JP2000289140A - Thermally discoloration property laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To visually observe a plurality of color changes with a single heat or a cold heat by constituting a thermal discoloration property laminate so as to be able to see through a transparent support from its front surface to its rear surface, and providing reversibly thermally discoloring layers at opposite positions of the front and rear surfaces of the support. SOLUTION: The thermally discoloration property laminate 1 adopts a transparent flat plate made of a vinyl chloride resin as a transparent support 2. The plate is constituted so as to be able to see through the plate from its front surface to the rear surface. One surface of the plate is coated with a reversibly thermal discoloration property ink uniformly mixed in a vehicle made of a microcapsule pigment enclosing a predetermined amount of a reversible discoloration composition, an ethylene vinyl acetate copolymer resin emulsion, an anti- foaming agent, a thickener, a leveling agent and antiseptics to form a thermal discoloration layer 3. Then, a reversibly thermal discoloration 4 is formed of the same material as that of a reversibly thermal discoloration layer 3 at an opposite position of the layer 3 on the other surface of the support 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermochromic laminate. More specifically, the present invention relates to a thermochromic laminate configured to change its color stepwise according to the time when heat or cold is applied and the elapsed time after the application of heat or cold.

[0002]

2. Description of the Related Art A laminate having a reversible thermochromic layer provided on a transparent support has been disclosed (JP-A-8-333).
567). In the laminate, the reversible thermochromic layer develops and discolors by application of heat or cold so that the appearance change can be visually recognized from both surfaces of the support. However, the laminate has a monotonous color change caused by a temperature change, and has a poor surprising property. In order to obtain a laminate exhibiting a complex color change by eliminating the monotony, a plurality of reversible thermochromic layers are laminated, or a reversible thermochromic material containing a plurality of reversible thermochromic materials having different color tones. It is also conceivable to provide a layer, but in the above-mentioned means, a plurality of reversible thermochromic layers, or a plurality of thermochromic materials contained in the layer are not discolored together by application of heat or cold. Must be set. Therefore, heat or cold at different temperatures must be applied, so that the discoloration method tends to be complicated, and it has been difficult to easily enjoy the color change.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a laminate capable of visually recognizing a plurality of color changes by a single heat or cold heat, thereby providing a laminate which can be suitably used in the decorative and toy fields. It is to provide a discolorable laminate.

[0004]

The present invention relates to a thermochromic laminate having a reversible thermochromic layer containing a reversible thermochromic composition that changes color with a change in temperature on a transparent support. The body is configured to be transparent from the front surface to the back surface, and a thermochromic laminate in which a reversible thermochromic layer is provided at a position opposed to the front surface and the back surface of the support, or a temperature change in the transparent resin. Thermochromic properties in which a reversible thermochromic composition containing a reversible thermochromic composition that changes color with temperature is provided on a support formed by kneading a reversible thermochromic composition that reversibly changes color to colorless A laminate is required. Furthermore,
The reversible thermochromic composition contained in the reversible thermochromic layer provided at each of the opposing positions on the front surface and the back surface of the support exhibits a different color tone due to a temperature change, and the support and the reversible thermochromic layer differ depending on the temperature change. It is required that the support has a color tone, that the support has irregularities, that the support is in the form of a container, and the like.

[0005] The thermochromic laminate of the present invention comprises a transparent support and a reversible thermochromic layer provided at a position facing the support with the support interposed therebetween. Therefore, when heat or cold is applied from the side on which one of the reversible thermochromic layers is provided, the heat or cold is transferred to the support after discoloring the reversible thermochromic layer, and the heat or cold is disposed at the opposite position. The reversible thermochromic layer is discolored.

