JP3177668B2 - 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 specifically, the present invention relates to a color-changing device that cools and thermally discolors 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.
The thermochromic layer of the object could not be immediately discolored irrespective of the location, 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 for discoloring a thermochromic layer by heat and heat.

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 1 of the present invention will be described with reference to the drawings. The present invention relates to a color-changing device for thermally discoloring a contact portion by contacting a thermochromic element on which a thermochromic layer is formed, wherein a P-type semiconductor element 21 and an N-type semiconductor element 22 are alternately formed by metal pieces 23. And a thermoelectric conversion element 2 having a Peltier effect as a heat source having a unitized structure in which the upper and lower surfaces are sandwiched by a heat conductive insulating plate 24, and the heat absorption side of the thermoelectric conversion element 2 The heat transfer member 4 is closely attached, and the radiator 3 is closely assembled on the heat generation side. The thermoelectric conversion element 2 is required to have a color changing tool 1 in which a power supply battery is connected in series via a resistor. I do.
Further, the thermochromic layer of the thermochromic element exhibits a large hysteresis characteristic due to a temperature change, and exhibits a coloring state and a colorless state or a tautomerism between the colored state [1] and the colored state [2]. The color changing device 1 applied in combination with a system that is colored with a color material containing a color-memorizing thermochromic dye capable of selectively storing and holding any of the states is required.

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 It absorbs heat and generates heat at the lower surface (see FIGS. 4 and 5).

[0008] P-type or N-type semiconductor element 2 in the above
1, 22 are Bi ₂ Te ₃ , Bi ₂ Se ₃ , Sb ₂ Te
₃ etc. can be exemplified. The logarithm of the semiconductor element is 1 to 511
Pairs, more practically 4-127 pairs, preferably 4-31
Paired systems are valid.

The radiator 3 according to the present invention has a radiating fin made of a metal material, a wrapped mesh-like sheet material made of a metal material, a processed metal plate piece, and a water radiating metal container. A radiator that is filled with a medium (containing an appropriate amount of polyhydric alcohols for imparting antifreezing properties and an appropriate amount of a rust preventive agent), glycerin, ethyl alcohol, ammonia water, etc. Etc. can be exemplified.

The voltage applied by the DC power supply for supplying electricity to the thermoelectric conversion element 2 is 0.1 to 50 V. It is difficult to operate with a battery in a system having a voltage of 0.1 V or less, and in a system having a voltage of 50 V or more. It is necessary to increase the number of couples, and it becomes expensive, unsuitable for application to general products such as toys, training, writing materials and the like, and is restricted to special applications. Usually, a combination with the thermoelectric conversion element 2 which functions with an applied voltage of 0.2 to 20 V is preferable.

The power supply battery 7 for applying the voltage can be housed in the shaft body 5 constituting the color changing tool 1 and connected to the thermoelectric conversion element 2 by a lead wire 8. Can be configured separately and applied. Examples of the resistor 6 include a carbon-coated resistor, an oxide-coated resistor, a metal oxide-coated resistor, a nichrome wire, a stainless wire, a processed body of copper, iron, aluminum, or the like, and various alloy members. In particular, those having a resistance value of 0.1 Ω to 10 Ω are effective.

The heat transfer member 4, which is in close contact with the insulating plate 24 (heat absorbing side) of the thermoelectric conversion element 2, is not limited to a metal material, but is formed of a thin, heat conductive rubber, plastic, ceramic material or the like. It may be a body. Further, in a system in which the heat transfer member 4 is formed of a metal material, a portion serving as a contact end to the thermochromic layer can be processed with a silicon resin or a fluorine resin to impart lubricity.

Further, a porous body having continuous pores is mounted on the front end of the heat transfer member 4 made of a metal material, and the porous body is impregnated with water or the like, so that 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. In the discoloring device of the present invention, by changing the polarity, the heat-absorbing side A can be converted to the heat-generating side to function as a heating discoloring device.

