.

Comparative Example 10 An element having a film made of a material irradiated with a xenon lamp was prepared and evaluated in the same manner as in Example 61 except that ethylene glycol (EG) was not used. Table 14 shows the results.

The metal fine particles in the element prepared in Example 61 before applying heat were too small to measure the particle diameter,
After the application of heat, the fine particles increased, and their particle diameter could be measured.

As shown in Table 14, it can be seen that the element manufactured in Example 61 is useful as a heat-sensitive element that increases the particle diameter of the metal fine particles by applying heat and develops color, and can confirm the temperature history. . On the other hand, the device of Comparative Example 10 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

Example 62 A solution composed of the materials shown in Table 15 below was prepared.

To this solution, AuHCl ₄ · 4H ₂ O of 0.18g metal compound
Was added and the mixture was stirred at room temperature for 1 hour.
Then, the mixture was cast on a flat plate and dried at room temperature for 3 days, followed by drying at 60 ° C. for 24 hours to obtain a 200 μm thick transparent light yellow gel film.

A circular sample having a diameter of 5 mm was cut out from this film, and this was filled with ethylene-sealed frozen food inside.
A sheet made of a vinyl acetate copolymer, an aluminum foil and a polyethylene sheet were sequentially laminated on the outside of a three-layer sheet packaging bag (substrate) using an epoxy adhesive. Next, the film portion of the circular sample was irradiated with white light for 5 minutes at room temperature using a 500 W xenon lamp at a distance of 30 cm from the film to obtain an element having a film made of a colorless material. Was. The obtained device was immediately stored in a refrigerator (dark place) at 0 ° C. for 2 months.

The device did not develop color during this storage. Two months later, the device was taken out of the refrigerator and kept in a dark place at 25 ° C. for 20 minutes. The color-developed device contains Au fine particles with a small particle size distribution having an average particle size of 5 nm, and is based on the surface plasmon absorption of the Au fine particles.
It had an absorption peak at 525 nm. Next, the device was placed again in a refrigerator at 0 ° C., and the temperature history was confirmed without losing the color tone of the color-developed device. Table 16 shows the results of the evaluation of the devices obtained in this example.

Examples 63 to 72 Except that the metal compounds, α-hydrogen-containing alcohols, and matrix forming materials shown in Table 16 were used, devices were produced in the same manner as in Example 62, and the devices were evaluated. Table 16 shows the results.

Comparative Example 11 A device was prepared and evaluated in the same manner as in Example 62 except that ethylene glycol (EG) was not used. Table 16 shows the results.

The metal fine particles in the element prepared in Examples 62 to 72 before applying heat were too small to measure the particle diameter, but after heat application, the fine particles increased, and the particles increased. The diameter could be measured.

As shown in Table 16, the devices manufactured in Examples 62 to 72 are useful as heat-sensitive devices that increase the particle diameter of metal fine particles by applying heat and develop color, and that can confirm the temperature history. I understand. On the other hand, the device of Comparative Example 11 manufactured without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

Of the devices obtained in Example 62 and Examples 66 to 72,
The device obtained in Example 62 containing Au fine particles clearly developed color with the best contrast as a heat-sensitive device.

Example 73 Devices A to C were produced in the same manner as in Example 62, except that the amounts of AuHCl ₄ .4H ₂ O were 0.018 g, 0.54 g, and 1.8 g, respectively. The obtained device was stored in a refrigerator at 0 ° C. for 2 months. None of the devices developed color during this storage. Then remove these elements from the refrigerator,
When placed at various temperatures for 30 minutes in a dark place, the device A
At a temperature of 28 ° C., a magenta color developed, device B developed a magenta color at a temperature of 15 ° C., and device C developed a magenta color at a temperature of 7 ° C.

From the above, it can be seen that the element obtained in this example is useful as a thermosensitive element. Furthermore, when these devices contain various concentrations of metal fine particles, and when these devices are heated for a certain period of time in a dark place, the temperature for obtaining a specific color tone is reduced by the concentration of the metal fine particles. It turns out that it changes depending on.

Example 74 A device was prepared in the same manner as in Example 62, and stored in a refrigerator at 0 ° C for 2 months. The devices were then removed from the refrigerator and left in the dark for 20 minutes at 25 ° C, 40 ° C.
And 60 ° C. respectively. Element temperature is 25 ℃
At 40 ° C to brownish purple,
Then, at 60 ° C., a brown color developed.

From the above, it can be seen that the element obtained in this example is useful as a thermosensitive element. Furthermore, when heat is applied to these elements in a dark place for a certain period of time, the color tone of the elements obtained by coloring changes depending on the temperature at that time.

Examples 75 to 82 Devices were produced in the same manner as in Example 62 and Examples 66 to 72 except that the temperature during irradiation with the xenon lamp was set to 0 ° C., and the devices were evaluated. The evaluation effects of the obtained devices were all the same as those of Example 62 and Examples 66 to 72, and were found to be useful as heat-sensitive devices.

Examples 83 and 84 Solutions composed of the materials shown in Table 17 below were prepared.

To this solution were added the types and amounts of metal compounds shown in Table 18 and stirred at room temperature to obtain a mixture. Next, a transparent and pale yellow film having a thickness of 200 μm was obtained from the mixture in the same manner as in Example 62. Further, in the same manner as in Example 62, a circular sample was obtained from this film, a device was produced, and the device was evaluated. The results are shown in Table 18.

Comparative Example 12 A device was prepared and evaluated in the same manner as in Example 83 except that ethylene glycol (EG) was not used. The results are shown in Table 18.

The metal fine particles in the device before heat application, prepared in Examples 83 and 84, were too small to measure the particle size, but after heat application, the fine particles increased, and the particles were increased. The diameter could be measured.

As shown in Table 18, the devices manufactured in Examples 83 and 84 are useful as heat-sensitive devices that increase the particle diameter of the metal fine particles by applying heat, develop color, and can confirm the temperature history. I understand. On the other hand, the device of Comparative Example 12 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

Example 85 Devices A to C were produced in the same manner as in Example 83, except that the amounts of AuHCl ₄ .4H ₂ O were 0.018 g, 0.54 g, and 1.8 g, respectively. The obtained device was stored in a refrigerator at 0 ° C. for 2 months. None of the devices developed color during this storage. Then remove these elements from the refrigerator,
When placed in a dark place at various temperatures for 30 minutes, the used device A developed reddish purple at a temperature of 28 ° C., the device B developed reddish purple at a temperature of 15 ° C., and the device C developed a reddish purple at a temperature of 15 ° C. At a temperature of 7 ° C.

From the above, it can be seen that the element obtained in this example is useful as a thermosensitive element. Furthermore, when these devices contain various concentrations of metal fine particles, and when these devices are heated for a certain period of time in a dark place, the temperature for obtaining a specific color tone is reduced by the concentration of the metal fine particles. It turns out that it changes depending on.

Example 86 A device was prepared in the same manner as in Example 83, and stored in a refrigerator at 0 ° C for 2 months. The devices were then removed from the refrigerator and left in the dark for 30 minutes at 25 ° C, 40 ° C.
And 60 ° C. respectively. Element temperature is 25 ℃
At 40 ° C to brownish purple,
Then, at 60 ° C., a brown color developed.

From the above, it can be seen that the element obtained in this example is useful as a thermosensitive element. Further, it can be seen that when heat is applied to these elements in a dark place for a certain period of time, the color tone of the elements obtained by coloring changes depending on the temperature at that time.

Examples 87 and 88 Devices were produced in the same manner as in Examples 83 and 84 except that the temperature during irradiation with the xenon lamp was set at 0 ° C., and the devices were evaluated. The obtained results were all the same as those of Examples 83 and 84, and were found to be useful as heat-sensitive elements.

Examples 89-101 Solutions composed of the materials shown in Table 19 below were prepared.

To this solution, the types and amounts of metal compounds shown in Table 20 were added and stirred at room temperature to obtain a mixture. Next, a transparent and pale yellow film having a thickness of 200 μm was obtained in the same manner as in Example 62 except that the mixture was dried at 80 ° C. for 2 hours. Further, in the same manner as in Example 62, a circular sample was obtained from this film, a device was produced, and the device was evaluated. Table 20 shows the results.

Comparative Example 13 A device was prepared and evaluated in the same manner as in Example 89 except that ethylene glycol (EG) was not used. Table 20 shows the results.

The metal fine particles in the element prepared in Examples 89 to 101 before the application of heat were too small to measure the particle diameter, but after the application of heat, the fine particles increased, and the particles were increased. The diameter could be measured.

As shown in Table 20, the devices manufactured in Examples 89 to 101 are useful as heat-sensitive devices capable of increasing the particle diameter of metal fine particles by application of heat, developing color, and confirming the temperature history. I understand. In contrast, the device of Comparative Example 13 fabricated without using an α-hydrogen-containing alcohol,
It turns out that it does not develop color by application of heat and cannot be used as a thermosensitive element.

Of the devices obtained in Examples 89 to 94, the device of Example 94 using a fluororesin was particularly transparent and excellent in mechanical strength. Furthermore, of the devices obtained in Example 89 and Examples 95 to 101, the device of Example 89 containing Au fine particles produced clear color with the best contrast as a heat-sensitive device.

