JP3177664B2 - Heating and cooling 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 heating and cooling discoloring device. More specifically, the present invention relates to a color changing device having a heating element at one end of a shaft barrel and a cooling element at the other end, and having both functions of heating and cooling, which is combined with a thermochromic element having a thermochromic layer formed thereon. The present invention relates to a current-carrying and cooling discoloring device for applying a heat-discoloring layer to heat or cool discoloration of a contact portion by contacting a tip portion with the thermochromic layer.

[0002]

2. Description of the Related Art Conventionally, in a thermochromic element having a thermochromic layer that changes color due to temperature change, an electric heating tool equipped with a resistance heating element such as tungsten or nickel as means for changing the color of the thermochromic layer is actually used. These are disclosed in Japanese Unexamined Patent Publication No. Sho 62-139573 and Japanese Unexamined Patent Publication No. Sho 62-201178. On the other hand, a portable light-weight cooling means for cooling and discoloring the thermochromic layer has not yet been disclosed, and application of a cooling medium such as cold water or ice pieces, or placing the target thermochromic element in a refrigerator, The discoloration operation due to the cold inside the refrigerator had to be performed.

[0003]

In the above-mentioned conventional electric heating device, the heating element itself does not have a self-temperature control function, and there is a danger of overheating as it is, and a temperature control switch or the like is required. Insulation treatment such as coating of the heating part with ceramics or the like was necessary to avoid the danger due to electric leakage.

[0004] Even if the above-mentioned conventional cooling / heating means is applicable to a specific place such as a home, it cannot immediately change the color of the thermochromic layer of the object regardless of the place, if necessary, and cannot be used in a low temperature range. The function of the thermochromic element having a color change point 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.

[0005] The present invention relates to a discoloring tool having both functions of heating and cooling, which eliminates the risk of the conventional overheating or short circuit, and promptly brings a heating element to an intended heating temperature by applying a low voltage. A heating element which raises the temperature and has a small change in the heat generation temperature due to the change in the outside air temperature is provided at one end of the shaft body, and the other end of the shaft body has a low temperature of a thermoelectric conversion element having a Peltier effect. By installing a cooling element that effectively utilizes the heat absorption effect by applying voltage, a discoloration tool with both heating and cooling functions is configured, and when the heating and cooling functions are optional,
Convenience to express immediately and effectively in any place,
It is an object of the present invention to provide a heating and cooling discoloring device having high portability and safety, and to effectively exhibit thermochromic functions of various thermochromic elements.

[0006] In particular, the thermochromic element of interest has a color-memorizing thermochromic dye (discoloration showing a large hysteresis characteristic due to temperature change, and has two discoloration points, a low-temperature side discoloration point and a high-temperature side discoloration 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. The aim is to diversify products and develop applications in various fields by effectively expressing the functions of color-memory thermosensitive dyes.

[0007]

The heating and cooling discoloring device of the present invention will be described with reference to the drawings. The present invention relates to a thermochromic element 12 provided with a thermochromic layer 121 that changes color with a change in temperature.
A heating and cooling element for discoloring the thermochromic layer 121, the heating element being provided at one end of the barrel 6 and a cooling element being provided at the other end thereof; Is provided with at least a current-carrying heating element 8 and a heat-conductive tip member 4 arranged in contact with the current-carrying heating element 8, wherein the current-carrying heating element 8 is (A) electrically operated at least in a temperature range of 25 ° C. to 70 ° C. The resistance heating element has a positive temperature coefficient of resistance, and (b) has a volume resistivity (ρ25) at 25 ° C. of 9.
8 × 10 ⁻³ Ω · cm to 2.97 × 10 ⁵ Ω · cm,
(C) Ratio of volume resistivity at 25 ° C. and 70 ° C. (ρ70
/ Ρ25) satisfies each requirement that the following expression 5 ≦ (ρ70 / ρ25) ≦ 400, generates heat by applying a voltage of 0.8 V to 50 V, and has a heat generation saturation temperature of 25 ° C. to 70 ° C. The cooling element is constituted by a thermistor self-temperature-controlled to an arbitrary temperature within the range, and the cooling element is a P-type semiconductor element 2.
A thermoelectric conversion element 2 having a Peltier effect, in which 1 and an N-type semiconductor element 22 are alternately joined by metal pieces 23, and upper and lower surfaces are sandwiched by a heat conductive insulating plate 24 to form a unit;
At least a heat conductive tip member 41 connected to the heat absorption side A of the thermoelectric conversion element 2 and a radiator 3 connected to the heat generation side B of the thermoelectric conversion element 2 are provided. At an environmental temperature of 10 ° C. to 35 ° C., the heat-absorbing side A is required to have a temperature drop function of at least 3 ° C. or more with respect to each environmental temperature within the above range. Is what you do.