Various forms of the discoloring tool 1 are effective, and examples thereof include writing tools, stamps, toy elements (for example, combs for doll toys, and other make-up tools). Next, the thermochromic material constituting the thermochromic layer of the thermochromic element applied in combination with the color changing device 1 of the present invention will be described.

A thermochromic material containing a conventionally known thermochromic dye, for example, 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.

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.

The thermochromic dye and the color-memory thermochromic dye described above are usually encapsulated in microcapsules, dispersed in a medium containing a binder, and used as a color material in the form of ink, paint or paint. It is applied to form a thermochromic layer on the support surface. In addition, thermochromic elements 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 is a thermochromic planar body, a thermochromic linear body, a thermochromic molded article having an uneven surface, or a thermochromic layer formed of the above-described thermochromic material on the surface layer. Includes all. Examples include writing boards, lessons, learning materials, picture books, and other toy elements.

The thermochromic layer having a color change point in the range of -10 ° C to + 100 ° C (preferably -5 ° C to + 70 ° C) is effective from a practical point of view.

[0020]

[Function] By applying a DC voltage (0.1 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 the heat absorbing side A and the heat generating side B (FIGS. 4 to 4).
(See FIG. 5).

By the action of the radiator 3 connected to the heat generating side B (converted to the heat absorbing side by reversing the polarity), the temperature of the heat absorbing side A is lowered and maintained in a desired temperature range.

Next, the effect of interposing the resistor 6 in series between the thermoelectric conversion element 2 and the power supply battery 7 will be described with reference to a graph (see FIG. 6).

The relationship between the cooling capacity of the thermoelectric conversion element 2 and the drive current is as shown in the graph. The color changing device of the present invention is a small-sized color changing device which is portable, and therefore, the number of PN junction pairs in the thermoelectric conversion element 2 to be applied is small, and the appropriate driving current is low. When such an element 2 is driven by a battery, the output current of the battery may be higher than the appropriate current range of the element 2. In this case, an excessive current exceeding the proper region of the drive current (e.g., _I.) Flows, cooling capacity _C. Becomes
However, if the driving current is reduced (for example, I ₁ ), the cooling capacity is C 2 _. Greater than C ₁ is obtained. Here, the driving current can be reduced by the interposition of the resistor, so that a large cooling capacity can be provided and the life of the power supply battery 7 can be prolonged.

When the color changing device 1 of the present invention is applied, in a system in which the thermochromic layer is formed of a coloring material containing a thermosensitive dye exhibiting a thermochromic characteristic with a small hysteresis width (ΔH), the color changing point may be changed before and after the color changing point. In the normal temperature range of the two states before and after the change, and the other state presents in the normal temperature range when the application of heat or cold required to develop that state is eliminated. Return to

On the other hand, a thermochromic layer formed of a color material containing a color-memorizing thermochromic dye has a low temperature below the low-temperature-side discoloring point.
Alternatively, by applying heat above the high-temperature side discoloration point, the colors are discolored to each other in a manner different from the normal state, and even if the application of cold or heat required to develop the state is eliminated, the state is retained and stored in the normal temperature range. The stored state is changed to the original state by a thermal means reverse to that required for the above-mentioned state to appear, and this is stored and stored in a normal temperature range.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A first embodiment will be described (see FIGS. 1 and 2).
A thermoelectric conversion element 2 (11 pairs of semiconductors) is attached to the front of the shaft body 5 having a large number of heat radiating holes 51 disposed on the side, and a metal tip having a writing tip shape is attached to the insulating plate 24 on the heat absorbing side A. The heating member 4 is closely arranged, and the insulating plate 24 on the heating side B is 1 mm thick × 8
Central part 1 of aluminum plate piece of mm width x 170 mm length
The radiator 3, which is bent in a “U-shape” with a 0 mm width as the base surface, is arranged in close contact with the base surface (heat-conductive grease is applied and the closeness is maintained). The thermoelectric conversion element 2 is connected to a dry cell 7 (1.5 V) via a lead wire 8, and its circuit is configured to be energized and operable with a resistor 6 (about 0.3Ω) interposed.