Example 102 Devices A to C were produced in the same manner as in Example 89, except that the amounts of AuHCl ₄ .4H ₂ O were 0.005 g, 0.15 g, and 0.5 g, respectively. The obtained device was stored in a refrigerator at 0 ° C. for 2 months. None of the devices developed color during this storage. Then remove these elements from the refrigerator,
After 30 minutes in the dark, device A developed a reddish purple color at a temperature of 29 ° C., device B developed a reddish purple color at a temperature of 16 ° C., and device C developed a reddish purple color at a temperature of 16 ° C. It developed a purple-red color.

From the above, it can be seen that the element obtained in this example is useful as a thermosensitive element. Furthermore, when these devices contain various concentrations of metal fine particles, and when these devices are heated for a certain period of time in a dark place, the temperature for obtaining a specific color tone is reduced by the concentration of the metal fine particles. It turns out that it changes depending on.

Example 103 A device was prepared in the same manner as in Example 89, and stored in a refrigerator at 0 ° C for 2 months. Next, these elements were taken out of the refrigerator and kept in the dark for 30 minutes at 25 ° C, 40 ° C,
And at a temperature of 60 ° C, respectively. The device developed a reddish purple color at 25 ° C., a brownish purple color at 40 ° C., and a brown color at 60 ° C.

From the above, it can be seen that the element obtained in this example is useful as a thermosensitive element. Furthermore, when heat is applied to these elements in a dark place for a certain period of time, the color tone of the elements obtained by coloring changes depending on the temperature at that time.

Example 104 A solution shown in Table 19 was prepared in the same manner as in Example 89,
To this solution was added AuHCl ₄ · 4H ₂ O in 0.05 g, was stirred at room temperature. Next, the obtained mixture was cast on a flat plate, thermocompression-bonded, and dried at 80 ° C for 2 hours to obtain a thickness of about 500 µm.
A bag made of a transparent light yellow sheet was prepared. The bag was filled with frozen food and sealed.

Using a 500W xenon lamp at room temperature in this bag,
By irradiating the film with white light for 5 minutes at an interval of 30 cm from the film, an element having a film made of a colorless material was obtained. The obtained device was immediately placed in a refrigerator at 0 ° C (in a dark place).
For 2 months.

The device did not develop color during this storage. Two months later, when the device was taken out of the refrigerator and kept in a dark place at 25 ° C. for 20 minutes, the device developed color and showed a purple-red color. The color-developed device contained Au fine particles having an average particle diameter of 4 nm and a small particle size distribution, and had an absorption peak at 530 nm based on the surface plasmon absorption of the Au fine particles. Next, the device was placed again in a refrigerator at 0 ° C., and the temperature history was confirmed without losing the color tone of the color-developed device. Table 21 shows the evaluation results of the devices obtained in this example.

Examples 105 to 109 Except that the metal compounds, α-hydrogen-containing alcohols, and matrix forming materials shown in Table 21 were used, devices were produced in the same manner as in Example 104, and the devices were evaluated. Table 21 shows the results.

Comparative Example 14 A device was produced and evaluated in the same manner as in Example 104 except that ethylene glycol (EG) was not used. Table 21 shows the results.

The metal fine particles in the element prepared in Examples 104 to 109 before applying heat were too small to measure the particle diameter, but after heat application, the fine particles increased, and the particles increased. The diameter could be measured.

As shown in Table 21, the devices fabricated in Examples 104 to 109 are useful as heat-sensitive devices that increase the particle diameter of the metal fine particles by applying heat, develop color, and can confirm the temperature history. I understand. In contrast, the device of Comparative Example 14 made without using an α-hydrogen-containing alcohol,
It turns out that it does not develop color by application of heat and cannot be used as a thermosensitive element.

Of the devices obtained in Examples 104 to 109, the device of Example 109 using a fluororesin was particularly transparent and excellent in mechanical strength. Furthermore, devices using polyvinyl alcohol described in Examples 104 and 105 had excellent transparency and could be manufactured at a relatively low cost.

Example 110 Devices A to C were produced in the same manner as in Example 104, except that the amounts of AuHCl ₄ .4H ₂ O were 0.005 g, 0.15 g, and 0.50 g, respectively. The obtained device was stored in a refrigerator at 0 ° C. for 2 months. None of the devices developed color during this storage. Then remove these elements from the refrigerator,
After 30 minutes in the dark, device A developed a reddish purple color at a temperature of 29 ° C., device B developed a reddish purple color at a temperature of 16 ° C., and device C developed a reddish purple color at a temperature of 16 ° C. It developed a purple-red color.

From the above, it can be seen that the element obtained in this example is useful as a thermosensitive element. Furthermore, when these devices contain various concentrations of metal fine particles, and when these devices are heated for a certain period of time in a dark place, the temperature for obtaining the color of the apprentice is reduced by the concentration of the metal fine particles. It turns out that it changes depending on.

Example 111 A device was prepared in the same manner as in Example 104, and stored in a refrigerator at 0 ° C for 2 months. Next, these elements were taken out of the refrigerator and kept in the dark for 30 minutes at 25 ° C, 40 ° C,
And at a temperature of 60 ° C, respectively. The device developed a reddish purple color at 25 ° C., a brownish purple color at 40 ° C., and a brown color at 60 ° C.

From the above, it can be seen that the element obtained in this example is useful as a thermosensitive element. Furthermore, when heat is applied to these elements in a dark place for a certain period of time, the color tone of the elements obtained by coloring changes depending on the temperature at that time.

Example 112 A solution composed of the materials shown in Table 22 below was prepared.

To this solution was added AuHCl ₄ · 4H ₂ O in 0.05 g, and was obtained mixture was stirred at room temperature. Next, the mixture was cast on a flat plate and dried at 80 ° C. for 2 hours to obtain a transparent, pale yellow film having a thickness of 200 μm.

A circular sample having a diameter of 5 mm was cut out from this film, and this was filled with ethylene-sealed frozen food inside.
A sheet made of a vinyl acetate copolymer, an aluminum foil and a polyethylene sheet were sequentially laminated on the outside of a three-layer sheet packaging bag (substrate) using an epoxy adhesive. Then, Example 62 was applied to the film portion of the circular sample.
Irradiation with a xenon lamp was performed in the same manner as in Example 1 to obtain a device having a film made of a colorless material on a substrate. Using this device, the same temperature history evaluation as in Example 62 was performed. The results are shown in Table 23.

Comparative Example 15 A device was prepared and evaluated in the same manner as in Example 112 except that ethylene glycol (eg) was not used. The results are shown in Table 23.

The metal fine particles in the element prepared in Example 112 before the application of heat were too small to measure the particle diameter, but after the application of heat, the fine particles increased, and the particle diameter was increased. Measurement was possible.

As shown in Table 23, the device manufactured in Example 112 was useful as a heat-sensitive device capable of increasing the particle diameter of the metal fine particles by applying heat to develop color and confirming the temperature history. Further, the device manufactured in Example 112 contained polyvinyl pyrrolidone to further uniformly disperse metal fine particles. On the other hand, the device of Comparative Example 7 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

Example 113 A solution shown in Table 15 was prepared in the same manner as in Example 62,
To this solution was added AuHCl ₄ · 4H ₂ O in 0.18 g, and was obtained mixture was stirred at room temperature. Next, the mixture was applied to a three-layer sheet (substrate) for packaging in which a 50 μm-thick ethylene-vinyl acetate copolymer sheet, an aluminum foil and a polyethylene sheet were sequentially laminated, and dried at room temperature for 5 minutes. Dry at 30 ° C. for 30 minutes. This coating and drying were repeated twice to obtain a laminate having a transparent, pale yellow thin gel film having a thickness of about 1 μm on the substrate.
Next, this laminate was irradiated with a xenon lamp for 3 minutes in the same manner as in Example 62, to obtain a device having a film made of a colorless material on a substrate. Using this element,
The same temperature history evaluation as in Example 62 was performed. Table 24 shows the results.
Shown in

Comparative Example 16 A device was prepared and evaluated in the same manner as in Example 113 except that ethylene glycol (EG) was not used. The results are shown in Table 24.

The metal fine particles in the element before heat application, which were produced in Example 113, were too small to be able to produce a particle diameter.However, after heat application, the fine particles increased, and the particle diameter was increased. Measurement was possible.

As shown in Table 24, it was found that the element manufactured in Example 113 was useful as a heat-sensitive element that increased the particle diameter of the metal fine particles by applying heat and developed color, and that could confirm the temperature history. . On the other hand, the device of Comparative Example 16 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

Example 114 A solution shown in Table 17 was prepared in the same manner as in Example 83,
Was added AuHCl ₄ · 4H ₂ O in 0.18 g, and was obtained mixture was stirred at room temperature. Next, this mixture was applied to kraft paper (substrate) having a thickness of 50 μm by a spin coating method, dried at room temperature for 30 minutes, and then dried at 60 ° C. for 30 minutes. This coating and drying were repeated twice to obtain a laminate having a transparent and pale yellow thin gel film having a thickness of about 0.5 μm on the substrate. This laminate was irradiated with a xenon lamp for 3 minutes in the same manner as in Example 62, to obtain a device having a film made of a colorless material. Using this device, the same temperature history evaluation as in Example 62 was performed. The results are shown in Table 25.