To explain this in terms of the color change, for example, a reversible thermochromic layer A that reversibly thermochromically changes from red to colorless on one side and a reversible thermochromic layer B reversibly thermochromic from blue to colorless on the other. By providing, the transparent or translucent laminate is visually recognized in a state where both of the reversible thermochromic layers show colorless. However, when heat or cold is applied to the reversible thermochromic layer A side of the laminate, the reversible thermochromic is applied. The layer A develops color and the red laminate is visually recognized. The heat or cold that has caused the color change of the reversible thermochromic layer A is transmitted to the support, and then reaches the reversible thermochromic layer B and the reversible thermochromic layer B develops a blue color, but from the reversible thermochromic layer A side. Visually, from red, a purple color in which red and blue are mixed is visually recognized, and a stepwise color change can be visually recognized depending on the elapsed time. When heat or cold is applied from the side of the reversible thermochromic layer B, the color change from blue to purple can be visually recognized stepwise according to the elapsed time. In addition, the reversible thermochromic layers A and B may have different color tones and may have the same color. In this case, the color density increases stepwise during color development, and gradually increases according to the elapsed time. Is obtained.

The above-mentioned color change is transparent or translucent, that is, a so-called colorless to first hue, and a second hue in which the first hue is mixed with another hue or a state in which the first hue becomes dark. Is visualized, but the present invention is not limited to this.
For example, from the state in which the reversible thermochromic layers A and B are colored and a mixed color is visually observed, a heat- or cold heat is applied, and the color changes stepwise according to the elapsed time, the color changes to a single color, and further a transparent or translucent laminate. Alternatively, the laminate may have a lighter color density and be more transparent or translucent.

The laminate showing the above-mentioned color change is provided with reversible thermochromic layers A and B at opposing positions on the front surface and the back surface of the support. The color tone of the mixed purple color differs depending on the viewer's side. The purple color seen from the reversible thermochromic layer A is reddish purple, and the purple color seen from the reversible thermochromic layer B is blue-violet. This is because the color tone of the reversible thermochromic layer provided on the surface is viewed preferentially, and by changing the angle, both reversible thermochromic layers can be viewed on the surface side. In a case where a reversible thermochromic layer is provided at a position facing the side wall of the container, another color tone can be visually recognized from the inner surface and the outer surface of the container, and magic property can be imparted. Furthermore, if the mirror is mounted so that the other can be viewed at the same time, magic can be easily provided regardless of the shape of the support.

The entire surface of the support may be transparent, but it is sufficient that at least the portion where the reversible thermochromic layer is provided at the opposing position has transparency. The transparent material used for the support is not particularly limited, but glass or a resin such as acryl, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyethylene terephthalate, or ABS is preferably used. The support is preferably formed entirely of a transparent material, but other portions may be formed of metal, porcelain, stone, wood, opaque glass, opaque resin, and the like. The transparency may be translucent, colored transparent, or colored translucent in addition to colorless and transparent.

Further, the thermochromic laminate of the present invention is prepared by kneading a reversible thermochromic composition, which changes color from color to colorless reversibly by a change in temperature, into a transparent resin, and molds the mixture on a support. And a reversible thermochromic layer that changes color due to the above. When heat or cold is applied to the laminate from the support or the side where the reversible thermochromic layer is provided, after the support or reversible thermochromic layer is discolored, the heat or cold is conducted and the other, that is, the opposing position Of the support or the reversible thermochromic layer.

This will be described in terms of the color change. For example, on a support formed of a transparent resin containing a reversible thermochromic composition that reversibly changes color from red to colorless, it is reversibly converted from blue to colorless. By providing a reversible thermochromic layer containing a reversible thermochromic composition that undergoes thermochromic discoloration, a transparent or translucent laminate can be visually recognized in a state in which both the support and the reversible thermochromic layer are colorless. When heat or cold is applied to the support side of the laminate, the support develops color and the red laminate is visually recognized. The heat or cold generated by discoloring the support reaches the reversible thermochromic layer and the reversible thermochromic layer develops a blue color.However, when viewed from the support side, from red, a purple color in which red and blue are mixed is visually recognized. Thus, a stepwise color change can be visually recognized according to the elapsed time. Further, when heat or cold is applied from the reversible thermochromic layer side, the color change from blue to purple can be visually recognized stepwise according to the elapsed time.

