JP3177659B2 - 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 changes color of the thermochromic layer by contacting the thermochromic element on which the thermochromic layer is formed.

[0002]

2. Description of the Related Art Conventionally, as a means for discoloring a thermochromic element, a current-carrying heating tool equipped with a resistance heating element such as tungsten or nickel has been disclosed, and is contacted with a thermochromic material formed on the surface of an animal toy or the like. An attempt to change the color of the contact portion is disclosed in Japanese Utility Model Laid-Open Publication 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 non-water-resistant thermochromic element, not only the direct contact of the cooling medium but also the 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 color changing device for changing the color of the thermochromic layer by cooling and heat, and further a color changing device having both functions of cooling and heating by switching the polarity of the applied voltage. 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 colored [1] and colored [2], and changed to a state different from the normal state by application of cold heat below the low-temperature side discoloration point or heat above the high-temperature side discoloration point. And a colorant containing a thermochromic layer colored with a coloring material containing a colorant having a function of allowing the aspect to be stored and maintained alternately in a normal temperature range. The purpose of the present invention is to provide a discoloring device that enables the diversification of products and the application and development in various fields by effectively expressing the function of the warm pigment.

[0005]

The discoloring device of the present invention will be described with reference to the drawings. The present invention relates to a color-changing tool for thermally discoloring a contact portion by contacting a thermochromic element on which a thermochromic layer 122 is formed.
A color changing tool 1 using a thermoelectric conversion element 2 having a Peltier effect as a heat source, in which a mold semiconductor element 22 is alternately joined by metal pieces 23 and upper and lower surfaces are sandwiched by a heat conductive insulating plate 24 to form a unit. In addition, a shaft body 8 for accommodating and holding the thermoelectric conversion element 2, a heat-conductive writing tip member 6 connected to the heat-absorbing side of the thermoelectric conversion element 2, and a connection end to the heat-generating side of the thermoelectric conversion element 2. The radiator 3 includes a radiator 3 operable by applying a DC voltage, and the radiator 3 has a thermal resistance of 0.1 to 150.
It has a heat radiation capacity of [° C./watt], and is configured such that, at an environmental temperature of 10 ° C. to 35 ° C., the heat absorbing side can exhibit a temperature drop function of at least 3 ° C. or more with respect to each environmental temperature within the above range. The discoloration tool 1 is a requirement. Further, by reversing the polarity of the DC current supplied to the thermoelectric conversion element 2 (e.g., by attaching a changeover switch 10 or reversing the positive and negative directions by replacing the dry batteries), the heat absorption side and the heat generation side are reversed, and heating is performed. The discoloring tool 1 having a dual-purpose function of cooling is required. Further, the thermochromic layer 121 of the thermochromic element 12 shows a large hysteresis characteristic due to a temperature change, and the colored state and the colorless state or the colored state [1] and the colored state [2]
Discoloration 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 one of the two states in the normal temperature range, exhibiting the alternation between the states. Tool 1 is a requirement.

[0006] In the above, the thermoelectric conversion element 2 having the Peltier effect has an object,
It is appropriately selected according to the application, the form of the radiator to be incorporated, and the like. 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. 8,
9) P-type or N-type semiconductor element 2 in the above.
Examples of 1, 22 include Bi ₂ Te ₃ , Bi ₂ Se ₃ , Sb ₂ Te _{3 and the} like. The number of pairs of semiconductor elements is 1 to 511 pairs, more practically 4 to 127 pairs, and preferably 4 to 31 pairs. Heat generation side B (heat absorption side A by switching polarity)
It is essential that the radiator 3 connected and arranged to have a heat radiation capacity of a thermal resistance value of 0.1 to 150 [° C./watt]. Therefore, a radiator that cannot exhibit a sufficient heat radiation capability and exhibits a value of less than 0.1 [° C./watt]
Difficult to manufacture. The method of measuring and calculating the thermal resistance value of the radiator 3 will be described below. The heat generating surface of the thermoelectric conversion element 2 emits a heat amount of W3 per unit time into the atmosphere by the radiator 3. W3 is the power W1 (voltage × voltage) applied to the thermoelectric conversion element 2.
Current) and the absolute value W2 of the amount of heat absorbed per unit time from the cooling surface. W3 = W1 + W2 The thermal resistance value (Rth) in the present application is calculated by measuring the temperature T and the room temperature Tr at the center of the surface where the thermoelectric conversion element 2 and the radiator 3 are in contact, and Rth = (T−Tr) / W3. The unit is T, Tr is ° C, W1, W
2, W3 is watts. In addition, Tr is performed at a temperature between 10 ° C and 35 ° C. The voltage applied by the DC power supply that energizes the thermoelectric conversion element 2 is 0.3 to 50 V. It is difficult to operate with a battery in a system having a voltage of 0.3 V or less, and in a system having a voltage of 50 V or more, the number of couples corresponding thereto is small. Therefore, it is 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 by an applied voltage of 0.5 to 20 V is preferable. The power supply unit 9 for applying the voltage can be housed and arranged integrally in the casing 8 of the color changing tool 1, but can be separately provided via a cord or the like. As a power source, various batteries such as a dry battery or an AC / DC converter may be connected to convert an alternating current into a direct current and apply. The temperature lowering function of the heat-absorbing side A in the 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. with respect to the temperature in the above range.
(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 increased by 3 ° C. to 60 ° C. (preferably 5 ° C. to 50 ° C.) within the environmental temperature range. It is configured so that the characteristics can be exhibited. 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. Discoloration tool 1
Various forms are effective, and examples thereof include a writing implement, a stamp, and a toy element (for example, a comb of a doll toy, other makeup equipment, and the like). 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, for example, a liquid crystal, an electron-donating color-forming organic compound, a 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. 10)