Comparative Example 17 A device was prepared and evaluated in the same manner as in Example 114, except that ethylene glycol (EG) was not used. The results are shown in Table 25.

The metal fine particles in the element prepared in Example 114 before the application of heat were too small to measure the particle size, but after the application of heat, the fine particles increased, and the particle size was increased. Measurement was possible.

As shown in Table 25, it was found that the element manufactured in Example 114 was useful as a heat-sensitive element which increased the particle diameter of the metal fine particles by applying heat, developed color, and confirmed the temperature history. . On the other hand, the device of Comparative Example 17 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

Example 115 A solution shown in Table 19 was prepared in the same manner as in Example 89,
To this solution was added AuHCl ₄ · 4H ₂ O in 0.05 g, and was obtained mixture was stirred at room temperature. Then, the mixture was applied to a three-layer sheet (substrate) for packaging in which a sheet made of an ethylene-vinyl acetate copolymer having a thickness of 100 μm, an aluminum foil and a polyethylene sheet were sequentially laminated, and dried at room temperature for 5 minutes. Dry at 30 ° C. for 30 minutes. This coating and drying were repeated twice to obtain a laminate having a transparent, pale yellow thin gel film having a thickness of about 1 μm on the substrate. Next, this laminate was irradiated with a xenon lamp for 3 minutes in the same manner as in Example 62, to obtain a device having a film made of a colorless material on a substrate. Using this device, the same temperature history evaluation as in Example 62 was performed. The results are shown in Table 26.

Example 116 A device was prepared and evaluated in the same manner as in Example 115, except that a rayon fabric having a thickness of 200 µm was used instead of the polypropylene bag. The results are shown in Table 26.

Comparative Example 18 A device was prepared and evaluated in the same manner as in Example 115 except that ethylene glycol (EG) was not used. The results are shown in Table 26.

The metal fine particles in the element prepared in Examples 115 and 116 before applying heat were too small to measure the particle diameter, but after heat application, the fine particles increased, and the particles were increased. The diameter could be measured.

As shown in Table 26, the devices manufactured in Examples 115 and 116 are useful as a heat-sensitive device that increases the particle diameter of metal fine particles by applying heat and develops a color, and that can confirm a temperature history. I understand. On the other hand, the device of Comparative Example 18 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

Example 117 A solution composed of the materials shown in Table 27 below was prepared.

To this solution, AuHCl ₄ · 4H ₂ O of 0.18g metal compound
Was added and the mixture was stirred at room temperature for 1 hour.
Then, the mixture was cast on a flat plate and dried at room temperature for 3 days, followed by drying at 60 ° C. for 24 hours to obtain a 200 μm thick transparent light yellow gel film.

The film was irradiated with white light for 5 minutes at room temperature using a 500 W xenon lamp at an interval of 30 cm from the film to obtain a film made of a colorless material. A metal tape having an adhesive layer on one side of an aluminum foil was adhered to both sides of the film to produce an element in which transmission of light from the outside was blocked. The device was immediately stored in a refrigerator (dark place) at 0 ° C. for 2 months.

The device did not develop color during this storage. Two months later, the devices were removed from the refrigerator and placed in direct sunlight at 25 ° C for 10 minutes. Next, by peeling the metal tape from the device, it was confirmed that the film in the device had developed a reddish purple color. The colored film in the device has an average particle size of about 5n
It contained Au fine particles having a small particle size distribution having m, and had an absorption peak at 525 nm based on the surface plasmon absorption of the Au fine particles. Next, the device was placed again in a refrigerator at 0 ° C., and the temperature history was confirmed without losing the color tone of the film formed in the device. Table 28 shows the types of the metal compound, the α-hydrogen-containing alcohol, and the matrix forming material used in this example, and the evaluation results of the obtained devices.

In addition, an element made of a material alone irradiated with a xenon lamp and manufactured in the same manner as described above without attaching a metal tape, was exposed to direct sunlight at room temperature for a considerably long time (approximately
It was found that if exposure was continued, color development proceeded and the color tone changed.

Examples 118 to 127 Except that the metal compounds, α-hydrogen-containing alcohols, and matrix forming materials shown in Table 28 were used, devices were produced in the same manner as in Example 117, and the devices were evaluated. The results are shown in Table 28.

Comparative Example 19 A device was prepared and evaluated in the same manner as in Example 117 except that ethylene glycol (EG) was not used. The results are shown in Table 28.

The metal fine particles in the device prepared in Examples 117 to 127 before applying heat were too small to measure the particle diameter, but after heating, the fine particles increased, and their particle diameter increased. Was possible.

As shown in Table 28, the devices manufactured in Examples 117 to 127 are useful as heat-sensitive devices that increase the particle diameter of metal particles by application of heat, develop color, and can confirm the temperature history. I understand. In contrast, the device of Comparative Example 19 produced without using an α-hydrogen-containing alcohol,
It turns out that it does not develop color by application of heat and cannot be used as a thermosensitive element.

In the above examples 117 to 127, devices using Si (OC ₂ H _{5) 4} as a matrix-forming material to form the most stable matrix substances and could be manufactured at relatively low cost. Further, among the devices obtained in Example 117 and Examples 121 to 128, the device of Example 117 containing Au fine particles clearly developed a color with the best contrast as a heat-sensitive device.

0.018g amounts of Example _{128 AuHCl 4 · 4H 2 O,} 0.54g, and except that the 1.8g An element in the same manner as each embodiment 117 A through C
Was prepared. The obtained device was stored in a refrigerator at 0 ° C. for 2 months. None of the devices developed color during this storage. The devices were then removed from the refrigerator and placed in direct sunlight for 10 minutes. Next, when the metal tape was peeled off from each of the devices, the device A developed a magenta color at a temperature of 28 ° C., the device B developed a magenta color at a temperature of 15 ° C., and the device C developed a temperature of 7 ° C. The color was reddish purple.

From the above, it can be seen that the element obtained in this example is useful as a thermosensitive element. Furthermore, when these devices contain various concentrations of metal fine particles, and when these devices are heated for a certain period of time in a dark place, the temperature for obtaining a specific color tone is reduced by the concentration of the metal fine particles. It turns out that it changes depending on.

Example 129 A device was prepared in the same manner as in Example 117, and stored in a refrigerator at 0 ° C for 2 months. The devices were then removed from the refrigerator and placed in direct sunlight for 10 minutes at 25 ° C.
Placed at temperatures of 40 ° C and 60 ° C, respectively. Then, when the metal tape was peeled off from the device, the film in the device developed a reddish purple color at 25 ° C, developed a brownish purple color at 40 ° C, and developed a brown color at 60 ° C.

From the above, it can be seen that the element obtained in this example is useful as a thermosensitive element. Furthermore, when heat is applied to these elements in a dark place for a certain period of time, the color tone of the elements obtained by coloring changes depending on the temperature at that time.

Examples 130 to 140 Except that the temperature at the time of irradiation with a xenon lamp was set to 0 ° C., devices were manufactured in the same manner as in Examples 117 to 127, respectively, and their evaluation was performed. The obtained results were all the same as those of Examples 117 to 127, and were found to be useful as thermal elements.

Example 141 A solution composed of the materials shown in Table 29 below was prepared.

To this solution, AuHCl ₄ · 4H ₂ O of 0.18g metal compound
Was added and stirred at room temperature to give a mixture. Then, the mixture was cast on a flat plate and dried at room temperature for 3 days, followed by drying at 60 ° C. for 24 hours to obtain a transparent, pale yellow film having a thickness of 200 μm. Example 117 except that this film was used and a glass tape was used as a light-shielding layer.
A device was prepared in the same manner as described above and evaluated. The results are shown in Table 30.

Examples 142 to 151 Except that the metal compounds, α-hydrogen-containing alcohols, and matrix forming materials shown in Table 30 were used, devices were manufactured in the same manner as in Example 141, and the devices were evaluated. The results are shown in Table 30.

Comparative Examples 20 to 22 Except that ethylene glycol (EG) was not used, devices were produced in the same manner as in Examples 141, 143, and 144, and the devices were evaluated. The results are shown in Table 30.

The metal fine particles in the device before applying heat, which were produced in Examples 141 to 151, were too small to measure the particle diameter, but after the heat application, the fine particles increased, and the particles increased. The diameter could be measured.

As shown in Table 30, the devices fabricated in Examples 141 to 151 are useful as heat-sensitive devices that increase the particle diameter of metal particles by applying heat and develop color, and that can confirm the temperature history. I understand. In contrast, the devices of Comparative Examples 20 to 22 prepared without using an α-hydrogen-containing alcohol,
It turns out that it does not develop color by application of heat and cannot be used as a thermosensitive element.

Of the devices obtained in Example 141 and Examples 145 to 151, the device of Example 141 containing Au fine particles had the best contrast as a heat-sensitive device and produced vivid color.
In Examples 141 to 151, the color tone of the colored film in the device could be confirmed through the glass tape without peeling the glass tape. Furthermore, all of the devices made of the material alone irradiated with the xenon lamp and produced in the same manner as in Examples 141 to 151 without attaching the glass tape, for a long time (approximately It was found that if exposure was continued, color development proceeded and the color tone changed.

