JPH11198598A - Bright thermally discoloring decorative body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the decorative property by imparting bright property and a thermally discoloring property to decorative pieces of this decorative body wherein the decorative pieces migrate in a medium. SOLUTION: In a hollow container 2 having transparency, a transparent medium 3 and bright thermally discoloring decorative pieces 4 are housed for this bright thermally discoloring decorative body 1. As a lamination structure for the bright thermally discoloring decorative pieces 4, a structure is formed by laminating a bright layer which shows optical characteristics such as optical coherency, iris property, hologram property, metallic gloss property and pearlescent luster property, and a reversible thermally discoloring layer, and when a material without light-permeability, e.g. an aluminum deposited film or a hologram film wherein a metal deposition is applied on an embossed surface, is used as the bright layer, the reversible thermally discoloring layer is provided on the upper layer of the bright layer, and the tone of the reversible thermally discoloring layer is made visible.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a brilliant thermochromic decorative body. More specifically, the present invention relates to a brilliant thermochromic decorative body in which a brilliant thermochromic decorative piece capable of exhibiting a unique visual effect combining a thermochromic effect and a brilliant effect migrates in a medium.

[0002]

2. Description of the Related Art Conventionally, as a decorative body in which a medium and a glittering strip are accommodated in a transparent container, a lamp provided with a container in which a medium and an aluminum foil piece are accommodated (Japanese Utility Model Laid-Open No. 55-14280).
Also, there is disclosed a game and decoration ball (Japanese Utility Model Laid-Open No. 5-37256) in which a medium and a silver foil film piece or a film piece colored in a silver or other color by vapor deposition or the like are accommodated in a transparent spherical container. .

[0003]

In the above-described conventional decorative body, the glittering strip migrates while exhibiting the glittering property together with the flow of the medium in the container. There is a limit to the brilliant effect of the decorative body, so that the decorative body may become tired when viewed for a long time or when used for a long time. An object of the present invention is to solve the above-described disadvantages of the conventional decorative body, that is, to provide a decorative body that can change the decorativeness and maintain the decorative effect.

[0004]

The present invention provides: A decorative body in which a transparent medium and a plurality of decorative pieces are built in a hollow container having at least a part of transparency, and the decorative pieces migrate according to the flow of the medium, wherein the decorative body is a photothermographic material. A brilliant thermochromic decorative body that is a decorative piece. 2. 2. The glitter thermochromic decorative body according to claim 1, wherein the glitter thermochromic decorative piece is a film-like decorative piece in which a reversible thermochromic layer and a glitter layer are laminated. 3. 3. The brilliant thermochromic decorative body according to item 2, wherein the brilliant layer is a layer exhibiting optical properties selected from light coherence, iris, pearl luster, metallic luster, and hologram properties. 4. The glittering thermochromic decorative body according to any one of claims 1 to 3, further comprising a device for heating and / or cooling the transparent medium. 5. The glittering thermochromic decorative body according to any one of claims 1 to 4, further comprising a device for flowing the transparent medium. 6. 6. The glitter thermochromic decorative body according to claim 5, wherein a specific gravity difference between the transparent medium and the glitter thermochromic decorative piece is within 0.1. 7. The brilliant thermochromic decorative body according to any one of claims 1 to 6, further comprising a light source. Is required.

[0005] The entire surface of the hollow container for accommodating the transparent medium and the glittering thermochromic decorative piece may be transparent, as long as at least the portion where the decorative piece is visible has transparency. The transparent material used for the container is not particularly limited, but glass or a plastic such as acryl, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, or polyethylene terephthalate is preferably used. Further, it is preferable that the whole hollow container is formed of the transparent material, but metal, ceramic,
The part other than the visual recognition of the decorative piece can also be constituted by stone, wood, opaque glass, opaque plastic or the like. The transparent portion of the hollow container may be colorless and transparent in addition to colorless and transparent, or may be translucent as long as it does not impair the visibility of the glittering thermochromic decorative piece.

The shape of the hollow container is not limited to a geometric shape such as a spherical shape, a cylindrical shape, a conical shape, a triangular prism shape, a triangular pyramid shape, a quadrangular prism shape, and a quadrangular pyramid shape, but also the shapes of animals, plants, buildings, and vehicles. , And various shapes such as a tube shape. or,
On the inner and outer surfaces of the hollow container, decorations such as patterns and pictures can be given, and numerals, letters and symbols can be attached.

Water is preferably used as the transparent medium, but a water-soluble solvent may be added to adjust the viscosity and specific gravity. In addition, oils can be used as a medium, and furthermore, a plurality of incompatible media can be used in combination to separate into multiple layers, thereby enhancing decorativeness.
Further, the medium can be colored by dissolving the coloring agent, or chemically stabilized by adding an ultraviolet absorber or an antioxidant.

The glittering thermochromic decorative piece is a decorative piece having glittering properties selected from light coherence, iris, pearl luster, metallic luster, hologram properties and the like, and thermochromic properties. The glittering thermochromic decorative piece migrates in the hollow container with the flow of the medium. Since the decoration pieces to be migrated have different movements, the glittering properties are also different, so that various glittering effects can be visually recognized. In addition, since the color tone of the decorative piece can be changed by the temperature change, the color change and the glitter effect are combined to provide a more colorful and excellent glitter piece.

The glitter thermochromic decorative piece is preferably a laminate of a glitter layer and a reversible thermochromic layer which changes color from colorless to colorless or from colored to a different color due to temperature change. As the laminated structure of the glittering thermochromic decorative piece, light interference, iris, hologram, metal gloss,
It is formed by laminating a glitter layer and a reversible thermochromic layer exhibiting optical properties such as pearl luster, but a material having no light transmittance as the glitter layer, for example, metal deposition on an aluminum-deposited film or embossed surface. In the case of using a hologram film that has been applied, it is necessary to provide the reversible thermochromic layer above the glittering layer so that the color tone of the reversible thermochromic layer can be visually recognized. or,
When the glitter layer has light transmittance, for example, iris,
In the case of a brilliant layer having optical properties such as pearl luster and a transparent hologram, it is preferable to provide a brilliant layer on the reversible thermochromic layer. This is because the glitter of the glitter layer is not impaired by the reversible thermochromic layer.