Further, the radiator 3 in the cooling element
Is required to be composed of a heat dissipating container 31 and water or a heat storage medium 32 mainly composed of water which is at least filled in the container when used.

Further, the thermochromic layer 12 of the thermochromic element 12
1 shows larger hysteresis characteristics due to temperature change,
A color containing a color storage state and a thermochromic dye capable of selectively changing and storing any of the above two states in a normal temperature range, in which the coloration state is a colorless state or a color change state between a colored state [1] and a colored state [2]. The heating and cooling discoloring device 1 having the above-described configuration, which is colored with a material and applied in combination with the thermochromic element 12, is a requirement.

In the above, the heating element 8 is made of BaTi
O ₃ -based sintered body (a semiconductor which is doped with a rare earth element to be converted into a semiconductor and further substituted with an element such as Sr if necessary, Si single crystal type, organic plastic type (low melting point crystalline plastic in graphite, etc.) In which a conductive fine powder is blended) and a low temperature region (25 to 70).
The above-mentioned BaTiO ₃ -based sintered body is effective in terms of the adjustment of the exothermic saturation temperature at (° C.), the temperature rise characteristics, and the like. The heating element 8 has a disk shape, a band shape, a honeycomb shape, or any other appropriate shape according to the purpose.

Next, the characteristics of the current-carrying heating element 8 applied to the present invention will be described with reference to graphs shown in FIGS.

The heating element 8 is at least 25.degree.
Within the range of ° C., it is an essential requirement (FIG. 4) that the temperature coefficient of electric resistance shows a positive value and that the increase of the resistance value with the temperature rise is steep. By being abrupt within the range, the calorific value decreases sharply, enabling self-temperature control within the temperature range.

The heating element 8 has a volume resistivity (ρ 25) at 25 ° C. of 9.8 × 10 ⁻³ Ω · cm to 2.97 × 1.
0 ⁵ Omega · cm, is in more detail within the tolerance volume resistivity at various temperatures ([rho) is shown in FIG. 5 (within the line indicating the upper limit value and the lower limit value), the volume at 25 ° C. and 70 ° C. The resistivity ratio (ρ70 / ρ25) is expressed by the following equation 5 ≦ (ρ70 / ρ25)
It must be within the range of ≦ 400.

By satisfying the above requirements, it is possible to supply the heating element 8 which satisfies the heat generation property in a low temperature range (70 ° C. or less, preferably 50 ° C. or less) and the self-temperature controllability. Heating element 8
The system outside the upper limit at each temperature, for example, in the system of volume resistivity exceeding the line of the upper limit, unless the voltage is increased, it is difficult to raise the temperature to the expected temperature range in a short time, the lower limit In a system with a volume resistivity lower than that of the wire, unless the voltage is made extremely low and a large current is applied, the expected heat generation temperature cannot be obtained, and the applicability in the low temperature range (for example, toy elements) will not be satisfied. .

FIG. 6 is a graph showing the relationship between the stable temperature of the heating element due to the change in room temperature, and the amount of heat generated per unit time by the heating element and the amount of heat radiation (per unit time) coincide. Heating element 8 stable at temperature and applicable to the present invention
Has less influence of the ambient temperature than the metal-based heating element system and shows stable thermal characteristics. FIG. 7 is a graph showing the relationship between the energization time and the heat generation temperature of the heating element. The experimental data was obtained from a BaTiO ₃ based sintered body [15.0 mmφ × 1 thickness.
mm, 2.5 Ω (25 ° C.) as a heating element, and a wiring test using a titanium wire (formed on a 0.1 mm polyester film) as a metal heating element was compared with a 30 mm square × thickness 0 mm. It was fixed on a 0.3 mm brass plate and obtained by applying a voltage of about 1 V.