The entire surface of the support may be transparent, as long as the portion on which the reversible thermochromic layer is provided has transparency. Examples of the transparent resin used for the support include the resins described above. The support may be entirely formed of a transparent resin, or may be formed of another portion of metal, porcelain, stone, wood, opaque glass, opaque resin, or the like.

The shape of the support is not only a planar shape but also
Various shapes such as a spherical shape, a cylindrical shape, a conical shape, a triangular prism shape, a triangular pyramid shape, a quadrangular prism shape, a quadrangular pyramid shape, and the like, a flora and fauna, a building, a vehicle, and a tube shape can be used. Further, when the unevenness composed of patterns, numbers, symbols, etc. is provided on one or both surfaces of the support so that the conduction speed of heat or cold varies depending on the unevenness, a laminate rich in appearance change in which an uneven image appears can be obtained. Can be In addition, the unevenness is provided with a step in the concave portion and the convex portion, and the entire uneven image appears at once due to a temperature change,
Erasure can be performed, or the step between the concave portion and the convex portion can be made gradual so that the uneven image gradually appears and is erased. Further, the support may be decorated with a pattern, a picture, or the like by using a non-thermochromic material, or may be provided with numerals, characters, and symbols.

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, JP-B-51-44706, JP-B-51-44706
44708, JP-B 52-7776, JP-B 1-2
No. 9398, JP-A-7-186540 and the like. 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 maintained while the heat or cold required for the state to develop is applied, but returns to the state exhibited in the normal temperature range if the application of the heat or cold disappears, so-called, It is a reversible thermochromic composition that exhibits a small hysteresis width (ΔH) in temperature-color density due to temperature change and changes color. In addition, a reversible thermochromic composition (Japanese Patent Application Laid-Open No. 11-5973) which uses an alkoxyphenol compound as an electron-accepting compound and exhibits color development upon heating can be used.

Although the above-mentioned reversible thermochromic composition is effective when used as it is, it is preferable to use it in a microcapsule. 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 encapsulating the microcapsules, chemically and physically stable microcapsule pigments can be formed, and the particle diameter is 0.1 to 100.
μm, preferably 1 to 50 μm, more preferably 2-3.
The range of 0 μm satisfies the practicality. The microencapsulation is performed by a conventionally known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from an aqueous solution, phase separation method from an organic solvent, melting dispersion cooling method, air suspension coating. And a spray-drying method, which are appropriately selected according to the application. Furthermore, on the surface of the microcapsule, a secondary resin film is further provided according to the purpose to impart durability,
The surface properties can 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 composition 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.
When the amount is less than 5% by weight, a clear thermochromic effect is difficult to visually recognize, and when it exceeds 40% by weight, the color is excessive, and the residual color is observed in a decolored state.

The reversible thermochromic layer is formed by a conventionally known method,
For example, it is formed by printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc. be able to. Further, the reversible thermochromic layer can be formed of a plastic material molded by blending the reversible thermochromic composition in a thermoplastic resin or a thermosetting resin.

When the reversible thermochromic layer is a plastic material, it is preferable that the layer is bonded to a support via an adhesive layer.
Examples of the adhesive include an acrylic resin, a vinyl acetate resin, a urethane resin, an epoxy resin, a vinyl chloride resin, a polyester resin, and a polyamide resin. After applying the adhesive to the reversible thermochromic layer or the support, each is adhered. Examples of the bonding method include a method such as heat fusion and ultrasonic fusion in addition to bonding with an adhesive.

Further, the laminate may be provided with a glittering layer exhibiting optical properties such as pearl luster, iris and hologram properties, or a layer containing a luminous pigment as long as transparency is not impaired. .