The glitter thermochromic decorative piece may be a commercially available glitter transfer foil. The glittering transfer foil has a structure in which a release layer, a glittering layer, a generally used adhesive layer or a hot melt adhesive layer are sequentially laminated on a film substrate.

The bright thermochromic decorative pieces may be triangular, square, hexagonal or other polygonal, circular or star-shaped planar decorative pieces, or may be spherical, cylindrical, conical, pyramidal or long. Cube,
Various three-dimensional decorative pieces such as regular polyhedron, animals and plants may be used. Further, the decorative pieces are not limited to the same size or the same shape, and a plurality of decorative pieces having different sizes or different shapes may be accommodated in the hollow container.

The reversible thermochromic layer and the glitter layer forming the glitter thermochromic decorative piece will be described below. For the reversible thermochromic layer, a reversible thermochromic composition containing three components of an organic compound medium that reversibly causes a color reaction between the electron-donating color-forming organic compound and the electron-accepting compound is used. Specifically, Japanese Patent Publication No. 51-35414,
JP-44706, JP-B-51-44708, JP-B-52-7776, JP-B-1-29398,
JP-A-7-186546 and the like are mentioned. The color changes before and after a predetermined temperature (discoloration point) as a boundary, and only one specific state can exist in a normal temperature range between the two states before and after the change. That is, the other state is
The state is maintained while the heat or cold required to develop the state is applied, but returns to the state exhibited in the normal temperature range if the application of the heat or cold is stopped, so-called temperature-color density due to temperature change. This is a type that shows a small hysteresis width (ΔH) and changes color.

Also, Japanese Patent Publication No. 4-171 proposed by the present applicant.
No. 54, JP-A-7-179777, JP-A-7-179777
The thermosensitive color-changing color memory composition which exhibits large hysteresis characteristics and discolors described in, for example, JP-A-339997, that is, the shape of a curve plotting a change in coloring density due to a temperature change indicates a temperature in a discoloration temperature range. A type of discoloring material that changes color following a significantly different path when the temperature is increased from a lower temperature side and conversely, when the temperature is decreased from a higher temperature side than the discoloration temperature range. A reversible thermochromic composition having a characteristic of being able to memorize and retain a state changed at a temperature below the low-temperature side discoloration point or above the high-temperature side discoloration point in a normal temperature range between the color change points is also effective.

Although the reversible thermochromic composition described above is effective even when applied as it is, it is preferable to use it by encapsulating it in microcapsules. That is, under various use conditions, the reversible thermochromic composition is maintained at the same composition and can exert the same function and effect. By being encapsulated in the microcapsules, chemically and physically stable microcapsule pigments can be formed, and the particle diameter is 0.1 to 1
00 μm, preferably 1 to 50 μm, more preferably 2 μm
The range of ３０30 μm satisfies the practicality. The microencapsulation is performed by a conventionally known interfacial polymerization method, in situ.
There are polymerization method, liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, air suspension coating method, spray drying method, etc., which are appropriately selected according to the application. You. Further, a secondary resin film may be further provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

The reversible thermochromic composition or the microcapsule pigment containing the same is dispersed in a medium containing a binder which is a film forming material and applied as a coloring material such as ink or paint. Can be formed. The reversible thermochromic material or the microcapsule pigment containing the same can be contained in the binder in an amount of 0.5 to 40% by weight, preferably 1 to 30% by weight. 0.5
When the amount is less than 40% by weight, it is difficult to see a clear thermal discoloration effect, and when the amount exceeds 40% by weight, the color is excessive, is in a decolored state, and a residual color is observed.

The reversible thermochromic material is vinyl chloride
Vinyl acetate-copolymer resin, vinyl chloride-vinyl acetate copolymer resin base blended with hindered amine compounds selected from piperidine derivatives, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinylidene chloride copolymer, etc. The reversible thermochromic layer can be formed by fixing the reversible thermochromic layer in a dispersed state, or by dispersing the reversible thermochromic material into fine particles in a saturated copolymerized polyester resin matrix to form a reversible thermochromic layer.

The pearlescent pigment layer used as an example of the glittering layer includes hitherto known titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, and acidic lead carbonate. Pearlescent pigments such as lead arsenate and bismuth oxychloride can be applied, and they are dispersed in a medium containing a binder and applied as a form of a paint, ink or the like. The pearlescent pigment layer has a thickness of 1 μm to 40 μm.
It is 0 µm, preferably 3 µm to 200 µm, and the content of the pearlescent pigment in the layer is 0.1 to 40% by weight (preferably 0.2 to 30% by weight).

The pearlescent pigment is, for example, a natural mica whose surface is coated with 14 to 68% by weight of titanium oxide. The coating layer has an optical thickness of 110 to 415 nm and a particle size of 5 to 5.
A pearlescent pigment in which a pearlescent pigment having a size of about 300 μm is fixed in a binder in a dispersed state is preferably used.

The optical thickness of the coating layer in the pearlescent pigment is the refractive index times the geometric thickness, which is related to the reflection of light having a certain wavelength. In other words, a specific optical thickness reflects light of a specific wavelength.

