JP3177662B2 - Discoloration equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color changing tool. More particularly, the present invention relates to a color changing device having a dual-purpose function of cooling or heating the color of a contact portion by contacting the thermochromic layer of various thermochromic objects.

[0002]

2. Description of the Related Art Conventionally, as a means for discoloring a thermochromic layer of a thermochromic object, a current-carrying heater equipped with a resistance heating element such as tungsten or nickel has been disclosed, and a heat formed on the surface of an animal toy or the like has been disclosed. An attempt to contact a discolored material and change the color of the contact area is disclosed in Japanese Utility Model Laid-Open No. 62-139573. As described above, an attempt on a heating means for discoloring the thermochromic layer has been disclosed, but no effective cooling means for cooling and discoloring the thermochromic layer has been disclosed yet, such as cold water, ice chips and the like. In this case, it is necessary to apply a cooling medium or to put a thermochromic element of interest into a refrigerator and perform a color changing operation by cold air in the refrigerator.

[0003]

The cooling / heating means is applicable to a specific place such as a home, but is required when necessary.
Regardless of the location, the thermochromic layer of the object could not be immediately discolored, and the function of the thermochromic element having a discoloration point in a low temperature range could not be effectively exhibited. In addition, the application of the cooling medium has a limitation in the duration of cooling and heating, and it has been troublesome to prepare these media each time. Further, in the case of the non-water-resistant thermochromic element, not only direct contact with the cooling medium but also indirect contact operation in which the cooling medium is accommodated in the container and applied to the container surface, The thermochromic element tends to deteriorate due to a condensed layer, water droplets, or water leakage.

The present invention solves the above-mentioned problems caused by the application of the conventional cooling means at a glance, and satisfies portability, immediate effect, cold heat continuity, convenience, and the like. It is an object of the present invention to provide a discoloring device having a heating function in addition to a function of discoloring a thermochromic layer.

In particular, the thermochromic element of interest is a color-memorizing thermochromic dye (discoloring showing a large hysteresis characteristic due to temperature change, and has two discoloring points, a low-temperature discoloring point and a high-temperature discoloring point. The coloration state and the colorless state or the alternation between the colored [1] and the colored [2] are exhibited, and by application of heat at a temperature lower than the low-temperature side discoloration point or at a temperature higher than the high-temperature side discoloration point, the appearance differs from the normal state. A pigment having a thermochromic layer colored with a coloring material containing a pigment having a function of being able to change and change the appearance of the aspect in a normal temperature range. An object of the present invention is to provide a discoloring device that enables the diversification of products and the application and development to various fields by effectively exhibiting the function of a color memory thermosensitive dye.

[0006]

The discoloring device of the present invention will be described with reference to the drawings. The present invention relates to a discoloration device for thermally discoloring the contact portion by bringing the P-type semiconductor element 21 into contact with the thermochromic element 12 on which the thermochromic layer 121 is formed.
And the N-type semiconductor element 22 are alternately joined by a metal piece 23,
A thermoelectric conversion element 2 having a Peltier effect and having a unitized structure in which the upper and lower surfaces are sandwiched between heat conductive insulating plates 24 is used as a heat source, and the thermoelectric conversion element 2 is applied by applying a DC voltage.
The heat dissipating device is configured to be operable. The heat conductive end member 4 is closely contacted with the heat absorbing side A of the thermoelectric conversion element 2 and the heat generating side B
The heat sink 3 is assembled by connecting the radiator 3 via the heat-conductive protrusion 6 to allow the tip member 4 and the protrusion 6 to function as a cooling and heating tip element. The discoloring device 1 is required to be constituted by the heat storage medium 32 which is at least filled in the container 31 at the time of use. Further, the heat conductive tip member 4, the heat conductive protruding piece 6, and the thermoelectric conversion element 2 are held by a holding member 5, and the holding member 5 is attached to one end of a heat radiating container 31, and A configuration in which the surface of the container 31 facing the heat generation side of the thermoelectric conversion element 2 is a shaft body made of at least a metal material;
The heat dissipating container 31 is made of a metal material, the heat dissipating medium 32 is water or an aqueous medium containing water as a main component, and further, the thermochromic layer 121 of the thermochromic element 12 shows a large hysteresis characteristic due to a temperature change. A color-memorizing thermochromic dye exhibiting a tautomerism between a colored state and a colorless state or between a colored state [1] and a colored state [2], and capable of selectively storing and holding one of the two states in a normal temperature range. The requirement is that the color changing tool 1 be applied in combination with a system that is colored with a coloring material.