In the structure of the laminate described above, a protective layer can be provided on the surface layer, and a light stabilizer layer can be provided at an appropriate position. Specifically, the light stabilizer layer is a light selected from an ultraviolet absorber, an antioxidant, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone quencher, a visible light absorber, and an infrared absorber. This is a layer in which a 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 color tone of the laminate having the above-described structure can be changed by contacting or spraying ice pieces, resistance heating elements, Peltier elements, hot or cold water, hot or cold air, or the like.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the thermochromic laminate include a doll, a doll costume, doll accessories such as an umbrella and a bag, a water gun target, a car and a ship. model,
Toys such as boards that show signs of humans and dolls, such as handprints and footprints, training tools, stationery, clothing such as raincoats, shoes such as rain boots, waterproof books, printed matter such as calendars, Recreational equipment such as various games, swimming equipment such as floating bags,
Examples include kitchen utensils such as coasters and cups, umbrellas, artificial flowers, accessories, sporting goods, makeup tools, lighting fixtures, indoor or outdoor decorations, advertising or advertising media, and the like.

[0023]

EXAMPLE 1 (see FIG. 1) A transparent flat plate made of vinyl chloride resin (5 m thick) was used as the support 2.
m), 40.0 parts by weight of a microcapsule pigment containing a reversible thermochromic composition (red at less than 15 ° C., colorless at 15 ° C. or more) was coated on one side of m) with an ethylene-vinyl acetate copolymer resin emulsion 58.0. Parts by weight, 3.0 parts by weight of antifoaming agent, 1.0 part by weight of thickener (sodium alginate), 3.0 parts by weight of leveling agent, 1.0 part by weight of preservative, uniformly mixed in a reversible vehicle The thermochromic ink was applied to form a reversible thermochromic layer A3. Next, a microcapsule pigment containing a reversible thermochromic composition (blue at less than 15 ° C., colorless at 15 ° C. or more) is provided on the other surface of the support 2 at a position facing the reversible thermochromic layer A3. Parts, 58.0 parts by weight of an ethylene-vinyl acetate copolymer resin emulsion, 3.0 parts by weight of an antifoaming agent, and 1 part of a thickener (sodium alginate).
A reversible thermochromic ink uniformly mixed in a vehicle consisting of 0 parts by weight, 3.0 parts by weight of a leveling agent, and 1.0 part by weight of a preservative is applied to form a reversible thermochromic layer B4 to form a thermochromic laminate. Obtained body 1.

The thermochromic laminate 1 is colorless and transparent at room temperature (25 ° C.). However, when cold water at 5 ° C. is applied to the reversible thermochromic layer A3, the reversible thermochromic layer A3 develops a color. Red is visible. After a while, the cold heat of the cold water is transmitted to the reversible thermochromic layer B4 through the support and the reversible thermochromic layer B4 develops blue, so that a red-purple mixed color of red and blue is seen. When the color change is viewed from the reversible thermochromic layer B4 side, the color changes to red when the reversible thermochromic layer A3 develops color, and to blue-violet when the reversible thermochromic layer B4 develops color.

When the discolored laminate 1 is left at room temperature, it returns to colorless and transparent again, and cool water at 5 ° C. is applied to the reversible thermochromic layer B4.
When applied from the side, the reversible thermochromic layer B4 develops color and blue color is visually recognized. After a while, the cold heat of the cold water is transmitted to the reversible thermochromic layer A3 through the support, and the reversible thermochromic layer A3 develops a red color, so that a blue-violet color in which blue and red are mixed is visually recognized. When the color change is viewed from the side of the reversible thermochromic layer A3, the reversible thermochromic layer B4 exhibits a blue color at the stage of color development,
At the stage where the reversible thermochromic layer A3 has developed color, it exhibits a purple-red color.