As the pearlescent pigment, for example, the surface of natural mica particles is coated with 26 to 57% by weight of titanium oxide. The coating layer has an optical thickness of 180 to 240 nm and a particle size of 5 to 5.
The 125 μm gold pearlescent pigment selectively transmits violet wavelength light and has a complementary color relationship of 550 to 600 nm.
Gives the property of reflecting light of the yellow wavelength, and becomes golden. When the lower layer is white, the transmitted violet light is also reflected to the white color of the base, reflects not only yellow light but also violet light, and reflects all wavelengths of visible light, so that it is seen as white. Therefore, by reversibly changing the lower reversible thermochromic layer from black to white, a reversible color change from gold to white can be seen.

The surface of natural mica particles is coated with titanium oxide, and the upper layer is coated with a non-thermochromic dye / pigment (preferably,
A gold metallic luster pigment (coated with 0.5 to 10% by weight) is also effective, and further various color changes can be exhibited depending on the color of the non-thermochromic dye / pigment to be coated.
For example, when a black to white reversible thermochromic layer is laminated as a lower layer, a reversible color change from gold to colored, such as gold to pink, can be seen.

Next, when a silver pearlescent pigment is used as the pearlescent pigment, the silver pearlescent pigment covers the surface of natural mica particles with 14 to 43% by weight of titanium oxide. 170 nm, particle size 1-180 μm
Is preferably used, and when the number is within the above-mentioned limited range, selectivity of the wavelength of the reflected light can be prevented. Outside the above range, the selectivity of the wavelength of the reflected light occurs, so that the reflected light does not become silver. The titanium oxide layer having the above-mentioned optical properties reflects light of all wavelengths of 380 to 700 nm without being irregularly reflected by the layered arrangement of mica, so that it looks silver. Therefore, when the metallic luster layer is silver, when the thermochromic layer is black, it is perceived as silver, and when the thermochromic layer is colorless, the color tone of the lower layer is perceived.

As the pearlescent pigment, a metallic pearlescent pigment in which the surface of natural mica particles is coated with titanium oxide, and a metallic pearlescent pigment in which the titanium oxide layer is coated with iron oxide are also used. In addition, dichroic pearlescent pigments coated on a titanium oxide coating with a non-thermochromic colored dye are also used.

The mica coated with titanium oxide separates visible light of red to purple into light of each color wavelength and reflects only light of a specific wavelength according to the coating weight of the titanium oxide and the optical thickness of the coating. Has the function of transmitting other light. On the other hand, mica does not diffusely reflect light but reflects light in parallel lines, so the light has a metallic luster. Light transmitted through the first layer is absorbed by the second thermochromic layer. In this way, the light of the metallic luster of a specific wavelength is reflected, so that a metallic color of a specific color is obtained.

If the coverage of titanium oxide is more than 68% by weight, the wavelength selectivity is deteriorated, so that a metallic color is not obtained.
When the iron oxide coverage is less than 4% by weight, the effect of the iron oxide is not sufficiently exhibited, and when it exceeds 10% by weight,
Although it becomes a metallic color, the coloring of the iron oxide is too strong to obtain a color change from a beautiful metallic color. in this way,
Depending on the coating amount of specific titanium oxide and the optical thickness, it reflects light of a specific wavelength, and the interference effect of mica and the color-changing effect of the reversible thermochromic layer from color to colorless or from color to color with different color tone, gold color The reversible color change of silver, other metallic colors and general tones can be seen.

The reversible thermochromic layer and the pearlescent pigment layer are
Conventionally known methods, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating , And the like. Further, the reversible thermochromic layer or the glitter layer may be formed of a plastic material molded by blending the reversible thermochromic composition or the pearlescent pigment in a thermoplastic resin or a thermosetting resin.

As the iris thin film layer, which is an example of the glitter layer, a conventionally known structure is effective. Specifically, a transparent thin film layer composed of a transparent thin film layer and an uneven transparent thin film layer (the transparent thin film layer is made of titanium oxide, silicon oxide, zinc oxide, antimony oxide, zinc sulfide, magnesium fluoride, fluoride fluoride). Metal compound thin film layer exemplified by calcium or the like, a copolymer of polyvinylidene chloride and vinyl chloride, vinyl acetate, vinyl alcohol, or polyvinyl chloride,
Polyvinylidene chloride, any one of polystyrene and vinyl chloride, a thin film layer having fine bubbles due to gas generated by being decomposed by various methods such as heat, and a thermoplastic resin such as styrene and a copolymer, a vinyl copolymer, Cellulose-based copolymers, urethane-based copolymers and various curing agents for curing them, compositions having curable functional groups, thin-film layers composed of organically substituted silicon-based compounds, and the above organic materials and titanium oxide , A thin film layer made of inorganic fine particles such as aluminum oxide and zirconium oxide, and a transparent thin film layer having irregularities has a refractive index difference of 0.05 or more from the thin film layer and a visible light transmittance of 10%. An uncolored or colored transparent thin film layer of a degree or higher, light scattering may be present on the surface and inside of the film, and a visible light transmittance of 50% or more: No. 227098], for example, an iris transfer foil in which a release layer, a resin layer, the iris thin film layer, a generally used adhesive layer or a hot melt adhesive layer is sequentially laminated on a film substrate, It is preferably used. Further, an iris film provided with the iris thin film layer on a transparent film, an oxide on one or both sides,
Optical interference pattern film provided with a vapor deposition layer of one or more of sulfides and fluorides (Japanese Patent Application Laid-Open No. 60-3264)
No. 5) Transparent multilayer film exhibiting an optical interference phenomenon in which at least 100 layers of two or more polymers having different refractive indices are provided in an intermediate layer (US: THE
Made by MEARL CORPORATION, trade name: ME
ARL IRIDESCENT FILM) can also be used.

Also, a hologram film can be used as the bright layer. The hologram film is obtained by pressing a hologram master plate having a hologram image formed on various resins and embossing. Further, on the embossed resin layer of the hologram film, Al, C
r, Ni, Sn, Fe, Co, Cu, Pb, Sb, M
A material formed by vapor deposition of a metal such as g, Cd, Bi, or the like to a thickness of 200 to 2000 ° may be used.