[0008] 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. 11) In the graph, point A (temperature t ₁ ) is a point at which the color becomes completely colored at a temperature lower than this, and point B (temperature t ₃ ) increases in temperature. The point at which substantial discoloration (decolorization) starts in the process, point C (temperature t ₄ ) is a point where the color is completely decolored at a temperature higher than this point, and the discoloration temperature range is t _1. And the temperature range between t ₄ and, in particular, both the colored state and the colorless state, or both the colored state [1] and the colored state [2] can coexist;
Substantial color change temperature range between t ₂ and t ₃ is a region having a large difference in color density, which is selectively storing holdable area either of the two states in normal temperature range. The thermochromic dye described above, the color-memorizing thermochromic dye are usually encapsulated in microcapsules and dispersed in a medium containing a binder to form an ink,
It is applied as a color material in the form of paint or paint, and a thermochromic layer is formed on the surface of the support. 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 comprises
It includes a thermochromic planar body, a thermochromic linear body, a thermochromic molded article having an uneven surface, and all the thermochromic layers 121 made of the above-described thermochromic material formed on the surface layer. Writing board,
Examples include teaching, learning materials, picture books, and other toy elements. The thermochromic layer 121 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 viewpoint.

[0009]

[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 the heat absorbing side A and the heat generating side B. A radiator 3 (having a specific range of thermal resistance value) connected to and arranged on the heat generating side B (converted to a heat absorbing side by reversing the polarity).
The temperature of the heat-absorbing side A is lowered and maintained in a desired range by the action of (1). When the color-changing device 1 is brought into contact with the thermochromic element 12 on which the surface layer is formed by the thermochromic layer 121, the thermochromic layer 121 in the contact portion is cooled and thermally discolored, and the heat-absorbing side A is changed by reversing the polarity. Heat discoloration is caused by reversing the heat generation side. The thermochromic layer 121 has a hysteresis width (Δ
In a system formed of a coloring material containing a thermosensitive dye exhibiting a small thermochromic property of H), the color changes before and after the color changing point,
Of the two states before and after the change, one specific state is present in the normal temperature range, and the other state returns to the state exhibited in the normal temperature range when the application of heat or cold required to develop the state 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.

[0010]

Embodiment 1 (See FIGS. 1 to 4) The thermoelectric conversion element 2 (semiconductor logarithm: 11 pairs) is attached to the front of the shaft body 8 having a large number of heat radiating holes 83 arranged on the side. A metallic heat conductive writing tip member 6 having a writing tip shape is closely arranged on the insulating plate 24 of A, and the insulating plate 24 on the heat generation side B is provided with a heat dissipating member made of an aluminum rod having a contact plane and an aluminum mesh. A radiator 3 (heat resistance value: 19 [° C./watt]) formed by winding a sheet-like material is disposed so as to be in close contact with the contact plane, and is connected to the thermoelectric conversion element 2 via a lead wire. DC power supply 9 installed outside the system
(1.5 V dry battery), and the direction of the current can be freely switched by a polarity change switch 11 attached thereto. Thus, the dual-purpose color changer 1 capable of reversibly applying cold and heat is constituted. The discoloring device 1 has a voltage of 1.0 V, a current of 0.7 A, a maximum temperature of 32 ° C. on the heat-generating side (about 3 minutes), and a minimum temperature of -3 ° C. on the heat-absorbing side (at about 18 minutes at room temperature). 3 minutes), endothermic rising characteristics (10
After 11 seconds). Using the color changing device 1, a colorant containing a color-memory thermosensitive dye [black ← → colorless (low-temperature side color change point (t ₁ ) 15 ° C., high-temperature side color change point (t ₂ ) 35 ° C.) on a white sheet material. When writing was performed on the thermochromic element 12 (having white color at room temperature) in which the thermochromic layer 121 was formed on the entire surface, the white color of the written portion changed color, and a black handwriting appeared. Was stored at room temperature of 17 ° C. to 30 ° C. When the sheet material was heated to 35 ° C. or higher, the black handwriting disappeared, and the whole surface was repeatedly used as a white writing surface, and it was put to practical use.