Example 2 A transparent flat plate made of acrylic resin (thickness: 3 mm) as a support
A microcapsule pigment enclosing a reversible thermochromic composition on one side (red below 35 ° C., colorless above 35 ° C.)
40.0 parts, 58.0 parts by weight of ethylene vinyl acetate copolymer resin emulsion, 3.0 parts by weight of defoamer, 1.0 part by weight of thickener (sodium alginate), leveling agent 3.
A reversible thermochromic ink was uniformly mixed in a vehicle consisting of 0 parts by weight and a preservative of 1.0 part by weight to form a reversible thermochromic layer A. Next, a microcapsule pigment containing a reversible thermochromic composition (blue at less than 35 ° C., 35 ° C.) is provided on the other surface of the support opposite to the reversible thermochromic layer 3.
50.0 parts by weight of an ethylene-vinyl acetate copolymer resin emulsion, 3.0 parts by weight of an antifoaming agent, 1.0 part by weight of a thickener (sodium alginate), and a leveling agent 3.0 A reversible thermochromic ink was uniformly mixed in a vehicle consisting of 1.0 part by weight of a preservative and printed to form a reversible thermochromic layer B to obtain a thermochromic laminate.

At room temperature (25 ° C.), the thermochromic laminate exhibits a reddish purple color when viewed from the reversible thermochromic layer A side, but the blowable warm air of 35 ° C. or more blows out the reversible thermochromic layer A. The color is perceived as blue by the reversible thermochromic layer B. After a while, the heat of the warm air is conducted to the reversible thermochromic layer B through the support and the reversible thermochromic layer B is decolorized, so that it becomes colorless and transparent. When the color change is viewed from the reversible thermochromic layer B side, the color changes from blue-violet to blue when the reversible thermochromic layer A decolorizes, and becomes colorless and transparent when the reversible thermochromic layer B decolorizes.

The color-changed laminate is colored again when left at room temperature, and similarly, when warm air of 35 ° C. or more is blown from the reversible thermochromic layer B side, the layer changes from a blue-violet state to a reversible thermochromic layer B.
And the red color due to the reversible thermochromic layer A is visually recognized. After a while, the heat of the warm air is conducted to the reversible thermochromic layer A through the support, and the reversible thermochromic layer A is decolorized, so that it becomes colorless and transparent. When the color change is viewed from the reversible thermochromic layer A side, when the reversible thermochromic layer B decolorizes from the magenta state, the reversible thermochromic layer A exhibits a red color, and the reversible thermochromic layer A decolorizes. Becomes colorless and transparent.

Example 3 (see FIG. 2) A reversible thermochromic composition (yellow below 15 ° C., colorless above 15 ° C.) was placed on the inner surface of a transparent cylindrical container (7 mm thick) made of an acrylic resin as the support 2. 15.0 parts by weight of a microcapsule pigment encapsulating the acrylic resin / xylene solution 4
0.0 parts by weight, 3.0 parts by weight of ultraviolet absorber, xylene 3
The reversible thermochromic layer A3 is spray-coated with a reversible thermochromic oil-based spray paint mixed and stirred in a vehicle consisting of 0.0 parts by weight, methyl isobutyl ketone 30.0 parts by weight, and isocyanate-based curing agent 10.0 parts by weight. Was formed. Next, a microcapsule pigment containing a reversible thermochromic composition (pink at less than 15 ° C and colorless at 15 ° C or more) is provided on the outer surface of the support 2 at a position facing the reversible thermochromic layer A3.
15.0 parts by weight of an acrylic resin / xylene solution
0 parts by weight, 3.0 parts by weight of ultraviolet absorber, 30 xylene.
A reversible thermochromic oil-based spray paint, which is stirred and mixed in a vehicle comprising 0 parts by weight, 30.0 parts by weight of methyl isobutyl ketone, and 10.0 parts by weight of an isocyanate-based curing agent, is spray-coated to form a reversible thermochromic layer B4. Thus, a thermochromic laminate 1 was obtained.