When a hologram is used as the bright layer, a commercially available hologram transfer foil may be used. The hologram transfer foil has a configuration in which a release layer, an embossed resin layer, a metal deposition layer, a generally used adhesive layer, or a hot melt adhesive layer are sequentially laminated on a film substrate. As the hologram transfer foil suitably used in the present invention, a PET film (biaxially stretched polyethylene terephthalate) having a film substrate having a thickness of 12 to 75 μm, a thickness of 12 to 100 μm
A film using a nylon film having a thickness of m, a polypropylene film having a thickness of 12 to 50 μm, a hard vinyl chloride film having a thickness of 16 to 50 μm, or the like is suitably used in terms of dimensional stability and cost. The release layer is used to facilitate peeling of the film substrate at the time of transfer, and an acrylic resin, an amino alkyd resin, a urethane resin, an epoxy resin, a vinyl acetate resin or the like having a thickness of 0.5 to 5 μm can be used. .

The glitter layer may be formed by laminating a plurality of glitter layers having different optical properties. Similarly, the reversible thermochromic layer may be composed of a plurality of reversible thermochromic layers having different colors and / or discoloration temperatures. You may laminate | stack and use a discoloration layer. Further, the glitter layer and the reversible thermochromic layer are not limited to those each having a laminated structure. For example, the glitter layer and the reversible thermochromic layer are formed by interposing a reversible thermochromic layer between a plurality of glitter layers or a glitter layer between a plurality of reversible thermochromic layers. May be.

When the glitter layer and the reversible thermochromic layer are in the form of a film, it is preferable to join them via an adhesive layer.
As the adhesive, acrylic resin, vinyl acetate resin,
Examples include urethane resin, epoxy resin, diacryl phthalate resin, olefin resin, vinyl chloride resin, polyester resin, polyamide resin and the like. After applying the adhesive to the glitter layer or the reversible thermochromic layer, they are bonded together. Examples of the bonding method include a method such as heat fusion and ultrasonic fusion in addition to bonding with an adhesive.

The glittering thermochromic decorative piece is formed by laminating a glittering layer and a reversible thermochromic layer. The decorative piece in which the glittering layer and the reversible thermochromic layer are appropriately laminated on a support, and the glittering layer itself is a support. A decorative piece having a reversible thermochromic layer laminated thereon, and a decorative piece having a reversible thermochromic layer itself as a support and having a glitter layer laminated thereon.
The shape of the support or the glitter layer or the reversible thermochromic layer used as a substitute for the support is not particularly limited.

Further, the decorative body may be provided with a layer containing a luminous pigment, or a luminous pigment may be blended in the layer. As the luminous pigment, all conventionally known pigments are effective. For example, CaS / Bi-based pigments, CaSrS / Bi
System, ZnS / Cu system, ZnCdS / Cu system, SrAl ₂
O ₄ / rare earth metal type or the like can be applied.

In the structure of the glittering thermochromic decoration described above, a protective layer may be provided on the surface, or a light stabilizer layer may be provided at an appropriate position. Specifically, the light stabilizer layer is selected from an ultraviolet absorber, an antioxidant, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone decolorant, a visible light absorber, and an infrared absorber. This is a layer in which the light stabilizer is fixed in a dispersed state. In addition, an anti-aging agent, an antistatic agent, a polarity-imparting agent, a thixotropic agent, an antifoaming agent and the like can be added to each layer as needed to improve the function.

The brilliant thermochromic decorative body having the above structure is
The color tone of the decorative piece can be changed by immersing it in hot or cold water, or blowing hot or cold air, etc., but if a device that directly heats or cools the medium is provided, the decorative piece can be efficiently used. Can be changed. As a device for directly heating or cooling the medium, for example, a device having a built-in heater in a hollow container may be mentioned.

Further, in the glittering thermochromic decorative body, a medium can be caused to flow by tilting or shaking the decorative body and the decoration piece can be migrated, but a device for mechanically flowing the medium is provided. You can also. Examples of the device include a device that rotates a screw provided in a hollow container, that ejects a medium from a pump that communicates with the inside of the hollow container, and that causes a convection of the medium by a heat-generating light source. When a device for mechanically flowing the medium is provided, the specific gravity difference between the medium and the decorative piece is preferably within 0.1, more preferably within 0.05. Due to the difference in specific gravity described above, the decorative piece in the medium is excellent in electrophoresis and can improve decorativeness.

Furthermore, by using a device for heating or cooling the medium and a device for flowing the medium in combination, a change in color tone can be caused in the course of migration of the decorative piece, so that a change can be imparted in addition to the decorativeness. .

Further, a light source for further improving the glitter of the decorative piece may be provided, or the light source may be used in combination with a device for heating or cooling or a device for flowing the medium.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION Specific embodiments of the brilliant thermochromic decorative body of the present invention include, for example, indoor or outdoor displays, decorations, advertising or advertising media, training tools, toys and the like.

[0040]

Examples are shown below. The parts in the examples are parts by weight. Example 1 (see FIGS. 1, 2, and 3) As the glittering layer 41, a transparent iris multilayer film (trade name:
IRIDESCENTFILM IF-8181R /
G, manufactured by Mearl Co., Ltd.), a microcapsule pigment containing a reversible thermochromic composition (pink at less than 15 ° C., 1
15 parts of a colorless resin at 5 ° C. or higher), 15 parts of a vinyl chloride-vinyl acetate copolymer resin, 35 parts of toluene, 34 parts of ethyl acetate, and 1 part of an antifoaming agent dispersed and mixed in a reversible thermochromic ink by doctor coating. Thus, a reversible thermochromic layer 42 was formed to obtain a brilliant thermochromic laminate. Next, the glitter thermochromic laminate was cut into a square of 10 × 10 mm to obtain a plurality of glitter thermochromic decorative pieces 4.