Examples 152 to 162 Devices were produced in the same manner as in Examples 141 to 151 except that the temperature at the time of irradiation with the xenon lamp was set to 0 ° C., and their evaluation was performed. The evaluation results of the obtained devices were all the same as those of Examples 141 to 151, and were found to be useful as heat-sensitive devices.

Examples 163-175 Solutions composed of the materials shown in Table 31 below were prepared. Materials shown in Table 32 below were used as matrix forming materials.

To this solution, the types and amounts of metal compounds shown in Table 32 were added and stirred at room temperature to obtain a mixture. Next, the mixture was cast on a flat plate and dried at 80 ° C. for 2 hours to obtain a transparent, pale yellow film having a thickness of 200 μm. A device was prepared and evaluated in the same manner as in Example 117 except that this film was used. The results are shown in Table 32.

The metal fine particles in the element prepared in Examples 163 to 175 before applying heat were too small to measure the particle diameter, but after heat application, the fine particles increased, and the particles increased. The diameter could be measured.

As shown in Table 32, the devices manufactured in Examples 163 to 175 increase the particle diameter of the metal fine particles by applying heat, develop color, and are useful as heat-sensitive devices capable of confirming the temperature history. I understand.

Among the devices provided with the thermosensitive coloring material containing Au fine particles obtained in Examples 163 to 168, the device of Example 168 using a fluororesin was transparent and excellent in mechanical strength. Furthermore, of the devices containing various metal compounds obtained in Example 163 and Examples 169 to 175, the device of Example 163 containing Au fine particles has the best contrast as a heat-sensitive device and has sharpness. It developed color.

Further, in Examples 163 to 175 above, devices using polyvinyl alcohol as the matrix forming material formed the most stable matrix material and could be manufactured at relatively low cost. In addition, without attaching a metal tape, manufactured in the same manner as in Examples 163 to 175,
It has been found that the color development of all the elements made of the material alone irradiated with the xenon lamp when exposed to direct sunlight at room temperature for a considerably long time (about 5 hours or more) progresses and the color tone changes.

In the same manner as in Example 176 Example 117, a solution shown in Table 27, the addition of AuHCl ₄ · 4H ₂ O of 0.18g metal compound, and to obtain a mixture was stirred at room temperature. The mixture is then
Apply on a 50μm stainless steel film (substrate)
Dry at room temperature for 5 minutes, then at 60 ° C. for 30 minutes. This coating and drying were repeated twice to obtain a laminate having a transparent and pale yellow gel film having a thickness of about 0.2 μm on the substrate. Using a 500 W xenon lamp at room temperature, this laminate was irradiated with white light for 30 cm at an interval of 30 cm from the laminate.
By irradiating for 2 seconds, an element having a film made of a colorless material containing Au fine particles was obtained. Further, a metal tape having an adhesive layer on one side of an aluminum foil was attached to both sides of the obtained element to produce an element in which transmission of light from the outside was blocked. This device was evaluated in the same manner as in Example 117. The results are shown in Table 33.

Except that the metal tape was not applied, the device produced in the same manner as described above, when exposed to direct sunlight at room temperature for a considerably long time (about 3 hours or more), the color development progressed and the color tone changed. I found out.

Comparative Example 23 A device was prepared and evaluated in the same manner as in Example 176, except that ethylene glycol (EG) was not used. The results are shown in Table 33.

The metal fine particles in the element before applying heat, prepared in Example 176, were too small to measure the particle diameter, but after heat application, the fine particles increased, and the measurement of those particles Was possible.

As shown in Table 33, the one made in Example 176
It can be seen that application of heat increases the particle diameter of the metal fine particles to develop color and is useful as a thermosensitive element capable of confirming the temperature history. On the other hand, the device of Comparative Example 23 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

In the same manner as in Comparative Example 177 Example 141, a solution shown in Table 29, the addition of AuHCl ₄ · 4H ₂ O of 0.18g metal compound, and to obtain a mixture was stirred at room temperature. The mixture is then
It was applied on a 50 μm transparent glass plate (substrate), dried at room temperature for 5 minutes, and then dried at 60 ° C. for 30 minutes. This coating and drying were repeated twice to obtain a laminate having a transparent and pale yellow film having a thickness of about 0.5 μm on the substrate. An element was fabricated and evaluated in the same manner as in Example 117 except that this laminate was used. The results are shown in Table 34.

Examples 178 and 179 Example 1 was performed using the matrix-forming materials shown in Table 34, except that the thickness of the obtained laminate was about 0.2 μm.
Elements were manufactured in the same manner as in 77, and the evaluation was performed. The results are shown in Table 34.

Comparative Examples 24 to 26 Except that ethylene glycol (EG) was not used, devices were produced in the same manner as in Examples 171 to 179, respectively, and their evaluation was performed. The results are shown in Table 34.

Prepared in Examples 177 to 179, the metal fine particles in the element before applying heat, the particle diameter could not be measured because it was too small, after heat application those fine particles increase, their particle diameter Was possible.

As shown in Table 34, the devices manufactured in Examples 177 to 179 increase the particle diameter of the metal fine particles by applying heat, develop color, and are useful as heat-sensitive devices capable of confirming the temperature history. I understand. On the other hand, it was found that the devices of Comparative Examples 24 to 26, which were produced without using the α-hydrogen-containing alcohol, did not develop a color due to the application of heat and could not be used as a thermosensitive device.

In addition, without sticking the metal tape,
Any device made of a material alone irradiated with a xenon lamp and manufactured in the same manner as 177 to 179 develops color when exposed to direct sunlight at room temperature for a long time (about 5 hours or more). It was found to change the color tone.

Examples 180 to 185 In the same manner as in Example 163, the solutions shown in Table 31 were prepared. Materials shown in Table 35 below were used as the matrix forming materials.

To this solution, the types and amounts of metal compounds shown in Table 32 were added and stirred at room temperature to obtain a mixture. Then, the mixture was applied on a transparent glass plate (substrate) having a thickness of 50 μm, dried at room temperature for 5 minutes, and then dried at 60 ° C. for 30 minutes. This coating and drying are repeated twice to obtain a thickness of about
A laminate having a 0.6 μm transparent, pale yellow film on the substrate was obtained. Example 11 except that this laminated pair was used
A device was prepared in the same manner as in 7, and the device was evaluated. The results are shown in Table 35.

Prepared in Examples 180-185, the metal fine particles in the element before applying heat, the particle size could not be measured because it was too small, but after heat application, the fine particles increased, those particles The diameter could be measured.

As shown in Table 35, the devices manufactured in Examples 180 to 185 are useful as heat-sensitive devices that increase the particle diameter of metal fine particles by applying heat and develop color, and that can confirm the temperature history. I understand.

Of the devices obtained in Examples 180 to 185, the device of Example 185 using a fluorine resin was particularly transparent and excellent in mechanical strength. Further, in the above Examples 180 to 185, the device using polyvinyl alcohol as the matrix forming material forms the most stable matrix material,
And could be manufactured at relatively low cost. In addition, all of the devices manufactured in the same manner as in Examples 180 to 185 described above without attaching a metal tape develop color when exposed to direct sunlight at room temperature for a long time (about 3 hours or more). To change its color.

In the same manner as in Example 186 Example 117, a solution shown in Table 27, the addition of AuHCl ₄ · 4H ₂ O of 0.18g metal compound, and to obtain a mixture was stirred at room temperature. The mixture is then
A 30 μm white paper tape (substrate having an adhesive layer on one side) is coated on the substrate surface, dried at room temperature for 5 minutes,
After drying at 60 ° C. for 30 minutes, a light yellow paper tape impregnated with the above mixture was obtained. The impregnated paper tape was illuminated with white light for 30 seconds at room temperature using a 500 W xenon lamp, at intervals of 30 cm from the paper tape, containing Au fine particles, and an adhesive layer was formed on one side. Was obtained. Further, a metal tape having an adhesive layer on one side of an aluminum foil was attached to the surface of the device opposite to the adhesive layer, thereby producing a device in which transmission of light from the outside was blocked.
This device was evaluated in the same manner as in Example 117. Table 3 shows the results
See Figure 6.

Except that the metal tape was not applied, the device fabricated in the same manner as described above, when exposed to direct sunlight at room temperature for a considerably long time (about 1 hour or more), color development progressed and the color tone changed. I found out.

Comparative Example 27 A device was prepared and evaluated in the same manner as in Example 186, except that ethylene glycol (EG) was not used. The results are shown in Table 36.

The metal fine particles in the element before applying heat, which were produced in Example 186, were too small to measure the particle diameter, but after the heat application, the fine particles increased, and the particle diameter was increased. Measurement was possible.