The thermochromic laminate 1 is colorless and transparent at room temperature (25 ° C.). However, when cold water at 10 ° C. is filled in the container, the reversible thermochromic layer A3 develops color and yellow is visually observed. You. After a while, the cold heat of the cold water is transmitted to the reversible thermochromic layer B4 through the support, and the reversible thermochromic layer B4 develops a pink color, so that a red color in which the yellow and pink colors are mixed is visually recognized. The color change is performed by a reversible thermochromic layer B4.
When viewed from the side (outer surface of the container), the color changes to yellow when the reversible thermochromic layer A3 has developed color, and orange when the reversible thermochromic layer B4 has developed color.

When the cold water is removed, the discolored laminate 1 returns to colorless and transparent again. When cold water of 5 ° C. is applied from the reversible thermochromic layer B4 side (outer surface of the container), the reversible thermochromic layer B4 develops color and becomes pink. Color is visible. After a while, the cold of the cold water is conducted to the reversible thermochromic layer A3 through the support,
Since the reversible thermochromic layer A3 emits yellow, an orange color in which pink and yellow are mixed is visually recognized. When the color change is viewed from the side of the reversible thermochromic layer A3 (the inner surface of the container), the color changes to pink when the reversible thermochromic layer B4 has developed and red when the reversible thermochromic layer A3 has developed color.

Example 4 A transparent flat plate made of polyethylene (10 m thick) was used as a support.
m), 30.0 parts by weight of a microcapsule pigment enclosing a reversible thermochromic composition (yellow below 35 ° C., colorless above 35 ° C.), an ethylene-ethyl acrylate copolymer resin (melt flow rate) 5.0) 1000.0 parts by weight, 10.0 parts by weight of an ultraviolet absorber, and 0.5 parts by weight of a metallic soap-based lubricant were mixed, uniformly dispersed by a tumbler mixer, and then pelletized using an extruder. At
The reversible thermochromic ethylene-ethyl acrylate copolymer resin film sheet formed by inflation molding was bonded to form a reversible thermochromic layer A. Then, a microcapsule pigment 30.0 containing a reversible thermochromic composition (pink below 35 ° C., colorless above 35 ° C.) at the other surface of the support opposite to the reversible thermochromic layer A. Parts by weight, 1000.0 parts by weight of an ethylene-ethyl acrylate copolymer resin (melt flow rate 5.0), 10.0 parts by weight of an ultraviolet absorber, and 0.5 part by weight of a metal soap-based lubricant were mixed, and the mixture was homogenized with a tumbler mixer. After dispersing in, a reversible thermochromic ethylene-ethyl acrylate copolymer resin film sheet formed by inflation molding is adhered to a pellet prepared using an extruder to form a reversible thermochromic layer B. A thermochromic laminate was obtained.

At room temperature (25 ° C.), the thermochromic laminate shows a red color when viewed from the side of the reversible thermochromic layer A. However, when hot air at 35 ° C. or higher is blown, the reversible thermochromic layer A disappears. Color is perceived as pink by the reversible thermochromic layer B.
After a while, the heat of the warm air is conducted to the reversible thermochromic layer B through the support and the reversible thermochromic layer B is decolorized, so that it becomes colorless and transparent. When the color change is viewed from the reversible thermochromic layer B side,
It becomes pink when the reversible thermochromic layer A has decolorized from the orange state, and becomes colorless and transparent when the reversible thermochromic layer B has decolored.

When the transparent laminate is left at room temperature, it is colored again. Similarly, when hot air of 35 ° C. or more is blown from the reversible thermochromic layer B side, the reversible thermochromic layer B disappears from the orange state. The color is seen and the yellow color due to the reversible thermochromic layer is visible. After a while, the heat of the warm air is conducted to the reversible thermochromic layer A through the support, and the reversible thermochromic layer A is decolorized, so that it becomes colorless and transparent. When the color change is viewed from the side of the reversible thermochromic layer A, the color changes from red to yellow when the reversible thermochromic layer B decolorizes, and becomes transparent when the reversible thermochromic layer A decolorizes.