In the above, as the thermoelectric conversion element 2 having the Peltier effect, a thermoelectric conversion element which has been widely used conventionally is effective. The thermoelectric conversion element 2 includes a couple of semiconductor elements of insufficient electron P-type and excess electron N-type, and a metal piece 23 (electrode).
The upper and lower surfaces are sandwiched by a thermally conductive insulating plate 24 made of alumina, ceramics or the like to form a unit. When a current flows from the N-side terminal to the P-side terminal, the Peltier effect causes Endothermic, generates heat at the bottom. (FIG. 6,
(See FIG. 7) The P-type or N-type semiconductor elements 21 and 22 described above are
_{Bi 2 Te 3, Bi 2 Se} 3, Sb 2 Te 3 or the like can be exemplified. The number of pairs of semiconductor elements is 1 to 511 pairs, more practically 4 to 127 pairs, and preferably 4 to 31 pairs. As described above, the radiator 3 according to the present invention includes the heat radiating container 31 and the heat storage medium 3 filled in the container 31.
The two components cooperate to effectively exhibit the intended heat dissipation function.

The heat dissipating container 31 does not hinder the application of a thin-walled container made of a plastic material. However, at least the surface of the thermoelectric conversion element 2 that contacts the insulating plate 24 (heating side) is made of a metal material. The effect of transferring heat to the heat storage medium 32 filled in the container is enhanced. A metallic container formed of aluminum, copper, brass, or the like is effective. Heat storage medium 32
Is a liquid that is relatively low in viscosity compared to the convection effect, is effective, has a large heat capacity per weight and volume, and additionally satisfies availability, safety and cost. And an appropriate amount of a polyhydric alcohol for imparting antifreezing property, or an appropriate amount of a rust preventive or the like can be blended. Examples of the liquid other than water include glycerin, ethyl alcohol, ammonia water, and the like. The voltage applied by the DC power supply for energizing the thermoelectric conversion element 2 is 0.3 to 50.
V, it is difficult to operate with a battery in a system of 0.3 V or less, and in a system of 50 V or more, the number of couples needs to be increased accordingly, and it is generally used in the fields of toys, training, writing materials, etc. It is expensive and unsuitable for application to products,
Restricted to special uses. Usually, a combination with the thermoelectric conversion element 2 which functions by an applied voltage of 0.5 to 20 V is preferable.

The power supply 10 for applying the voltage includes a color changing device 1.
Although it can be arranged in the power supply accommodating portion 8 integrally formed with the power supply, it can be separately provided via a cord or the like. As the power source 10, various batteries such as dry batteries, AC
It is also possible to connect an / DC converter and convert AC to DC for application. Endothermic side of thermoelectric conversion element 2 (insulating plate 2
4) The heat conductive tip member 4 and the insulating plate 2 on the heating side
The heat-conductive protruding piece 6 interposed between the front end face 4 and the heat-radiating container 31 is not limited to a metal material, and may be a thin processed body made of a heat-conductive rubber, plastic, ceramic material, or the like. The heat-conductive tip member 4 and the heat-conductive protruding piece 6 may be a writing or application tip shape, a shape having an image, a shape having a tip surface shaped into a target shape such as a circle or a polygon, a toy element (for example, a doll). Toy combs, makeup tools, etc.). In a system in which the tip member 4 and the protruding piece 6 are formed of a metal material, a portion serving as a contact tip with the thermochromic layer 121 may be processed with a silicon resin or a fluoro resin to impart lubricity. By attaching a porous body having continuous pores and impregnating the porous body with water or the like, a soft touch and smooth applicability can be imparted.