As shown in Table 36, it was found that the device manufactured in Example 186 was useful as a heat-sensitive device capable of increasing the particle diameter of the metal fine particles by applying heat, developing color, and confirming the temperature history. . On the other hand, the device of Comparative Example 27 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

In the same manner as in Example 187 Example 117, a solution shown in Table 27, the addition of AuHCl ₄ · 4H ₂ O of 0.18g metal compound, and to obtain a mixture was stirred at room temperature. The mixture is then
It was coated on a 100 μm glass plate (substrate made of ground glass having an adhesive layer on one side), dried at room temperature for 5 minutes, and then dried at 60 ° C. for 30 minutes. The glass plate coated with this mixture showed a light yellow color. Next, a white light was applied to the glass plate coated with this mixture at room temperature using a 500 W xenon lamp at a distance of 30 cm from the glass plate.
By irradiating for 2 seconds, an element having a film made of a material containing Au fine particles and having an adhesive layer on one side was obtained. Further, a metal tape having an adhesive layer on one side of an aluminum foil was adhered on the film of this element to produce an element in which transmission of light from the outside was blocked. This device was evaluated in the same manner as in Example 117. Table 37 shows the results.
Shown in

It should be noted that, except that the metal tape was not adhered, the element produced in the same manner as described above, when exposed to direct sunlight at room temperature for a considerably long time (about 2 hours or more), the color development proceeds and the color tone changes. I understand.

Comparative Example 28 A device was prepared and evaluated in the same manner as in Example 187 except that ethylene glycol (EG) was not used. The results are shown in Table 37.

The metal fine particles in the element prepared in Example 187 before the application of heat were too small to measure the particle diameter because the particle diameter was too small. Measurement was possible.

As shown in Table 37, the element manufactured in Example 187 was found to be useful as a heat-sensitive element capable of developing a color by increasing the particle diameter of metal fine particles by applying heat, and confirming the temperature history. . On the other hand, the device of Comparative Example 28 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

In the same manner as in Example 188 Example 141, a solution shown in Table 29, the addition of AuHCl ₄ · 4H ₂ O of 0.18g metal compound, and to obtain a mixture was stirred at room temperature. The mixture is then
A 100 μm white glass tape (substrate made of a glass fiber cloth having an adhesive layer on one side) is applied on a substrate, dried at room temperature for 5 minutes, and then dried at 60 ° C. for 30 minutes to impregnate the mixture. A light yellow glass tape was obtained. Using a 500 W xenon lamp at room temperature, the impregnated glass tape was irradiated with white light for 5 minutes at a distance of 30 cm from the glass tape to have a film containing Au fine particles, and A white element having an adhesive layer on one side was obtained. Further, a metal tape having an adhesive layer on one side of an aluminum foil was stuck on the film of this element to produce an element in which light from the outside was blocked.
This device was evaluated in the same manner as in Example 117. Table 3 shows the results
See Figure 8.

In addition, it was found that the element produced in the same manner as described above, except that the metal tape was not attached, developed color more when exposed to direct sunlight at room temperature for a considerably long time (about 2 hours or more).

Comparative Example 29 A device was fabricated and evaluated in the same manner as in Example 188 except that ethylene glycol (EG) was not used. The results are shown in Table 38.

The metal fine particles in the element before applying heat, which were produced in Example 188, were too small to measure the particle size, but after the heat application, the fine particles increased, and the particle size was increased. Measurement was possible.

As shown in Table 38, it was found that the device manufactured in Example 188 was useful as a heat-sensitive device capable of increasing the particle diameter of the metal fine particles by applying heat to develop color, and confirming the temperature history. . On the other hand, the device of Comparative Example 29 produced without using the α-hydrogen-containing alcohol did not develop color due to the application of heat, indicating that it could not be used as a thermosensitive device.

Example 189 In the same manner as in Example 163, the solutions shown in Table 31 were prepared. As the matrix forming material, a material shown in Table 39 described later was used. In this solution, as a metal compound
Was added AuHCl ₄ · 4H ₂ O in 0.05 g, and was obtained mixture was stirred at room temperature. The mixture is then applied to a 30 μm thick white paper tape (substrate having an adhesive layer on one side), dried at room temperature for 5 minutes, and then dried at 60 ° C. for 30 minutes to impregnate the mixture. A light yellow paper tape was obtained.
The impregnated paper tape was irradiated with white light for 30 seconds at room temperature using a 500 W xenon lamp, at a distance of 30 cm from the paper tape, with a film containing Au fine particles, and on one side. A white element having an adhesive layer was obtained. Further, a metal tape having an adhesive layer on one side of an aluminum foil was adhered on the film of this element to produce an element in which transmission of light from the outside was blocked. This device was evaluated in the same manner as in Example 117. Table 39 shows the results.
Shown in

Except that the metal tape was not applied, the device fabricated in the same manner as described above, when exposed to direct sunlight at room temperature for a considerably long time (about 1 hour or more), color development progressed and the color tone changed. I found out.

Comparative Example 30 A device was prepared and evaluated in the same manner as in Example 189 except that ethylene glycol (EG) was not used. The results are shown in Table 39.

The metal fine particles in the element before applying heat produced in Example 189 were too small to measure the particle diameter, but after the heat application, the fine particles increased, and the particle diameter was increased. Measurement was possible.

As shown in Table 39, it can be seen that the element manufactured in Example 189 is useful as a heat-sensitive element that develops color by increasing the particle diameter of the metal fine particles by applying heat, and that can confirm the temperature history. . On the other hand, the element of Comparative Example 30 produced without using the α-hydrogen-containing alcohol did not develop a color due to the application of heat, and was found to be unusable as a thermosensitive element.Example 190 Substrate as shown in 8B
A thermosensitive element 80 having a thermosensitive coloring material 82 containing metal fine particles 81 and a coloring reference 84 on 83 will be described. Here, FIG. 8A shows the thermosensitive element of the present example when stored in a dark place at a relatively low temperature (for example, 0 ° C. or lower) before heat application, and FIG. 8B shows the metal element after heat application. The thermosensitive element of this example in which fine particles are aggregated is shown.

First, a solution composed of the materials shown in Table 40 below was prepared.

To this solution, AuHCl ₄ · 4H ₂ O of 0.06g metal compound
Was added and the mixture was stirred at room temperature for 1 hour.
Then, the mixture is applied to a predetermined area on the filter paper (substrate) 83 by 5 m.
g / cm ² and dried at room temperature for 2 days, followed by 60
After drying at 48 ° C. for 48 hours, a laminate having a transparent and pale yellow gel film having a thickness of 0.1 μm on the substrate was obtained.

The laminate was irradiated with white light for 5 minutes at room temperature using a 500 W xenon lamp at an interval of 30 cm from the film to form a film 82 of a colorless material on the base 83. To the remaining area of the substrate 83, paper (see coloring) printed with a color tone (purplish red) obtained by leaving the film in a dark place at 25 ° C. for 30 minutes using an adhesive, is attached. An element 80 shown in 8A was obtained. The obtained device 80 was immediately stored in a dark place at 0 ° C. or lower for 2 months.

Device 80 did not develop color during this storage. Two months later,
When the device was taken out of the refrigerator and left in a dark place at 25 ° C. for a predetermined period of time, the film 82 in the device 80 developed color and showed reddish purple. Since the color tone of the film 82 after color development was the same as the color tone of the color development reference, the time left in a dark place at 25 ° C. was approximately
It turned out to be 30 minutes.

The element obtained in this example was found to be useful as a heat-sensitive element capable of quantifying the time when exposed to a specific temperature in a dark place by providing the coloring reference as described above. Was.

FIG. 9 shows the relationship between the time when the colorless material produced as described above was exposed to a predetermined temperature in a dark place and the color tone change rate. The color tone change rate (%) is measured by using a luminance meter to measure the luminance of the material prepared above before and after color development, respectively, and the following formula: Obtained from As shown in FIG. 9, when the colorless material manufactured in this example is exposed to a predetermined temperature in a dark place, the higher the temperature is, the faster the color development starts. The material produced by the xenon lamp produced in this example does not decrease the color tone change rate with the elapse of time, which indicates that the material is useful as a material capable of confirming a temperature range.

Examples 191 to 212 Except that the metal compounds, matrix forming materials, and bases shown in Tables 41 to 45 below were used, devices were produced in the same manner as in Example 190, and the devices were evaluated.

It has been found that any of the devices obtained above is useful as a heat-sensitive device capable of quantifying the time when exposed to a specific temperature in a dark place by providing a coloring reference.

Comparative Example 31 A device was prepared and evaluated in the same manner as in Example 190 except that ethylene glycol was not used.
Since the obtained device did not develop color, it was found that the time when it was exposed to a specific temperature in a dark place could not be quantified, and it could not be used as a thermosensitive device.

Examples 213 to 235 Devices were prepared and evaluated in the same manner as in Examples 190 to 212 except that the temperature at the time of irradiation with the xenon lamp was set to 0 ° C. or lower. All the obtained results were the same as those of Examples 190 to 212, and were found to be useful as heat-sensitive elements capable of quantifying the time when exposed to a specific temperature in a dark place. .

Example 236 This example illustrates the formation of a substrate 103, as shown in FIG.
Thermosensitive coloring material 102 containing metal fine particles 101 and coloring reference
The fabrication of the thermosensitive element 100 having 105, 106, and 107 will be described.