Example 5 (See FIG. 3) A transparent plate made of vinyl chloride resin having a plurality of heart-shaped convex patterns formed on one surface as a support 2 (thickness: 1 to 2 mm)
15.0 parts by weight of a microcapsule pigment containing a reversible thermochromic composition (red at less than 15 ° C., colorless at 15 ° C. or more) on the surface on which the convex pattern was formed,
40.0 parts by weight of xylene solution, 3.0 parts by weight of ultraviolet absorber, 30.0 parts by weight of xylene, 30.0 parts by weight of methyl isobutyl ketone, 10.0 parts of isocyanate curing agent
The reversible thermochromic layer A3 is spray-coated with a reversible thermochromic oil-based spray paint mixed and stirred in a vehicle consisting of parts by weight.
Was formed. Then, on the other surface of the support 2 opposite to the reversible thermochromic layer A3, a microcapsule pigment containing a reversible thermochromic composition (blue at less than 15 ° C., 15
15.0 parts by weight), 40.0 parts by weight of an acrylic resin / xylene solution, 3.0 parts by weight of an ultraviolet absorber,
A reversible thermochromic layer is spray-coated with a reversible thermochromic oil-based spray paint mixed and stirred in a vehicle consisting of 30.0 parts by weight of xylene, 30.0 parts by weight of methyl isobutyl ketone, and 10.0 parts by weight of an isocyanate-based curing agent. By forming B4, a thermochromic laminate 1 was obtained.

The thermochromic laminate 1 is colorless and transparent at room temperature (25 ° C.). However, when cold water at 5 ° C. is applied to the reversible thermochromic layer A3, the reversible thermochromic layer A3 develops color and becomes red. Is seen. After a while, the cold heat of the cold water is transmitted to the reversible thermochromic layer B4 through the support, and the reversible thermochromic layer B4 emits blue color, so that the red-purple mixed color of red and blue is visually recognized. At this time, the part without the heart pattern (concave part) discolors faster than the heart pattern (convex part) due to rapid heat conduction, and the heart pattern also changes color. The state sequentially changes from a state having a red heart pattern on a red-purple background to an entire state having a red-purple heart pattern being a red-purple state. When the color change is viewed from the reversible thermochromic layer B4 side, the color changes to red when the reversible thermochromic layer A3 develops a color,
The state changes to a state having a red heart pattern on a blue-violet background, and the entire state changes to a blue-violet state.

The discolored laminate 1 returns to colorless and transparent again when left at room temperature, and cool water at 5 ° C. is applied to the reversible thermochromic layer B4.
When applied from the side, the reversible thermochromic layer B4 develops color and blue color is seen. After a while, the cold heat of the cold water is transmitted to the reversible thermochromic layer A3 through the support and the reversible thermochromic layer A3 emits red, so that a blue-violet color in which blue and red are mixed is visually recognized. At this time, since the heat conduction is fast, the part without the heart pattern (concave part) changes color faster than the heart pattern (convex part), and the heart pattern also changes color. The state has a blue heart pattern, and the whole sequentially changes to a blue-violet state. When the color change is viewed from the side of the reversible thermochromic layer B4, the reversible thermochromic layer A3 exhibits a blue color at the stage of color development, sequentially changes to a state having a blue heart pattern on a reddish purple background, and a state of a reddish purple as a whole. I do.