The temperature lowering function of the heat-absorbing side A in the above-mentioned system has a temperature drop of at least 3 ° C. or more, more specifically 3 ° C. to 40 ° C., in an environment temperature of 10 ° C. to 35 ° C. (Preferably 10 to 25 ° C.). When the temperature falls below 3 ° C., the color change function cannot be sufficiently exhibited with respect to the fluctuation in room temperature. on the other hand,
If the temperature falls below 40 ° C., water vapor freezes, which is not practical. When converting the heat absorption side A to the heat generation side by switching the polarity, the temperature of the heat generation side is set to the temperature within the environmental temperature range plus 3 ° C. to 60 ° C. (preferably 5 ° C.).
(50 ° C. to 50 ° C.).
Note that the direct current referred to in the present application means a direct current for effectively operating the thermoelectric conversion element 2, and does not mean that a reverse voltage must not be applied even for a moment during cooling or heating. Since the thermoelectric conversion element 2 itself has a heat capacity, if the reverse voltage is applied for a short time, the cooling surface and the heating surface do not always reverse. It may include application of such a reverse voltage. As is well known, when controlling the temperature using the thermoelectric conversion element 2, a reverse voltage may be applied in order to speed up the thermal response. Next, the thermochromic material constituting the thermochromic layer 121 of the thermochromic element 12 applied in combination with the color changing device 1 of the present invention will be described.

A conventionally known thermochromic material containing a thermochromic dye, such as a liquid crystal, an electron-donating color-forming organic compound, a color developer of the compound, and a medium for causing a color reaction between the two. A thermochromic material containing three components of the following compound or a thermochromic material exhibiting a color change in the form of fine particles of a resin solid solution of the component (for example, JP-B-51-35414, JP-B-51-44706, 52-77
No. 64, Japanese Patent Publication No. 1-293898). The color changes before and after a predetermined temperature (color change point), 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, This type changes color by showing a small hysteresis width (ΔH) for temperature-color density due to temperature change. (See Fig. 9)

Further, Japanese Patent Application Laid-Open No.
The system described in JP-A-264285, which is colored with a thermochromic material containing a color-memorizing thermochromic dye that exhibits a large hysteresis characteristic and changes color, is effective. The dye changes color with a large hysteresis width (ΔH). That is, the shape of the curve plotting the change in the coloring density due to the temperature change is different from the case where the temperature is increased from a temperature lower than the color change temperature range to the case where the temperature is decreased from the temperature higher than the color change temperature range. It is a type that changes color following a very different path. (See Fig. 10)

The point A (temperature t ₁ ) in the graph is a point at which the color becomes completely colored at a temperature lower than this point, and the point B (temperature t ₃ ) in the process of increasing the temperature. The point at which substantial discoloration (decolorization) starts, point C (temperature t ₄ ) is a point at which the color is completely decolored at a temperature higher than this point, and the discoloration temperature range is t ₁ and t _{1. 4} is a temperature range of between, in particular both states of the colored state and the colorless state or a colored [1] can coexist both states of the colored (2), a region having a large difference in color density t ₂ and t ₃ The space between the two states is a substantial discoloration temperature range and a normal temperature range in which either of the two states can be selectively stored and held. The thermochromic dye described above, the color-memorizing thermochromic dye is usually encapsulated in microcapsules, dispersed in a medium containing a binder, and applied as a coloring material in the form of ink, paint, or paint, Thermochromic layer 12 on support surface
1 is formed. In addition, the thermochromic elements 12 of various shapes obtained by kneading the microcapsule pigment in a thermoplastic and melt-molding the same are effectively applied in combination with the color changing device 1 of the present invention. The thermochromic element 12 includes a thermochromic planar body, a thermochromic linear body, a thermochromic molded article having an uneven surface,
In addition, it includes all the thermochromic layers 121 made of the above-described thermochromic material formed on the surface layer. Examples include writing boards, lessons, learning materials, picture books, and other toy elements. The thermochromic layer 121 having a color change point in the range of −10 ° C. to + 70 ° C. (preferably −5 ° C. to 50 ° C.) is effective from a practical viewpoint.