First, a mixture was prepared which was obtained in analogy to example 190 containing AuHCl ₄ · 4H ₂ O. Then, the mixture is filtered with filter paper (substrate) 10
3 Apply 5mg / cm ² to the specified area at room temperature.
Dried for 60 days, followed by drying at 60 ° C for 48 hours, thickness 0.1 μm
Having a transparent and pale yellow gel film on a substrate.

This laminate was irradiated with a xenon lamp in the same manner as in Example 190, to obtain a film 102 of a colorless material.
Was formed on the base 103. In the remaining area of the base 103,
Paper (see color development) 105 printed with a color tone (purple) obtained by leaving the film in a dark place at 25 ° C. for 20 minutes, a color tone obtained by leaving the film in a dark place at 25 ° C. for 40 minutes (see Red (purple) printed paper (see color development) 106, and paper (see brown) printed with a color tone (brown) 107 obtained by leaving the film in a dark place at 25 ° C. for 60 minutes were applied with an adhesive, respectively. Then, an element 100 shown in FIG. 10 was obtained.
The obtained device 100 was immediately stored in a dark place at 0 ° C. or lower for 2 months.

Device 100 did not develop color during this storage. Two months later, the device was taken out of the refrigerator and left in a dark place at 25 ° C. for a predetermined time, whereby the film 102 in the device 100 developed color. Since the color tone of the film 102 after color development was almost the same as the color tone of the color development reference 107, the time left in a dark place at 25 ° C. was approximately
It turned out to be 60 minutes.

By providing a plurality of color references as described above, the element obtained in this example was found to be useful as a thermosensitive element capable of quantifying the time when exposed to a specific temperature in a dark place. Was issued.

Example 237 On the remaining area of the substrate 103, a paper (see color development) 105 printed with a color tone (brown) obtained by allowing the film produced in Example 190 to stand in a dark place at 30 ° C. for 60 minutes, and the above film 20
A paper (see color development) 106 printed with a color tone (purple) obtained by leaving it in a dark place at 60 ° C. for 60 minutes, and the film at 10 ° C.
The element 100 was manufactured in the same manner as in Example 236, except that paper (see color development) 107 printed with a color tone (light purple) obtained by being left in a dark place for 60 minutes was adhered using an adhesive.
I got The obtained device 100 was immediately stored in a dark place at 0 ° C. or lower for 2 months.

Device 100 did not develop color during this storage. After two months, remove the device from the refrigerator and place it in a dark place
After standing for minutes, the film 102 in the device 100 developed color.
Since the color tone of the film 102 after color development was almost the same as the color tone of the color reference 106, the temperature when left in a dark place was
It was found to be about 20 ° C.

By providing a plurality of color references as described above, the element obtained in this example was found to be useful as a thermosensitive element capable of quantifying the temperature when exposed to a specific time in a dark place. Was issued.

Example 238 This example illustrates the use of a heat sensitive portion 111 having different heat sensitive properties on a substrate 113, as shown in FIGS. 11A and 11B.
An example for manufacturing the thermosensitive element 110 including the 112 will be described. Here, FIG. 11A shows a thermosensitive element of the present invention when stored in a dark place at a relatively low temperature (for example, 0 ° C. or lower) before heat application, and FIG. 11B shows metal fine particles after heat application. 1 shows a heat-sensitive element of the present invention in which color is formed by aggregation.

First, solutions A and B composed of the materials shown in Table 40 were prepared in the same manner as in Example 190. Then added AuHCl ₄ · 4H ₂ O of 0.10g as a metal compound in the solution A, and then stirred at room temperature to give a mixture A. On the other hand, the addition of AuHCl ₄ · 4H ₂ O of 0.05g as a metal compound in the solution B, and stirred at room temperature to obtain a mixture B.

Then, mixture A was applied at a rate of 5 mg / cm ² to predetermined areas on the filter paper (substrate) 113, and mixture B was applied at a rate of 5 mg / cm ² to the remaining area of the substrate. Was dried at room temperature for 2 days, followed by drying at 60 ° C. for 48 hours.
Thus, a laminate having transparent and pale yellow gel films 111 ′ and 112 ′ on a substrate 113 as shown in FIG. 12A was obtained.

This laminate was irradiated with a xenon lamp (hν) in the same manner as in Example 190 (see FIG. 12B), and Au particles 11 were placed on a substrate 113 as shown in FIG. 12C.
Thermal part 111 made of a colorless material containing 6 in different concentrations
An element 110 was obtained, comprising Element 110 obtained
Was immediately stored in a refrigerator (dark place) at 0 ° C. or lower for 2 months.

Element 110 did not develop color during this storage. Two months later, when the device was taken out of the refrigerator and left in a dark place at 25 ° C., the heat-sensitive portion 111 in the device 110 was colored in 5 minutes and showed a purple-red color, whereas the heat-sensitive portion 112 was colored. It took 30 minutes to show reddish purple.

From this, the device obtained in this example was 25% dark place.
It can be seen that the present invention is useful as a heat-sensitive element capable of quantifying the heat-sensitive time when exposed to a temperature of ° C. That is, (1) when the heat-sensitive portion 111 is not colored (the heat-sensitive portion 112 is not colored), the heat-sensitive time at that time is less than 5 minutes;
(2) If the heat sensitive portion 111 has developed color but the heat sensitive portion 112 has not developed color, the heat sensitive time at that time is 5 minutes or more and less than 30 minutes; and (3) the heat sensitive portion 112 has developed color (the heat sensitive portion 111). ), The heat-sensitive time at that time is 30 minutes or more.

In the above embodiment, when heat of a constant temperature is applied in a dark place, the time until each of the heat-sensitive portions 111 and 112 develops a predetermined color tone is measured, and the difference between them is obtained in advance. Was exposed to heat (heat sensitive time). Similarly, when heat is applied for a certain period of time in a dark place, the heat-sensitive portions 111 and 1
The temperature at which the element was exposed to heat under these conditions (thermal temperature) can be quantified by previously calculating the difference in the color tone obtained by developing the color of No. 12.

Example 239 This example demonstrates the use of a thermosensitive coloring material 111 having different thermosensitive properties on a substrate 113, as shown in FIGS. 11A and 11B.
Another example for manufacturing the thermosensitive element 110 including the steps 112 and 112 will be described.

First, a mixture was prepared which was obtained in analogy to example 190 containing AuHCl ₄ · 4H ₂ O. Then, the mixture is filtered with filter paper (substrate) 11
3 was applied at a rate of 5 mg / cm ² and dried at room temperature for 2 days, followed by drying at 60 ° C. for 48 hours. Thus, a laminate having transparent and pale yellow gel films 111 ′ and 112 ′ on the base 113 as shown in FIG. 13A was obtained.

Then, as shown in FIG. 13B, each of the films 111 ′ and 112 ′ of the laminate was irradiated with light of different intensity. More specifically, the film 112 'of this laminate is covered with a photomask (not shown), and the film 111' is placed 20 cm from the film using a 500 W xenon lamp at room temperature. At intervals of, white light was irradiated (hν) for 4 minutes. Next, the photomask on the film 112 'was removed, and the light-irradiated film 111' was removed.
Is covered with a photomask (not shown), and a film 111 ′
Then, irradiation with a xenon lamp (h
v ') for 1 minute. By these light irradiation, FIG.
The element 110 provided with heat-sensitive portions 111 and 112 made of a colorless material containing Au fine particles 116 at different concentrations on the base 113 shown in FIG. The obtained device 110 was immediately stored in a freezer (dark place) at 0 ° C. or lower for 2 months.

Element 110 did not develop color during this storage. Two months later, when the device was taken out of the freezer and left in a dark place at 25 ° C., the heat-sensitive portion 111 in the device 110 developed color in 5 minutes and showed reddish purple, whereas the heat-sensitive portion 112 developed color. It took 20 minutes to show reddish purple.

From this, the device obtained in this example was 25% dark place.
It can be seen that the present invention is useful as a heat-sensitive element capable of quantifying the heat-sensitive time when exposed to a temperature of ° C. That is, (1) when the heat-sensitive portion 111 is not established (the heat-sensitive portion 112 is not colored), the heat-sensitive time at that time is less than 5 minutes;
(2) If the heat sensitive part 111 has developed color but the heat sensitive part 112 has not developed color, then the heat sensitive time is 5 minutes or more and less than 20 minutes; and (3) the heat sensitive part 112 has developed color (the heat sensitive part 111). ), The heat-sensitive time at that time is 20 minutes or more.

In the above embodiment, when heat of a constant temperature is applied in a dark place, the time until each of the heat-sensitive portions 111 and 112 develops a predetermined color tone is measured, and the difference between them is obtained in advance. Was exposed to heat (heat sensitive time). Similarly, if heat is applied for a certain period of time in dark
The temperature at which the element was exposed to heat under these conditions (thermal temperature) can be quantified by previously calculating the difference in the color tone obtained by developing the color of No. 12.

Example 240 This example illustrates the use of a heat sensitive portion 111 having different heat sensitive properties on a substrate 113, as shown in FIGS. 11A and 11B.
Still another example for manufacturing the thermosensitive element 110 including the 112 will be described.