The obtained glittering thermochromic decorative piece 4 is placed in a cylindrical hollow container 2 made of acrylic resin (container height: 30 c).
m, diameter 10 cm, container thickness 0.5 cm)
Water was filled and sealed as the transparent medium 3 to obtain a brilliant thermochromic decorative body 1. The cylindrical hollow container 2 includes an open container 21 and a lid 22, and the open container 21 and the lid 22 are bonded to form the cylindrical hollow container 2.

When the bright thermochromic decorative body 1 is shaken at room temperature of 25 ° C., the transparent medium 3 in the container flows, and the bright thermochromic decorative piece 4 having iris migrates. The optical aspect that changes every moment can be visually recognized. When the brilliant thermochromic decorative body 1 is immersed in cold water of 15 ° C. or lower and shaken, the brilliant thermochromic decorative piece 4 inside migrates,
The color changed to pink, which is rich in iris, and became more decorative. Further, when the glittering thermochromic decorative body 1 cooled to 15 ° C. or lower is returned to room temperature, the glittering thermochromic decorative piece 4 returns to the original color tone, and this appearance change can be repeated by the temperature change. Was.

Example 2 A transparent iris multilayer film (trade name: IRI) as a bright layer
DESCENT FILM IF-8181R / G, M
earl), 30 parts of microcapsule pigment (pink below 20 ° C., colorless above 20 ° C.) containing the reversible thermochromic composition, 5 parts of fluorescent yellow pigment, 70 parts of acrylate resin emulsion, A reversible thermochromic ink in which 1 part of a crosslinking agent was dispersed was applied by a doctor coat to form a reversible thermochromic layer to obtain a brilliant thermochromic laminate. Next, the glitter thermochromic laminate was cut into a regular triangle having a side of 5 mm to obtain a plurality of glitter thermochromic decorative pieces.

The obtained brilliant thermochromic decorative piece is housed in a spherical hollow glass container (diameter of container 15 cm, thickness of container 0.5 cm), filled with water as a transparent medium, and sealed therein. A brilliant thermochromic decorative body was obtained.

When the bright thermochromic decorative body is shaken at a room temperature of 25 ° C., the transparent medium in the container flows, and the yellow bright thermochromic decorative piece rich in iris is electrophoresed. And the changing optical aspect can be visually recognized. When the brilliant thermochromic decorative body is immersed in cold water of 20 ° C. or less and shaken, the brilliant thermochromic decorative piece migrates, discolors to a red color rich in iris gloss, and is more excellent in decorativeness. It became something. Furthermore, when the glitter thermochromic decorative body cooled to 20 ° C. or lower was returned to room temperature, the glitter thermochromic decorative piece returned to the original color tone, and this appearance change could be repeated by the temperature change.

Example 3 (see FIG. 4) A transparent iris multilayer film (trade name: I)
RIDESCENTFILM IF-8181R / G,
30 parts of a microcapsule pigment (blue below 35 ° C., colorless above 35 ° C.) containing 5 parts of a fluorescent pink pigment, 70 parts of an acrylic resin emulsion, A reversible thermochromic ink in which 1 part of a cross-linking agent is dispersed is applied by a doctor coat to form a reversible thermochromic layer 42, and a transparent iris multilayer film similar to the above is stuck on the upper surface thereof to form a glitter layer 41. Provided,
A brilliant thermochromic laminate was obtained. Next, the glitter thermochromic laminate was cut with a slitter so as to form a square having a side of 10 mm to obtain a plurality of glitter thermochromic decorative pieces 4.

The obtained brilliant thermochromic decorative piece is housed in a spherical hollow container made of acrylic resin (diameter of container 15 cm, thickness of container 0.5 cm), filled with water as a transparent medium, and sealed. Thus, a brilliant thermochromic decorative body was obtained.

When the bright thermochromic decorative body is shaken at room temperature of 25 ° C., the transparent medium in the container flows, and the purple bright thermochromic decorative piece rich in iris migrates and moves every moment. And the changing optical aspect can be visually recognized. When the brilliant thermochromic decorative body is immersed in warm water of 35 ° C. or more and shaken, the brilliant thermochromic decorative piece inside migrates, discolors to a pink color rich in iris, and becomes more decorative. It was excellent. Further, when the bright thermochromic decorative body heated to 35 ° C. or more was returned to room temperature, the bright thermochromic decorative piece returned to the original color tone, and this appearance change could be repeatedly performed by the temperature change. .

Example 4 A transparent iris multilayer film (trade name: IRI) as a bright layer
DESCENT FILM IF-8181R / G, M
earl), 30 parts of a microcapsule pigment (pink color →→ colorless, high-temperature side discoloration point: 35 ° C., low-temperature side discoloration point: 15 ° C.) containing a thermochromic color memory composition, 30 parts fluorescent yellow A reversible thermochromic ink in which 5 parts of a pigment, 70 parts of an acrylate resin emulsion, and 1 part of a cross-linking agent are dispersed is applied by a doctor coat to form a reversible thermochromic layer. The multilayer film was laminated to obtain a brilliant thermochromic laminate. Next, the glitter thermochromic laminate was cut into a regular triangle having a side of 10 mm to obtain a plurality of glitter thermochromic decorative pieces.

The obtained glittering thermochromic decorative piece was placed in a cylindrical hollow container made of glass (having a height of 30 cm and a diameter of 10 cm).
m, container thickness 0.5 cm), and filled and sealed with water as a transparent medium to obtain a glittering thermochromic decorative body.