[0014]

[Function] By applying a DC voltage (0.3 to 50 V), N
When a current flows from the side terminal to the P side terminal, heat is absorbed at the upper surface and heat is generated at the lower surface by the Peltier effect, and is transferred to the heat conductive insulating plates 24 on both the upper and lower surfaces to form a heat absorbing side A and a heat generating side B (FIGS. 7 to 7).
See FIG. 8). A heat dissipator 3 (heat dissipating container 3) closely arranged on the heat generating side B (converted to a heat absorbing side by reversing the polarity).
1 and the heat radiation medium 32), the heat absorption side A
Temperature is lowered and maintained in a desired range. The function of the radiator 3 to release the heat generated from the heat generation side B is based on the heat storage effect of the radiator 3 itself and the effect of the radiator 3 radiating heat to the atmosphere. Immediately after the heat generation side B starts generating heat, the amount of generated heat is mainly used for heating the radiator 3, and the ability to radiate heat to the atmosphere is small. That is, the heat storage effect is large. Radiator 3
As the temperature increases, the amount of heat released to the atmosphere increases, and when the temperature of the radiator 3 becomes constant, the heat storage effect is no longer present. In other words, even if the ability to radiate heat to the atmosphere is small, if the elapsed time from the start of heat generation is short, the heat radiating effect can be obtained by the heat storage effect. The radiator 3 according to the present invention has a configuration in which the above requirements are taken into consideration. Among the functions of the radiator, the radiator 3 mainly focuses on improving the heat storage capacity. By filling the large heat storage medium 32, the ability to absorb the amount of heat generated from the heat generation side B of the thermoelectric conversion element 2 is enhanced, and the function as the radiator 3 is sufficiently performed for short-time use. When the thermoconductive element 12 having a surface layer formed by the thermochromic layer 121 is brought into contact with the thermoconductive tip member 4 side of the color changing tool 1, the thermochromic layer 121 at the contact portion is color-changed with heat and heat. When the heat conductive protruding piece 6 is brought into contact with the thermochromic layer 121, the contact portion is heated and discolored. By reversing the polarity, the heat absorbing side A can be reversed to the heat generating side and the heat generating side B can be reversed to the heat absorbing side, so that the function as the cooling and heating tip can be reversed. In a system in which the thermochromic layer 121 is formed of a coloring material containing a thermosensitive pigment exhibiting thermochromic characteristics with a small hysteresis width (ΔH), the color changes before and after the color changing point as a boundary. In the normal temperature range, one specific state exists, and the other state returns to the state exhibited in the normal temperature range when the application of heat or cold required for the state to develop is eliminated.
On the other hand, the thermochromic layer 121 formed of a color material containing a color-memory thermochromic pigment has a color different from that of a normal state due to the application of heat below the low-temperature side color change point or above the high-temperature side color change point. The state can be stored and maintained in a normal temperature range even if the application of cold or heat required for the state to develop is eliminated, and the retained state is required to develop the state. The color is changed to the original state by the reverse thermal means, and this is stored and stored in the normal temperature range.