First, a mixture was prepared which was obtained in analogy to example 190 containing AuHCl ₄ · 4H ₂ O. Then, the mixture is filtered with filter paper (substrate) 11
3 was applied at a rate of 5 mg / cm ² and dried at room temperature for 2 days, followed by drying at 60 ° C. for 48 hours. Further, a predetermined region of the dried mixture was dried at 100 ° C. for 24 hours using a heater. As a result, as shown in FIG. 14A, a laminate having transparent and pale yellow gel films 111 ′ and 112 ′ on the base 113 was obtained. It should be noted that the film 111 'is a film in an area that has not been further dried by a heater, and the film 112' is a film in an area that has been further dried by a heater.

This laminate was irradiated (hν) with a xenon lamp in the same manner as in Example 190 (see FIG. 14B), and Au particles 11 were placed on a substrate 113 as shown in FIG. 14C.
An element 110 having heat-sensitive portions 111 and 112 made of a colorless material containing 6 was obtained. The obtained device 110 is immediately replaced with 0
It was stored for 2 months in a freezer (dark place) at a temperature of ℃ or less.

Element 110 did not develop color during this storage. Two months later, when the device was taken out of the freezer and left in a dark place at 25 ° C., the heat-sensitive portion 111 in the device 110 developed color in 5 minutes and showed reddish purple, whereas the heat-sensitive device 112 developed color. It took 45 minutes to show magenta.

From this, the device obtained in this example was 25% dark place.
It can be seen that the present invention is useful as a heat-sensitive element capable of quantifying the heat-sensitive time when exposed to a temperature of ° C. That is, (1) when the heat-sensitive portion 111 is not colored (the heat-sensitive portion 112 is not colored), the heat-sensitive time at that time is less than 5 minutes;
(2) If the heat-sensitive portion 111 has developed color but the heat-sensitive portion 112 has not developed color, then the heat-sensitive time is 5 minutes or more and less than 45 minutes; and (3) the heat-sensitive portion 112 has developed color (the heat-sensitive portion 111). ), The heat-sensitive time at that time is 45 minutes or more.

In the above embodiment, when heat of a constant temperature is applied in a dark place, the time until each of the heat-sensitive portions 111 and 112 develops a predetermined color tone is measured, and the difference between them is obtained in advance. Was exposed to heat (heat sensitive time). Similarly, when heat is applied for a certain period of time in a dark place, the heat-sensitive portions 111 and 1
The temperature at which the element was exposed to heat under these conditions (thermal temperature) can be quantified by previously calculating the difference in the color tone obtained by developing the color of No. 12.

Example 241 HOCH ₂ CH ₂ OH, C ₂ H ₅ OH, H ₂ O, and HCl at a weight ratio of 1: 1:
A solution containing 1: 0.01 was prepared. To this solution, the weight of the solution relative to the addition of AuHCl ₄ · 4H ₂ O 0.05 wt%, and gave the mixture was stirred at room temperature. The mixture was then impregnated with filter paper (containing 99% cellulose; thickness 230 μm; weight per unit area 110 g / m ₂ ) (substrate) at a rate of 3 mg / cm ² . The filter paper was dried at room temperature for 20 minutes, followed by drying at 80 ° C. for 60 minutes to obtain a transparent, pale yellow sheet.

The sheet was irradiated with white light for 30 seconds at a distance of 5 cm from the sheet using a 500 W xenon lamp at room temperature to obtain a white element. The obtained device is
Immediately, it was stored in a freezer (dark place) at -10 ° C for 2 months.

The device did not develop color during this storage. Two months later, when the device was taken out of the freezer and left in a dark place at 25 ° C. for 10 minutes, the device developed a purple-red color. Next, the color-developed element was placed again in a freezer at −10 ° C., but the temperature history was confirmed without losing the color tone.

From the above, the device manufactured in the present example increases the particle diameter of the metal fine particles by applying heat, and develops a color,
Further, it is found that it is useful as a heat-sensitive element capable of confirming the temperature history.

Comparative Example 32 H ₂ O was added AuHCl ₄ · 4H ₂ O 0.05 wt% to obtain a mixture, except for performing 300 seconds irradiation by a xenon lamp, obtaining a white element in the same manner as in Example 241 Was. The same evaluation as in Example 241 was performed using this device. Even when the obtained device was left in a dark place at 25 ° C. for 30 minutes, the device did not develop color, and it took 2 hours to develop reddish purple. From the above, it was found that the element of this comparative example could not be used as a thermosensitive element.

Comparative Example 33 The mixture obtained in Example 241 was directly irradiated with a xenon lamp for 3 hours without using a substrate. The mixture did not react to light and did not develop color even at a temperature of 25 ° C.

Example 242 The mixture was impregnated with filter paper in the same manner as in Example 241.
Then, irradiation with a xenon lamp was performed. A metal tape requiring an adhesive layer on one side of an aluminum foil was attached to both sides of the filter paper irradiated with the light, thereby producing an element in which transmission of light from the outside was blocked. The device was immediately stored in a freezer (dark place) at -10 ° C for 2 months.

The device did not develop color during this storage. Two months later, the devices were removed from the refrigerator and placed in direct sunlight at 25 ° C for 10 minutes. Next, by peeling off the metal tape from the device, it was confirmed that the device had developed a purple-red color. Next, the color-developed element was placed again in a freezer at −10 ° C., but the temperature history was confirmed without losing the color tone.

From the above, the device manufactured in the present example increases the particle diameter of the metal fine particles by applying heat, and develops a color,
It was also found to be useful as a heat-sensitive element capable of confirming the temperature history.

Examples 243 to 246 Instead of using filter paper as the substrate, except that a cloth made of silica fiber or a white cloth made of cotton was used,
Devices were produced in the same manner as in Examples 241 and 242, and the evaluation was performed. The obtained results were the same as those of Examples 241 and 242, and were found to be useful as heat-sensitive elements.

Example 247 A mixture obtained in the same manner as in Example 241 was mixed with a porous glass (containing 99% of SiO ₂ ; thickness: 100 µm; specific surface area: 230 m ² / g).
(Substrate) was impregnated at a rate of 10 mg / cm ₂ . The porous glass plate was dried at room temperature for 60 minutes, followed by drying at 110 ° C. for 120 minutes to obtain a transparent light yellow plate.

This plate was irradiated with the same xenon lamp as in Example 241 for 50 seconds to obtain a colorless element. The obtained device was immediately stored in a freezer (dark place) at -10 ° C for 4 months.

The device did not develop color during this storage. Four months later, when the device was taken out of the freezer and left in a dark place at 25 ° C. for 10 minutes, the device developed a purple-red color. Next, the color-developed element was placed again in a freezer at −10 ° C., but the temperature history was confirmed without losing the color tone.

From the above, the device manufactured in the present example increases the particle diameter of the metal fine particles by applying heat, and develops a color,
Further, it is found that it is useful as a heat-sensitive element capable of confirming the temperature history.

It was added AuHCl ₄ · 4H ₂ O 0.05% by weight Comparative Example 34 H ₂ O to obtain a mixture, except for performing 800 seconds irradiation by a xenon lamp to obtain a device in the same manner as in Example 247. The same evaluation as in Example 247 was performed using this device. Even if the obtained device was left in a dark place at 25 ° C. for 30 minutes, the device did not develop color, and it took 4 hours to develop reddish purple. From the above,
It was found that the device of this comparative example could not be used as a thermosensitive device.

Example 248 As in Example 247, the mixture was impregnated into porous glass, and irradiated with a xenon lamp. A metal tape having an adhesive layer on one side of an aluminum foil was attached to both sides of the filter paper irradiated with the light, thereby producing an element in which transmission of light from the outside was blocked. The device was immediately stored in a freezer (dark cell) at -10 ° C for 6 months.

The device did not develop color during this storage. Six months later, the devices were removed from the refrigerator and placed in direct sunlight at 25 ° C. for 10 minutes. Next, by peeling the metal tape from the device, it was confirmed that the device had developed a purple-red color. Next, the color-developed element was placed again in a freezer at −10 ° C., but the temperature history was confirmed without losing the color tone.

From the above, the device manufactured in the present example increases the particle diameter of the metal fine particles by applying heat, and develops a color,
It was also found to be useful as a heat-sensitive element capable of confirming the temperature history.

Examples 249 and 250 Example 247 was repeated except that a porous glass was used instead of a porous glass as a substrate, and a zeolite plate having 5 nm diameter pores was used.
In the same manner as in Examples 248 and 248, devices were produced and evaluated. The obtained results were all the same as those of Examples 247 and 248, and were found to be useful as heat-sensitive elements.

Various other modifications will be apparent to and readily made by those skilled in the art without departing from the scope and spirit of the invention. Therefore, it is not intended that the appended claims be limited to the description set forth herein, but rather that the claims be interpreted broadly.

INDUSTRIAL APPLICABILITY The present invention relates to a product which needs to be stored at a relatively low temperature (for example, about -20 ° C to about 4 ° C), such as frozen foods and pharmaceuticals, is once exposed to a temperature near room temperature. It is useful as a thermosensitive coloring material and a thermosensitive element which can confirm a change in temperature in such a case.