After the brilliant thermochromic decoration is cooled to 15 ° C. or less, the transparent medium in the container flows in a temperature range of 35 ° C. or less, and the brilliant thermochromic decoration of red is rich in iris. The pieces migrate and you can see the ever-changing optical appearance. When the brilliant thermochromic decorative body is immersed in warm water of 35 ° C. or more and shaken, the brilliant thermochromic decorative piece migrates and discolors to iris-rich yellow, and this aspect becomes 15
It was kept in the temperature range of ℃ or more. When cooled again to 15 ° C. or less, the color changed to red with rich iris, and this aspect change could be repeated by changing the temperature.

Example 5 (see FIG. 5) 30 parts of a microcapsule pigment (black at less than 15 ° C., colorless at 15 ° C. or more) containing a reversible thermochromic composition on a PET film as a support 43, fluorescent pink 5 parts of pigment,
70 parts of acrylate resin emulsion, crosslinking agent 1
Part is formed by printing a reversible thermochromic layer 42 on which an ink is dispersed, and the surface of natural mica is coated with 43% by weight of titanium oxide on the upper surface.
An ink in which 10 parts of a metal gloss pigment of 0 to 60 μm, 40 parts of an acrylate resin resin, 0.5 part of a silicon-based defoamer, 20 parts of butyl acetate, and 15 parts of an aromatic medium boiling point solvent are uniformly dispersed is printed. The glitter layer 41 was provided to obtain a glitter thermochromic laminate. Next, the bright thermochromic laminate was treated with a diameter of 1
A plurality of glittering thermochromic decorative pieces 4 were obtained by punching out into a 5 mm circle.

The obtained brilliant thermochromic decorative piece was placed in an acrylic resin regular hexahedral container (one side of the container having a length of 15 c).
m, container thickness 0.5 cm), and filled and sealed with water as a transparent medium to obtain a glittering thermochromic decorative body.

When the bright thermochromic decorative body is shaken at room temperature of 25 ° C., the transparent medium in the container flows, and the appearance of the pink bright thermochromic decorative piece can be visually recognized. When the brilliant thermochromic decorative body is immersed in cold water of 15 ° C. or less and shaken, the brilliant thermochromic decorative piece inside migrates, discolors to gold, and becomes more excellent in decorativeness, In addition, the optical aspect that changes every moment can be visually recognized.
Further, when the glitter thermochromic decorative body cooled to 15 ° C. or lower was returned to room temperature, the glitter thermochromic decorative piece returned to the original color tone, and this appearance change could be repeatedly performed by the temperature change.

Example 6 (see FIG. 6) 30 parts of a microcapsule pigment (pink below 20 ° C., colorless above 20 ° C.) containing a reversible thermochromic composition on the upper surface of a transparent PET film as a support 43; 5 parts of a fluorescent yellow pigment, 70 parts of an acrylate resin emulsion,
Printing reversible thermochromic layer 4 by printing ink in which 1 part of crosslinking agent is dispersed
2, the surface of which is coated with 48% by weight of titanium oxide on the surface of natural mica, and has an optical thickness of 295 nm.
Metallic gloss ink in which 10 parts of a metallic gloss pigment having a particle size of 10 to 60 μm, 40 parts of an acrylate resin, 0.5 part of a silicon-based defoamer, 20 parts of butyl acetate, and 15 parts of an aromatic medium boiling point solvent are uniformly dispersed. Was provided to provide a glitter layer 41, and the same metallic gloss ink was also printed on the lower surface of the transparent PET film to provide a glitter layer 41, thereby obtaining a glitter thermochromic laminate. Next, the glitter thermochromic laminate was punched out into a star shape of about 10 mm to obtain a plurality of glitter thermochromic decorative pieces 4.

The obtained brilliant thermochromic decorative piece was placed in a conical container made of polypropylene (container height 10 cm, bottom diameter 10 cm, container thickness 0.5 cm), and water was used as a transparent medium. It was filled and sealed to obtain a brilliant thermochromic decorative body.

When the bright thermochromic decorative body is shaken at room temperature of 25 ° C., the transparent medium in the container flows and the appearance of the yellow bright thermochromic decorative piece migrates can be visually recognized. When the brilliant thermochromic decorative body is immersed in cold water of 15 ° C. or less and shaken, the brilliant thermochromic decorative piece inside discolors to metallic pink while migrating, and is more excellent in decorativeness. , And the optical aspect that changes every moment can be visually recognized. Further, when the glitter thermochromic decorative body cooled to 15 ° C. or lower was returned to room temperature, the glitter thermochromic decorative piece returned to the original color tone, and this appearance change could be repeatedly performed by the temperature change.

Example 7 A microcapsule pigment containing a reversible thermochromic composition (black at less than 30 ° C., 3
15 parts of a vinyl chloride-vinyl acetate copolymer resin, 20 parts of a ketone-based medium boiling solvent, 30 parts of an aromatic medium-based solvent, 30 parts, and 0.5 part of a silicone-based antifoaming agent are uniformly dispersed. The resulting ink was printed to form a reversible thermochromic layer to obtain a brilliant thermochromic laminate. Next, the glitter thermochromic laminate was punched into a circle having a diameter of 10 mm to obtain a plurality of glitter thermochromic decorative pieces.

The obtained brilliant thermochromic decorative piece was placed in a regular hexahedral container made of polypropylene (length of one side of the container was 15 c).
m, container thickness 0.5 cm), and filled and sealed with water as a transparent medium to obtain a glittering thermochromic decorative body.

When the bright thermochromic decorative body is shaken at room temperature of 25 ° C., the transparent medium in the container flows, and the bright thermochromic decorative piece having hologram properties migrates and changes every moment. The optical appearance of the light is visible. When the brilliant thermochromic decorative body is immersed in cold water of 15 ° C. or less and shaken, the brilliant thermochromic decorative piece migrates, discolors to a holographic black while migrating, and is more excellent in decorativeness. It became something. Further, when the glitter thermochromic decorative body cooled to 15 ° C. or lower was returned to room temperature, the glitter thermochromic decorative piece returned to the original color tone, and this appearance change could be repeatedly performed by the temperature change.