Example 6 After mixing 10.0 parts by weight of a microcapsule pigment containing a reversible thermochromic composition (yellow at 35 ° C. or higher, colorless at less than 35 ° C.) and 300 parts of a polypropylene resin (melt flow 45), Then, a cylindrical support (container) with a bottom was formed. 30.0 parts by weight of a microcapsule pigment containing a reversible thermochromic composition (pink at 35 ° C. or higher, colorless at 35 ° C. or less) on the outer surface of the support, an ethylene-ethyl acrylate copolymer resin (melt flow rate 5 .0) 100
After mixing 0.0 parts by weight, 10.0 parts by weight of an ultraviolet absorber and 0.5 parts by weight of a metal soap lubricant, and uniformly dispersing the mixture using a tumbler mixer, inflation is performed using pellets formed using an extruder. The reversible thermochromic ethylene-ethyl acrylate copolymer resin film sheet formed was adhered to form a reversible thermochromic layer to obtain a thermochromic laminate.

The thermochromic laminate shows colorless and transparent at room temperature (25 ° C.), but when warm water of 35 ° C. or more is filled in the support, the support develops color and yellow color is observed. After a while, the heat of the warm water is transferred to the reversible thermochromic layer through the support and the reversible thermochromic layer develops a pink color, so that a red color in which the yellow and pink colors are mixed is seen. When the color change is viewed from the reversible thermochromic layer side (outer surface of the container), the color changes to yellow when the support is colored, and orange when the reversible thermochromic layer is colored.

When the hot water is removed, the discolored laminate 1 returns to colorless and transparent again, and when hot water of 35 ° C. or more is applied from the reversible thermochromic layer side, the reversible thermochromic layer develops color and a pink color is seen. After a while, the heat of the hot water is transferred to the support to develop a yellow color, so that an orange color in which the pink color and the yellow color are mixed is visually recognized. When the color change is viewed from the support side (the inner surface of the container), the color change is pink when the reversible thermochromic layer is colored, and red when the support is colored.

[0041]

According to the present invention, a reversible thermochromic layer containing a reversible thermochromic composition is provided at each of opposing positions on the front surface and the back surface of a transparent support, or a transparency obtained by kneading the reversible thermochromic composition. By providing a reversible thermochromic layer containing a reversible thermochromic composition on a support molded from a resin, the color changes stepwise by the time of application of heat or cold and the elapsed time after the application of heat or cold. It is possible to provide a laminate capable of visualizing a plurality of color changes by a single heat or cold heat, and to provide a thermochromic laminate having a wide variety of applications that is excellent in variety of changes and can be used in the decoration field, toy field, etc. Can be provided.

[Brief description of the drawings]

FIG. 1 is an explanatory longitudinal sectional view of one embodiment of the thermochromic laminate of the present invention.

FIG. 2 is an explanatory longitudinal sectional view of another embodiment of the thermochromic laminate of the present invention.

FIG. 3 is an explanatory longitudinal sectional view of another embodiment of the thermochromic laminate of the present invention.

[Explanation of symbols]

 Reference Signs List 1 thermochromic laminate 2 support 3 reversible thermochromic layer A 4 reversible thermochromic layer B

Claims (6)

[Claims] 1. A thermochromic laminate comprising a transparent support and a reversible thermochromic layer containing a reversible thermochromic composition that changes color by a change in temperature, wherein the support is transparent from the front surface to the back surface. And a thermochromic laminate having a reversible thermochromic layer at each of opposing positions on the front and back surfaces of the support. 2. The reversible thermochromic composition contained in each of the reversible thermochromic layers provided on the front surface and the back surface of the support at positions facing each other has a different color tone due to a change in temperature.
The thermochromic laminate according to the above. 3. A reversible thermochromic composition that changes color by a change in temperature on a support formed by kneading a reversible thermochromic composition that changes color from a colorless to a colorless by a change in temperature in a transparent resin. A thermochromic laminate comprising a reversible thermochromic layer comprising: 4. The thermochromic laminate according to claim 3, wherein the support and the reversible thermochromic layer exhibit different color tones due to a change in temperature. 5. The thermochromic laminate according to claim 1, wherein the support has irregularities. 6. The method according to claim 1, wherein said support is in the form of a container.
6. The thermochromic laminate according to any one of items 1 to 5.