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 8-264282 (32) Priority date Hei 8 (1996) October 4 (33) Priority claim country Japan (JP)

Claims (35)

(57) [Claims] 1. A thermosensitive coloring material, wherein the metal fine particles are at least one selected from the group consisting of gold, platinum, silver, copper, tin, rhodium, palladium, and iridium.
And a matrix material comprising (1) a group consisting of an inorganic material formed of at least one inorganic alkoxide containing silicon, aluminum, or titanium; or (2) at least one composite with at least one complex-forming inorganic component. Formed by a body-forming organic component, wherein the complex-forming inorganic component is at least one inorganic alkoxide containing silicon, aluminum, or titanium; and the complex-forming organic component is polyacrylic acid,
A group consisting of an inorganic / organic composite selected from polyacrylates and polyethylene oxide, or (3) polyvinyl alcohol, polyvinyl butyral,
At least one selected from those described in the above three groups of the group consisting of polystyrene, acrylonitrile-styrene copolymer, and resins selected from fluororesins
Containing, the size of the metal fine particles are irreversibly increased by aggregating with each other due to a temperature rise from low temperature to room temperature,
material. 2. The material according to claim 1, wherein the matrix material selected from the group consisting of polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-styrene copolymer, and fluororesin further contains polyvinyl pyrrolidone. 3. A thermosensitive element comprising a substrate and a thermochromic material held on the substrate, wherein the thermochromic material is a metal fine particle of gold, platinum, silver, copper, tin, rhodium. , Palladium, and at least one selected from the group consisting of iridium, and a matrix material,
(1) a group consisting of an inorganic substance formed by at least one inorganic alkoxide containing silicon, aluminum, or titanium; or (2) a group formed by at least one complex-forming inorganic component and at least one complex-forming organic component. Wherein the complex-forming inorganic component is at least one inorganic alkoxide containing silicon, aluminum, or titanium, and the complex-forming organic component is selected from polyacrylic acid, polyacrylate, and polyethylene oxide. (3) Polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-styrene copolymer, and a resin selected from the group consisting of resins described in the above-mentioned three groups. At least One was contained, the size of the metal particles irreversibly increases in aggregate with each other due to a temperature rise to room temperature from a low temperature, the thermal element. 4. The matrix material selected from polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-styrene copolymer, and fluororesin, further comprising polyvinylpyrrolidone.
4. The heat-sensitive element according to item 1. 5. The thermosensitive element according to claim 3, wherein said thermosensitive coloring material is directly disposed on said base as a coloring layer. 6. The heat-sensitive element according to claim 5, wherein the substrate is a sheet or a plate made of at least one material selected from the group consisting of a metal film, a plastic film, a fabric, paper, and glass. 7. The material according to claim 5, wherein said substrate is a packaging material. 8. The heat-sensitive color-forming material is disposed as a color-forming layer on the substrate via an adhesive layer.
4. The heat-sensitive element according to item 1. 9. The heat-sensitive element according to claim 8, wherein the substrate is a sheet or plate made of at least one material selected from the group consisting of a metal film, a plastic film, a fabric, paper, and glass. 10. The thermosensitive element according to claim 8, wherein said base is a packaging material. 11. The thermosensitive element according to claim 3, wherein the thermochromic material is impregnated in the base. 12. The heat-sensitive element according to claim 11, wherein the substrate is a sheet that is at least one material selected from the group consisting of cloth and paper, and a metal film and a plastic film having a large number of pores. . 13. The thermosensitive coloring material according to claim 3, wherein the thermosensitive coloring material is held in a plurality of regions in the substrate to form a coloring region, and the coloring region contains the metal fine particles at different concentrations. Thermosensitive element. 14. The heat-sensitive element according to claim 13, wherein the plurality of coloring regions are arranged in a barcode shape as a whole. 15. The heat-sensitive color-forming material is held in each of a plurality of regions in the substrate to form a color-forming region, and the color-forming region contains the fine metal particles having different average particle diameters. 4. The thermosensitive element according to 3. 16. The matrix material, wherein the thermosensitive coloring material is respectively held in a plurality of regions in the substrate to form a coloring region, and each of the thermosensitive coloring materials is formed under different drying conditions. The thermosensitive element according to claim 3, wherein the thermosensitive element contains: and the metal fine particles. 17. The thermosensitive element according to claim 3, further comprising a coloring sample for confirming the temperature when the thermosensitive coloring material develops a color at a predetermined temperature. 18. The thermosensitive element according to claim 3, further comprising a light shielding layer for preventing the thermosensitive coloring material from being colored by light. 19. The heat-sensitive element according to claim 3, wherein a color tone obtained when heat of a predetermined temperature is applied differs depending on a concentration of the metal fine particles. 20. The heat-sensitive element according to claim 3, wherein the obtained color tone is different depending on the temperature of the applied heat. 21. At least one selected from gold, platinum, silver, copper, tin, rhodium, palladium, and iridium.
A thermosensitive element comprising a substrate containing two metal fine particles, wherein the metal fine particles aggregate with each other and increase irreversibly due to a rise in temperature from low temperature to room temperature. 22. The heat-sensitive element according to claim 21, wherein the substrate is a sheet made of at least one material selected from the group consisting of paper, cloth, and porous material. 23. A method for producing a thermosensitive coloring material, wherein the metal ions include gold ions, platinum ions, silver ions,
At least one selected from the group consisting of copper ions, tin ions, rhodium ions, palladium ions, and iridium ions, an α-hydrogen-containing alcohol, and (1) silicon, aluminum, or titanium as a matrix forming material A group consisting of an inorganic substance formed by at least one inorganic alkoxide, or (2) formed by at least one complex-forming inorganic component and at least one complex-forming organic component, wherein the complex-forming inorganic component is silicon or aluminum. Or at least one inorganic alkoxide containing titanium,
And the complex forming organic component is a group consisting of an inorganic / organic composite selected from polyacrylic acid, polyacrylate, and polyethylene oxide; or (3) polyvinyl alcohol, polyvinyl butyral,
At least one selected from those described in the above three groups of the group consisting of polystyrene, acrylonitrile-styrene copolymer, and resins selected from fluororesins
Preparing a mixture comprising: and irradiating the mixture with ultraviolet light. 24. The method according to claim 23, wherein the α-hydrogen-containing alcohol is a dihydric alcohol selected from the group consisting of ethylene glycol and propylene glycol. 25. The method according to claim 23, wherein the matrix material selected from the group consisting of polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-styrene copolymer, and fluororesin further contains polyvinyl pyrrolidone. 26. A method of manufacturing a thermosensitive element comprising a base and a thermosensitive coloring material held on the base, wherein the metal ions are gold ions, platinum ions, silver ions,
At least one selected from the group consisting of copper ions, tin ions, rhodium ions, palladium ions, and iridium ions, an α-hydrogen-containing alcohol, and (1) silicon, aluminum, or titanium as a matrix forming material A group consisting of an inorganic substance formed by at least one inorganic alkoxide, or (2) formed by at least one complex-forming inorganic component and at least one complex-forming organic component, wherein the complex-forming inorganic component is silicon or aluminum. Or at least one inorganic alkoxide containing titanium,
And the complex forming organic component is a group consisting of an inorganic / organic composite selected from polyacrylic acid, polyacrylate, and polyethylene oxide; or (3) polyvinyl alcohol, polyvinyl butyral,
At least one selected from those described in the above three groups of the group consisting of polystyrene, acrylonitrile-styrene copolymer, and resins selected from fluororesins
Preparing a mixture containing the two components; holding the mixture on the substrate; and irradiating the mixture held on the substrate with ultraviolet light to form the thermochromic material. 27. The method according to claim 26, wherein said α-hydrogen-containing alcohol is a dihydric alcohol selected from the group consisting of ethylene glycol and propylene glycol. 28. The method according to claim 26, wherein the matrix material selected from the group consisting of polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-styrene copolymer, and fluororesin further contains polyvinyl pyrrolidone. 29. The method according to claim 26, wherein the substrate is a sheet or plate made of at least one material selected from the group consisting of a metal film, a plastic film, a fabric, paper, and glass. 30. The method according to claim 26, wherein said substrate is a packaging material. 31. The method according to claim 26, wherein the holding of the mixture on the substrate is performed by a coating method, a spin coating method, or a dipping method. 32. The method according to claim 26, further comprising a step of disposing a light-shielding layer to prevent the thermosensitive coloring material from being colored by light. 33. The fine metal particles include gold, platinum, silver, copper,
A method for producing a thermosensitive element including a substrate containing at least one selected from tin, rhodium, palladium, and iridium, wherein the metal ions include gold ions, platinum ions, silver ions,
Preparing a mixture containing at least one selected from copper ions, tin ions, rhodium ions, palladium ions, and iridium ions, and an α-hydrogen-containing alcohol; impregnating the mixture with the substrate; and Irradiating the mixture impregnated with the ultraviolet rays with ultraviolet rays to form the metal fine particles. 34. The method according to claim 33, wherein the α-hydrogen-containing alcohol is a dihydric alcohol selected from ethylene glycol and propylene glycol. 35. The method according to claim 33, wherein the substrate is a sheet or plate made of at least one material selected from the group consisting of paper, fabric, and porous material.