It is effective to provide electrodes to the heating element 8 in terms of energizing assembly processing. Specifically, the opposite surface of the heating element 8 itself is sprayed with aluminum or plated with nickel, tin, or the like. , Or provided on the heat-conductive tip member 4 arranged in contact with the energizing heating element 8.

The heat conductive tip member 4 is not limited to a metal material.
It may be a thin rubber, plastic, ceramic, or the like, or may have a configuration in which the heating element 8 is coated with the above-described material. The heat-conductive tip member 4 includes a writing or coating tip shape, a shape having an image, a shape having a tip surface formed into a target shape such as a circle or a polygon, a toy element (for example, a comb of a doll toy, Up tool etc.). In a system in which the tip member 4 is formed of a metal material, a portion serving as a contact tip with the thermochromic layer 121 may be subjected to a silicon resin processing or a fluoro resin processing to impart moisture, and By attaching a porous body having pores and impregnating the porous body with water or the like, a soft touch and smooth applicability can be imparted.

The electrodes are provided on the opposite surface of the electric heating element 8, one electrode can be provided on the back surface of the electric heating element 8, and the counter electrode can be provided on the front surface of the heat conductive tip member 4 (conductive member). . The electrode is set so as to be able to conduct electricity to a power source 9 via a conductive member such as a lead wire 11.

As the power supply 9, various kinds of batteries and commercial power supplies are adjusted to a predetermined voltage (0.8 to 50 V) and applied. Power supply 9
For example, in the case of a dry battery or the like, a discoloring device can be configured by being removably housed in the main body, but can be connected to a power supply provided outside the system so as to be able to conduct electricity. The heat-generating element composed of the heat-conductive tip member 4 and the current-carrying heat-generating body 8 closely arranged on the back of the heat-generating tip member 4 is usually held by the holding member 5 and attached to one end of the shaft body 6. Next, a cooling element provided at the other end of the shaft cylinder 6 will be described. As the thermoelectric conversion element 2 having the Peltier effect in the above, a conventionally widely used thermoelectric conversion element is effective.
A couple of excess electron N-type semiconductor elements is
(Electrodes) alternately, and the upper and lower and lower surfaces are sandwiched by a thermally conductive insulating plate 24 of alumina, ceramic or the like to form a unit. When a current flows from the N-side terminal to the P-type terminal, the Peltier effect As a result, heat is absorbed on the upper surface and heat is generated on the lower surface.
(See FIGS. 8 and 9)

The 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 51.
1 pair, more practically 4-127 pairs, preferably 4-3
A pair of systems is effective.

Heat generation side B (heat absorption side A by switching polarity)
Radiator 3 connected and arranged
Must have a heat radiation capability of a thermal resistance value of 0.1 to 150 [° C./watt].
In a system exceeding the above, a sufficient heat radiation capability cannot be exhibited, and conversely, a radiator showing a value less than 0.1 [° C./watt] is difficult to design and manufacture.

The method of measuring and calculating the thermal resistance 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 obtained by adding the power W1 (voltage × current) applied to the thermoelectric conversion element 2 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 obtained by measuring the temperature T and the room temperature Tr at the center of the contact surface between the thermoelectric conversion element 2 and the radiator 3.

Calculated as Rth = (T−Tr) / W3.

The unit is T, Tr is ° C, W1, W2, W
3 is watts.

Tr is performed at a temperature between 10 ° C. and 35 ° C.

The voltage applied by the DC power supply for supplying electricity to the thermoelectric conversion element 2 is 0.3 to 50 V. In a system of 0.3 V or less, it is difficult to operate with a battery. 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 by an applied voltage of 0.5 to 20 V is preferable. The radiator 3 that satisfies the above requirements may be one having a heat radiation fin made of a metal material, one having a mesh sheet material made of a metal material wound thereon, and the like. Further, the radiator 3 is composed of a heat radiating container 31 and a heat storage medium 32 which is filled at least in the container at the time of use, and the two can work together to effectively exhibit an intended heat radiating function. it can. The heat dissipating container 31 does not hinder the application of a thin container made of a plastic material, but at least the surface of the thermoelectric conversion element 2 that is in contact with the insulating plate 24 (heating side) is made of a metal material. The effect of heat transfer to the heat storage medium 32 to be filled is enhanced. A metallic container made of aluminum, copper, brass or the like is effective. The heat storage medium 32 is a liquid, and it is effective to use a liquid having a relatively low viscosity compared to the convection effect, and has a large heat capacity per weight and volume, and also satisfies availability, safety, and cost. The water to be used is optimal, and an appropriate amount of a polyhydric alcohol for imparting antifreezing property or an appropriate amount of a rust preventive can be blended. Examples of the liquid other than water include glycerin, ethyl alcohol, ammonia water, and the like.