[0015]

Embodiment 1 (see FIGS. 1 to 4) A holding member 5 made of a plastic material and having a central hole and an enlarged hole which communicates with the central hole and opens at the other end, is made of aluminum. The thermoelectric conversion element 2 (the logarithm of the semiconductor) in which the tip of the pen tip of the thermal tip member 4 (having a pen tip shape and having a base surface connected to the bottom) is mounted in a protruding state, and the base surface is mounted in an enlarged hole : 7 pairs) in close contact with the insulating plate 24 on the heat absorbing side A, and the insulating plate 24 on the heat generating side B has a heat conductive protruding piece 6 (a circular surface having a contact surface with the insulating plate 24 and being connected to the contact surface). The protruding piece is attached to the side surface of the holding member 5 in a protruding state to form a tip element. In the enlarged hole of the holding member 5, a heat dissipating container 31 made of an aluminum shaft drum (diameter 15 mm, total length 10 cm) is inserted with its front surface in contact with the contact surface of the heat conductive projecting piece 6. A tail plug 312 is provided at the rear end opening of the aluminum barrel 31.
Are removably screwed together, and the shaft body is filled with about 15 cc of water (heat storage medium 32) to constitute the radiator 3, which is put into practical use. Further, the thermoelectric conversion element 2 includes:
A lead wire 7 is connected, connected to a power storage unit 8 (power supply: 1.5 V battery) provided outside the system, and configured to be switchable between energization and polarity by a switch 11. The temperature of the heat conductive tip member 4 of the discoloring device 1 is about 7 ° C. 30 seconds after the start of energization at room temperature of 25 ° C.
The surface temperature of the circular bowl-shaped protruding piece was about 45 ° C. Using the color changing device 1, a color-memorizing thermosensitive dye [black ← → colorless (low-temperature side color change point (t ₁ ) 15 ° C., high-temperature side color change point (t ₂ ) color material) When writing is performed by contacting the thermoconductive element 12 (having a white color at room temperature) with the thermoconductive element 12 formed on the entire surface 121, the white color of the written portion is discolored and a black handwriting is formed. The black handwriting is stored at room temperature of 17 ° C. to 33 ° C. However, when the heat conductive protruding piece 6 (circular bowl-shaped protruding piece) is brought into contact with the handwriting, the black handwriting disappears. , And could be repeatedly put to practical use as a white writing surface.

[0016]

Embodiment 2 (see FIGS. 5 and 6) A tip element was formed in the same manner as in Embodiment 1 except that a bent heat conductive projecting piece 6 made of a metal plate piece was attached as shown in the figure. The radiator 3 is configured by filling water (heat storage medium 32) into the heat-radiating container 31 (aluminum barrel). A plastic cover member 9 integrally formed with a power supply accommodating portion 8 accommodating the radiator 3 and a power supply battery 10 is prepared by injection molding. On the front side surface of the plastic cover member 9, heat radiation openings 91 are provided at four places at appropriate intervals to assist heat radiation of the radiator 3 housed therein.

[0017]

The color-changing device of the present invention is applied in combination with a thermochromic element provided with a thermochromic layer. In particular, the function of a thermochromic element having a color-changing point in a low-temperature region is effectively exhibited. It is provided with a cooling means capable of performing the above-described steps. At any time, at any place, the desired place of the thermochromic layer of the object can be easily and immediately compared with the conventional cooling means using cold water, ice chips or the like as a cooling medium. It satisfies the convenience of cooling discoloration, applicability to non-water resistant objects, portability, and the like. Furthermore, in addition to the cooling function, it has a heating function, and can be practically used as a color changing tool having both functions of cooling and heating. In addition, it can function effectively at a low applied voltage (50 V or less),
There is no danger of electric leakage. The function can be made permanent by replacing batteries such as dry batteries. Furthermore, since the heat radiator of the thermoelectric conversion element is configured to function by filling the heat radiating container with a heat storage medium of liquid such as water without using a metal radiating fin or the like, it can be supplied at a relatively low cost and is practical. It is. As described above, it is possible to easily apply cold heat, and it is possible to combine with various thermochromic elements having a configuration in which a thermochromic layer having a color changing point in a low temperature region is provided. In particular, the thermochromic element of interest is a color-memorizing thermochromic dye (discoloring showing a large hysteresis characteristic due to temperature change, having two discoloring points, a low-temperature side discoloring point and a high-temperature side discoloring point, And a colorless state or a tautomerism between the colored [1] and the colored [2], and can be changed to a state different from the normal state by the application of cold heat below the low-temperature discoloration point or heat above the high-temperature discoloration point. , A dye having a function of storing and maintaining the appearance in a normal temperature range) by applying in combination with a system having a thermochromic layer colored with a coloring material containing the color-memorizing thermochromic dye. Can be effectively expressed to enable diversification of products and application development to various fields.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a use state of an embodiment of the color changing device of the present invention.