[0011]

Second Embodiment (See FIG. 5) A thermoelectric conversion element 2 (semiconductor logarithm: 11 pairs) is mounted on the front part of a shaft body 8 having a large number of heat radiation holes 83 arranged on the side, and the heat absorption side A is insulated. A metal heat conductive writing tip member 6 having a writing tip shape is closely arranged on the plate 24, and the insulating plate 24 on the heat generation side B includes:
A radiator 3 having a large number of fins formed by die-casting of aluminum is connected and arranged.
A cooling / discoloring device 1 was provided, in which a 5 V dry battery was arranged, which was set to be able to conduct electricity through the thermoelectric conversion element 2 and a lead wire, and which was turned on and off by a power switch 10 provided at the front of the shaft body.

[0012]

Third Embodiment (See FIG. 6) A thermoelectric conversion element 2 (semiconductor logarithm: 17 pairs) is sucked at the front of a shaft body 8 having a large number of heat radiation holes 83 arranged on the side, and the heat generation surface is in the axial direction. A comb-shaped radiator 3 made of an aluminum material is disposed on the heat-generating side (which becomes the heat-absorbing side by switching the polarity) with its base end surface close to the heat-generating side, and a pen-shaped metal is provided on the heat-absorbing side. The heat conductive writing tip member 6 is arranged with its side flat surfaces in close contact with each other, is set on a DC power supply (6V) (not shown) arranged outside the system, and is provided with a polarity switching switch for both cooling and heating. The color changing tool 1 is configured. The DC power supply is not limited to a system including a battery or the like, but may be a system to which an AC / DC converter is connected.

[0013]

Embodiment 4 (See FIG. 7) A thermoelectric conversion element 2 (semiconductor logarithm: 11 pairs) is housed and attached to a short shaft body 8, and the heat absorbing surface of the element 2 has a base end face and the base end face. A metal heat transfer tip member 6 having a writing portion protruding from a central portion of the element 2 is attached so that the base end face is in close contact with the heat absorbing surface. A radiator 3 having a through-hole and having comb-shaped fins on its peripheral surface is mounted so that the front end face is in close contact, a lead wire is inserted through the through-hole, and one end is connected to the element 2 and the other end is connected to the system. By connecting to a power supply element (according to Example 3) provided outside, a discoloring device 1 for both cooling and heating was constructed.

[0014]

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. In contrast to conventional cooling means using cold water, ice chips or the like as a cooling medium, the thermochromic layer of the object can be quickly and easily discolored at any time and in any place. Satisfies convenience, applicability to non-water resistant objects, portability, etc. Further, by changing the polarity of the power supply, a discoloring tool having both functions of cooling and heating can be provided. In addition, it can function effectively when the applied voltage is low (50 V or less), and there is no danger of electric leakage or the like. The function can be made permanent by replacing batteries such as dry batteries. 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.

[0015]

[Brief description of the drawings]

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

FIG. 2 is a longitudinal sectional view of the color changing tool of FIG.

FIG. 3 is a sectional view taken along line AA of FIG. 2;

FIG. 4 is an exploded perspective view of a main part of the color changing tool of FIG. 1;

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

FIG. 6 is an explanatory longitudinal sectional view of a main part of another embodiment of the color changing device of the present invention.

FIG. 7 is an explanatory longitudinal sectional view of another embodiment of the color changing device of the present invention.

FIG. 8 is a perspective view of a thermoelectric conversion element applied to the color changing device of the present invention.

FIG. 9 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. 10 is an explanatory graph of a color change characteristic of a thermochromic dye due to a temperature change.

FIG. 11 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-absorbing side B Heating side 3 Radiator 6 Heat-conductive writing tip member 8 Shaft body 83 Heat-dissipating hole 9 Power supply unit 10 Switch Reference Signs List 11 power 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 (3)

(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 discoloring tool using a thermoelectric conversion element having a Peltier effect as a heat source having a configuration in which the upper and lower surfaces are sandwiched by a heat conductive insulating plate as a heat source. A thermoconductive writing tip member connected to the heat absorption side of the thermoelectric conversion element and a radiator connected to the heat generation side of the thermoelectric conversion element are provided, and the thermoelectric conversion element is configured to be operable by application of a DC voltage. The radiator has a thermal resistance value of 0.1 to 150 [° C /
And a heat-dissipating ability at a temperature of 10 ° C. to 35 ° C. so that the heat-absorbing side can exhibit a temperature drop function of at least 3 ° C. or more with respect to each environmental temperature within the above range. 2. The discoloring tool according to claim 1, wherein the heat absorbing side and the heat generating side are reversed by reversing the polarity of the DC current supplied to the thermoelectric conversion element, and the discoloring tool has both heating and cooling functions. 3. 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 a colored state [1] and a colored state [2], and has a normal temperature range. The color-memorizing thermochromic pigment capable of selectively storing and holding any one of the two states in a color material, and applied in combination with the thermochromic element. 2. The discoloration tool according to 2.