Example 8 (see FIG. 7) 25 parts of a microcapsule pigment (pink →→ colorless, discoloration temperature 20 ° C.) containing a reversible thermochromic composition on the surface of a polystyrene sphere having a diameter of 5 mm as a support 43, An ink in which 5 parts of a fluorescent yellow pigment, 20 parts of an acrylate ester, 20 parts of butyric acid-cellulose acetate, 15 parts of methyl isobutyl ketone, and 15 parts of xylene are dispersed is spray-coated to form a reversible thermochromic layer 42. The surface of natural mica was covered with 48% by weight of titanium oxide, and the optical thickness was 2
95 nm, metal luster pigment 10 having a particle size of 10 to 60 μm
Parts, 40 parts of acrylate resin, 0.5 parts of silicone defoamer, 20 parts of butyl acetate, aromatic medium boiling solvent 15
Spray-painted ink with parts dispersed uniformly, glitter layer 4
1 to obtain a spherical bright thermochromic decorative piece 4.

The obtained plurality of glittering thermochromic decorative pieces were
It was accommodated in a spherical container made of polypropylene (container diameter 15 cm, container thickness 0.5 cm), filled with water as a transparent medium, and sealed to obtain a glittering thermochromic decorative body.

When the bright thermochromic decorative body is shaken at room temperature of 25 ° C., the transparent medium in the container flows, and the appearance of the yellow bright thermochromic decorative piece migrating can be visually recognized. When the brilliant thermochromic decorative body is immersed in cold water of 15 ° C. or less and shaken, the brilliant thermochromic decorative piece inside discolors to metallic pink while migrating, and is more excellent in decorativeness. , And the optical aspect that changes every moment can be visually recognized. Further, when the glitter thermochromic decorative body cooled to 15 ° C. or lower was returned to room temperature, the glitter thermochromic decorative piece returned to the original color tone, and this appearance change could be repeatedly performed by the temperature change.

Example 9 As a reversible thermochromic layer, a microcapsule pigment containing a reversible thermochromic composition [pink →→ colorless, color change temperature of 20
[° C], 20 parts of a fluorescent yellow pigment, 2 parts of a benzotriazole-based ultraviolet absorber, and 1000 parts of a polypropylene having a Vicat softening point of 100 ° C. A star-shaped molding was formed. 48% by weight of the surface of natural mica on the surface of the molded product
10 parts of a metallic gloss pigment having an optical thickness of 295 nm and a particle size of 10 to 60 μm coated with titanium oxide, 40 parts of an acrylate resin resin, 0.5 part of a silicon-based defoamer, 20 parts of butyl acetate, and an aromatic resin An ink in which 15 parts of a medium-boiling point solvent was uniformly dispersed was spray-coated to form a glittering layer to obtain a star-like glittering thermochromic decorative piece.

The obtained plurality of glittering thermochromic decorative pieces were
It was accommodated in a spherical container made of polypropylene (container diameter 15 cm, container thickness 0.5 cm), filled with water as a transparent medium, and sealed to obtain a glittering thermochromic decorative body.

When the bright thermochromic decorative body is shaken at room temperature of 25 ° C., the transparent medium in the container flows and the appearance of the yellow bright thermochromic decorative piece can be visually recognized. When the brilliant thermochromic decorative body is immersed in cold water of 15 ° C. or less and shaken, the brilliant thermochromic decorative piece inside discolors to metallic pink while migrating, and is more excellent in decorativeness. , And the optical aspect that changes every moment can be visually recognized. Further, when the glitter thermochromic decorative body cooled to 15 ° C. or lower was returned to room temperature, the glitter thermochromic decorative piece returned to the original color tone, and this appearance change could be repeatedly performed by the temperature change.

Example 10 A quadrangular pyramidal hollow container made of acrylic resin (height of container: 30 c
m, length of one side of the bottom 15 cm, thickness of the container 1 cm) A heater is housed in the bottom, water is filled in the container as a transparent medium, and the glittering thermochromic decorative piece prepared in Example 3 To obtain a brilliant thermochromic decorative body. When the medium is heated by a built-in heater at a room temperature of 25 ° C., the brilliant thermochromic decorative piece, which is rich in iris, migrates due to convection and changes every moment. When the temperature of the medium reached 35 ° C. or more, the medium turned pink with rich iris, and the decoration became more excellent. Further, when the heating by the heater was stopped and the temperature of the medium became 35 ° C. or lower, the glittering thermochromic decorative piece returned to a brilliant purple color, and this appearance change could be repeated.

Example 11 A rectangular parallelepiped hollow container made of acrylic resin (container height: 20 c
m, side length of the bottom 5cm, container thickness 0.5cm)
A manual pump is provided at the bottom, the container is filled with water as a transparent medium, and the medium is caused to flow by the operation of the pump. The glittering thermochromic decorative piece prepared in Example 3 To obtain a brilliant thermochromic decorative body.
When the pump of the glittering thermochromic decorative body is operated at room temperature of 25 ° C., the transparent medium in the container flows,
A purple glittering thermochromic decorative piece rich in iris gloss migrates,
You can see the optical aspect that changes every moment. When the glitter thermochromic decorative body is immersed in warm water of 35 ° C. or higher and the pump is operated, the glitter thermochromic decorative piece inside migrates, and the ever-changing optical aspect can be visually recognized. ,
The color changed to a pink color rich in iris gloss, and the decoration was more excellent. Further, when the bright thermochromic decorative body heated to 35 ° C. or more was returned to room temperature, the bright thermochromic decorative piece returned to the original color tone, and this appearance change could be repeatedly performed by the temperature change. .