The power supply unit 9 for applying the voltage can be used in common with a power supply for energizing the heating element. By switching the switch 10, the energization of the cooling element and the energization of the heating element can be switched. As a power source, various batteries 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 absorption 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. with respect to the temperature in the above range at an environmental 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. Endothermic side of the thermoelectric conversion element 2 (insulating plate 24)
Is not limited to a metal material, and may be a thin processed body made of rubber, plastic, ceramic material, or the like. The heat-conductive tip member 41 has a writing or coating tip shape, a shape having an imprint, a shape having a tip surface shaped into a target shape such as a circle or a polygon, a toy element (for example, a comb of a doll toy, makeup, Tool etc.). In a system in which the tip member 41 is formed of a metal material, a portion serving as a contact tip with the thermochromic layer 121 may be subjected to a silicon resin processing or a fluorine resin processing to provide lubricity, By attaching a porous body having pores and impregnating the porous body with water or the like, a soft touch and smooth applicability can be imparted.

Note that the direct current referred to in the present application is the thermoelectric conversion element 2.
Means a direct current for effectively operating the, and does not mean that a reverse voltage must not be applied even momentarily 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.

In the present invention, various forms of the electric heating, cooling and discoloring tools are effective. For example, writing tools, applicators, handwriting erasers, stamps, toy elements (for example, combs for doll toys, other makeup tools) Etc.).

Next, a thermochromic material constituting the thermochromic layer 121 of the thermochromic element 12 applied in combination with the heating / cooling color changing device 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 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)

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)

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) is substantially in the process of increasing the temperature. The point C (temperature t4) is a point where the color is completely erased at a temperature higher than this point, and the discoloration temperature range is the temperature between t1 and t4. In particular, both the colored state and the colorless state, or both the colored state [1] and the colored state [2] can coexist, and the substantial discoloration temperature is between t2 and t3, which is a region having a large difference in color density. It is an area in which one of the above two states can be selectively stored and held in a temperature range and a normal temperature range.

The aforementioned thermochromic dye and color-memory thermochromic dye are usually encapsulated in microcapsules and dispersed in a medium containing a binder to form a coloring material such as ink, paint or paint. It is applied to form a thermochromic layer on the support surface. 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 a writing board, a lesson, a learning material, a picture book, various display bodies, 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.

[0039]

The discoloring device of the present invention is provided with a cooling element at one end and a heating element at the other end. The tip of each element is brought into contact with a thermochromic object to cool or discolor the contact area. Has functions. In the heating element, when a voltage is applied, the current-carrying heating element 8 self-heats and rises in temperature. As the temperature rises, the resistance value sharply increases and the temperature rise decreases. Stable self-temperature control.
Looking at the relationship between the elapsed time after energization and the heat generation temperature, the amount of heat generated per unit time due to the temperature rise becomes almost constant due to the extremely low rate of change in resistance of the metal heat generation system due to temperature. While the temperature of the heating element of the present invention rises slowly, a large current flows immediately after the current is applied, and the temperature rise rate is large and quickly rises to a predetermined temperature.

With respect to changes in room temperature, the current-carrying heating element 8 is stable at about 33 ° C. when the ambient temperature is 20 ° C., and is stable at about 38 ° C. when the ambient temperature is 28 ° C. ° C
On the other hand, in a metal heating element system, the stable temperature is about 32 ° C. when the ambient temperature is 20 ° C. and the ambient temperature is 28 ° C., depending on a small change in the calorific value per unit time depending on the temperature. As shown in the experimental data (see FIG. 6) in which the stable temperature at this time is 39 ° C. and the difference is 7 ° C., the current-carrying heating element 8 applied to the present invention has a temperature change due to the ambient temperature as compared with the metal heating element system. Shows small behavior.