FIG. 2 is an explanatory view showing another use state of one embodiment of the color changing device of the present invention.

FIG. 3 is an explanatory longitudinal sectional view of the color changing tool of FIG. 1;

FIG. 4 is a front view of the color changing tool of FIG. 3;

FIG. 5 is an explanatory longitudinal sectional view of another embodiment of the color changing device of the present invention.

FIG. 6 is a front view of the color changing tool of FIG. 5;

FIG. 7 is a perspective view of a thermoelectric conversion element applied to the color changing device of the present invention.

FIG. 8 is an explanatory diagram of the structure and operation of a thermoelectric conversion element applied to the color changing device of the present invention.

FIG. 9 is an explanatory graph of a color change characteristic of a thermochromic dye due to a temperature change.

FIG. 10 is an explanatory graph of a color change characteristic of a color memory memorizing thermochromic dye due to a temperature change.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Discoloration tool 2 Thermoelectric conversion element 21 P-type semiconductor element 22 N-type semiconductor element 23 Metal piece 24 Insulating plate A Heat absorption side B Heat generation side 3 Radiator 31 Heat dissipation container 32 Heat storage medium 4 Heat conductive tip member 5 Holding member 6 Heat transfer property Projection piece 7 Lead wire 8 Power supply housing 9 Cover member 10 Power supply 11 Switch 12 Thermochromic element 121 Thermochromic layer 122 Thermochromic image

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) A63H 30/02 A63H 33/22 B41K 1/00 B43K 8/00 B43K 19/00-19/12 B43L 1 / 00 B43L 19/00

Claims (4)

(57) [Claims] 1. A color-changing device for thermally discoloring a contact portion by contacting a thermochromic element having a thermochromic layer formed thereon, wherein a P-type semiconductor element and an N-type semiconductor element are alternately joined by a metal piece. Then, using a thermoelectric conversion element having a Peltier effect of a unitized structure in which the upper and lower surfaces are sandwiched by a heat conductive insulating plate as a heat source, a color changing tool configured to be able to operate the thermoelectric conversion element by applying a DC voltage. A heat conductive tip member is closely attached to the heat absorbing side of the thermoelectric conversion element, and a radiator is connected to the heat generating side via a heat conductive protruding piece to assemble and cool the tip member and the protruding piece. It is a configuration to function as, the radiator is a heat dissipating container,
A discoloring device comprising at least a heat storage medium that is filled in the container during use. 2. A heat conductive tip member, a heat conductive projecting piece, and a thermoelectric conversion element are held by a holding member, and the holding member is mounted on one end of a heat radiating container. The discoloring tool according to claim 1, wherein a surface facing the heat generation side of the element is a shaft body made of at least a metal material. 3. The color changing device according to claim 1, wherein the heat radiation container is made of a metal material, and the heat storage medium is water or an aqueous medium containing water as a main component. 4. The thermochromic layer of the thermochromic element exhibits a large hysteresis characteristic due to a temperature change, exhibits a colorless state and a colorless state, or exhibits a tautomerism between the colored [1] and the colored [2] states, The color change according to claim 1, wherein the color change is performed by using a color material containing a color storage thermosensitive color changeable pigment capable of selectively storing and holding one of the two states, and applied in combination with the thermochromic element. Utensils.