FIG. 3 shows a second embodiment. This is a color changing tool 1 in which the power supply accommodating portion 9 is configured as a separate body, and the other configuration is the same as that of the first embodiment.

The temperature of the writing tip of the discoloring device 1 was about 0 ° C. 20 seconds after the start of energization and −7 ° C. 60 seconds after the energization at room temperature of 25 ° C.

Using the color changing device 1 (for cold / hot), a white sheet material is heated with a color material containing a color-memory thermosensitive dye [black ← → colorless (low-temperature side color change point 15 ° C., high-temperature side color change point 35 ° C.)]. When writing was performed on a thermochromic element (having a white color at room temperature) in which the color-changing layer was formed on the entire surface, the white color of the written portion changed color, and a black handwriting appeared. The handwriting is 17 ° C
Retained at room temperature of 〜30 ° C. The sheet material is 3
When it is heated to 5 ° C. or more, the black handwriting disappears, and the whole surface is repeatedly used as a white writing surface, and is practically used.

Incidentally, in the system in which the resistor 6 is not applied in the color changing device 1, the time in which the writing tip is maintained at a temperature of 8 ° C. or less is 105 minutes, whereas the system in which the resistor 6 is applied is not applied. Thus, a temperature of 8 ° C. or less could be maintained for about 180 minutes. Further, when the resistor 6 having a resistance value of about 1Ω is applied, the temperature at the tip of the writing cannot be effectively lowered.

[0031]

The color-changing device of the present invention is applied in combination with a thermochromic element provided with a thermochromic layer. In particular, the color-changing function of a thermochromic element having a color-changing point in a low-temperature region is effectively exhibited. A thermochromic discoloration device that can be used to cool and discolor the thermochromic layer of an object quickly and easily at any time and at any place, compared to conventional cooling means using cold water or ice chips as a cooling medium. It satisfies the convenience, the applicability to non-water resistant objects, the portability, and the like. In addition, it can function effectively with a low applied voltage, and there is no danger of electric leakage or the like. The function can be made permanent by replacing batteries such as dry batteries. Further, the presence of the resistor can appropriately reduce the output current of the power supply battery to function effectively and prolong the battery life. Furthermore, since the amount of heat generated by the thermoelectric conversion element is reduced, it can function effectively even if the heat dissipation capability of the radiator is small, a small-capacity radiator can be applied, and a compact and easy-to-use discoloring tool is configured. can do. As described above, the color-changing device of the present invention can easily apply cold heat, and can be combined 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 a longitudinal sectional view of an embodiment of the color changing device of the present invention.

FIG. 2 is a circuit diagram of the color changing device of FIG. 1;

FIG. 3 is a longitudinal sectional view of another embodiment of the color changing device of the present invention.

FIG. 4 is a perspective view of a thermoelectric conversion element applied to the color changing device of the present invention.

FIG. 5 is an operation explanatory view of a thermoelectric conversion element applied to the color changing device of the present invention.

FIG. 6 is a graph showing a relationship between a cooling capacity of a thermoelectric conversion element and a drive current.

[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-absorbing side B Heating side 3 Radiator 4 Heat transfer member 5 Shaft 6 Resistor 7 Power battery 8 Lead wire 9 Power supply Housing unit 10 switch

Continuation of front page (58) Fields investigated (Int.Cl. ⁷ , DB name) A63H 30/02 A63H 33/00 A63H 33/22 B41K 1/00 B43K 8/00 B43K 19/00-19/12 B43L 1 / 00 B43L 19/00

Claims (2)

(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. A color changing device using a thermoelectric conversion element having a Peltier effect as a heat source, in which the upper and lower surfaces are sandwiched by a heat conductive insulating plate as a unit, wherein a heat transfer member is closely attached to a heat absorbing side of the thermoelectric conversion element. A discoloring tool comprising a radiator closely assembled on the heat generating side, and a power battery connected in series to the thermoelectric conversion element via a resistor. 2. The thermochromic element 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 a colored state [1] and a colored state [2], and a normal temperature range. 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.