Example 12 A hollow container in which polyvinyl chloride tubes were joined in a ring shape (inner diameter of the tube: 5 cm, thickness of the tube: 0.5 c
m, the length of a tube is 30 cm), a heater and a screw are accommodated therein, water is filled in the container as a transparent medium, and the glittering thermochromic decorative piece prepared in Example 3 is housed. A thermochromic decorative body was obtained. When the medium is heated by a built-in heater at a room temperature of 25 ° C. and the screw is rotated, the brilliant thermochromic decorative body is irradiated with a violet brilliant thermochromic rich in iris when the screw is rotated. The decorative piece migrates and the optical aspect that changes every moment can be visually recognized, and when the temperature of the medium reaches 35 ° C or more, the color changes to a pink color rich in iris, which makes the decoration more excellent. Was. Further, the heating by the heater was stopped and the rotation of the screw was maintained, and when the temperature of the medium became 35 ° C. or less, the glittering thermochromic decorative piece returned to purple with rich iris while migrating. By performing heating by the heater again, this aspect change could be repeatedly performed.

Example 13 A hollow container in which a polyvinyl chloride tube was joined in a ring shape (the inner diameter of the tube was 3 cm, and the thickness of the tube was 0.5 c
m, a length of a tube of 80 cm), an electric pump for injecting a heater and a medium was accommodated, and a cooling device was provided at a position different from a portion where the heater was provided. The container was filled with water as a transparent medium, and the glitter thermochromic decorative piece prepared in Example 3 was accommodated to obtain a glitter thermochromic decorative body. When the pump is operated at room temperature of 25 ° C., the brilliant thermochromic decorative piece, which is rich in iris, migrates along with the circulation of the medium in the tube and changes every moment. Since the optical appearance of the medium can be visually recognized and the temperature of the medium near the heater becomes 35 ° C. or higher, the decorative piece changes color to a pink color rich in iris, and is more excellent in decorativeness. became. The iris-rich pink decorative piece returned to the iris-rich purple color again because the temperature of the medium was reduced to 35 ° C. or lower by the cooling device during the circulation in the container. When it reached the vicinity where the heater was again provided, it became pink with rich iris, and this aspect change could be repeatedly performed.

Example 14 An acrylic columnar hollow container (container height: 30 cm, inner diameter: 10 cm, container thickness: 1 cm) An exothermic light source was provided on the outer bottom surface, and the container was filled with water as a transparent medium. In addition, the glitter thermochromic decorative piece prepared in Example 3 was accommodated to obtain a glitter thermochromic decorative body. When the light source is turned on at room temperature of 25 ° C., the brilliant thermochromic decorative piece, which is rich in iris, migrates along with the convection of the medium, and the luminous thermochromic decorative piece migrates and changes every moment. You can see the appearance.
In addition, the glitter of the decorative piece is improved by the light source, and it is visually perceived that the decorative piece itself emits light. Further, when the temperature of the medium became 35 ° C. or more due to the heat of the light source, the medium was changed to a pink color rich in iris gloss, and the decoration was more excellent.
When the light source was stopped and the temperature of the medium reached 35 ° C. or lower, the glittering thermochromic decorative piece returned to purple with rich iris, and this aspect change could be repeated.

[0072]

According to the present invention, the glittering thermochromic decorative piece accommodated has glittering properties and thermochromic properties selected from light coherence, iris, pearlescent, metallic gloss, hologram, etc. When the decoration piece migrates in the hollow container along with the flow of the medium, the glitter effect can be visually recognized and the color tone can be changed by the temperature change. A thermochromic decorative body can be provided.

[Brief description of the drawings]

FIG. 1 is a perspective view of one embodiment of a brilliant thermochromic decorative body of the present invention.

FIG. 2 is a longitudinal sectional view of the bright thermochromic decorative body of FIG. 1;

FIG. 3 is a longitudinal sectional view of one embodiment of a glittering thermochromic decorative piece.

FIG. 4 is a longitudinal sectional view of another embodiment of a glittering thermochromic decorative piece.

FIG. 5 is a longitudinal sectional view of another embodiment of a glittering thermochromic decorative piece.

FIG. 6 is a longitudinal sectional view of another embodiment of a glittering thermochromic decorative piece.

FIG. 7 is a longitudinal sectional view of another embodiment of a glittering thermochromic decorative piece.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Brilliant thermochromic decorative body 2 Hollow container 21 Open container 22 Lid 3 Transparent medium 4 Brilliant thermochromic decorative piece 41 Brilliant layer 42 Reversible thermochromic layer 43 Support

Claims (7)

[Claims] 1. A decorative body having a transparent medium and a plurality of decorative pieces built in at least a part of a hollow container having transparency, wherein the decorative pieces migrate according to the flow of the medium.
A brilliant thermochromic decorative body, wherein the decorative body is a brilliant thermochromic decorative piece. 2. The glittering thermochromic decorative body according to claim 1, wherein the glittering thermochromic decorative piece is a film-like decorative piece in which a reversible thermochromic layer and a glittering layer are laminated. 3. The brilliant thermochromic decorative body according to claim 2, wherein the brilliant layer is a layer exhibiting optical properties selected from the group consisting of light coherence, iris, pearl luster, metallic luster, and hologram properties. 4. The glittering thermochromic decorative body according to claim 1, further comprising a device for heating and / or cooling the transparent medium. 5. The glittering thermochromic decoration according to claim 1, further comprising a device for flowing the transparent medium. 6. The glitter thermochromic decorative body according to claim 5, wherein the difference in specific gravity between the transparent medium and the glitter thermochromic decorative piece is within 0.1. 7. The brilliant thermochromic decorative body according to claim 1, further comprising a light source.