The current-carrying heating element 8 comprises (a), (b), and (c)
By satisfying each of the requirements, a low voltage (0.8 to 50
By the application of V), the above-described behavior is exhibited, and the self-temperature control function is performed in a low temperature range of 70 ° C. or less, and the desired thermal characteristics are exhibited. The appropriate heat-generating temperature is thus transmitted to the heat-conductive tip member 4 arranged in contact with the electric heating element 8.

In the cooling element, a DC voltage (0.3 to
When a current is applied from the N-side terminal to the P-side terminal by applying 50 V), heat is absorbed on the upper surface and heat is generated on the lower surface due to the Peltier effect.
Heat is transferred to the heat conductive insulating plates 24 on the upper and lower surfaces to form a heat absorbing side A and a heat generating side B. By the action of the radiator 3, the temperature on the heat absorption side A is lowered and maintained in a desired range. As the radiator 3,
In a system in which a metal radiating fin, a mesh sheet material, or the like is wound, the thermal resistance value is 0.1 to 150 [° C./watt].
By setting the resistance value to an appropriate value in the range described above, the desired heat radiation ability is developed. 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 radiator 3
Due to the effect of dissipating 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. As the temperature of the radiator 3 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 provided.
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. In the system in which the heat storage medium 32 is filled into the heat radiating container 31 and applied as the radiator 3, in view of the above requirements, the function of the radiator 3 is mainly focused on improving the heat storage capacity. By filling a heat storage medium 32 having a large heat storage capacity into the heat radiating container 31, the ability to absorb the amount of heat generated from the heat generation side B of the thermoelectric conversion element 2 is increased, and the heat storage medium 32 is sufficiently used for a short time. It functions as the radiator 3. The proper cold temperature is thus transmitted to the heat conductive tip member 41 closely arranged on the heat absorbing side A.

The heating tip member 4 or the cooling tip member 41 is brought into contact with the thermochromic element 12 having a surface layer formed by the thermochromic layer 121 (having a discoloration point in the range of -10 ° C. to 60 ° C.). And discolor the contact area.

The thermochromic layer 121 has a hysteresis width (ΔH).
In a system formed of a coloring material containing a thermosensitive dye exhibiting a small thermochromic property, the color changes before and after the color change point, and one of the two states before and after the change exists in the normal temperature range. 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-memorizing thermochromic dye has a different appearance from the normal state by applying heat below the low-temperature discoloration point or above the high-temperature discoloration point. Discolored to each other, and even without the application of cold or heat required for the state to develop, the state can be stored and maintained in the room temperature range, and the stored mode is developed for the state. The color is changed to the original state by the thermal means reverse to that required in step (1), and this is stored and stored in the normal temperature range.

[0046]

Embodiment 1 (see FIGS. 1 to 3) An electric heating element 8 [BaTiO ₃ -based sintered body (15 mmφ) is provided on the inner bottom surface of a bottomed short aluminum cylinder (heat-conductive tip member 4).
× 1 mm thick, conductive plating layers formed on both sides, heat generation saturation temperature 45 with a resistance value of 2.5 Ω (25 ° C.)
Are connected by a conductive adhesive to form a heating element. Lead wires 11 are respectively connected to the inner walls of the current-carrying heating element 3 and the short cylindrical body, and are connected to a power supply 9 (comprising four 1.5 V batteries) provided outside the system, and are set to be able to conduct electricity. . The heat-generating element is attached to the holding member 5 made of a plastic material, with the bottomed portion protruding, and attached to one end of the shaft body 6 to constitute a heating discoloration tool. The cooling element is configured as follows. A holding member 51 formed of a plastic material and having a center hole and an enlarged hole communicating with the center hole and opening at the other end.
And a heat conductive tip member 41 made of aluminum is inserted into the center hole, and the rear end face is closely attached to the insulating plate 24 on the heat absorption side A of the thermoelectric conversion element 2 (semiconductor logarithm: 7 pairs) attached to the enlarged hole. Attach to condition. A lead wire 11 is connected to the thermoelectric conversion element 2, and the thermoelectric conversion element 2 is set so as to be able to conduct electricity and generate heat. In the enlarged hole of the holding member 51, the bottom of the radiator 3 configured by filling a water radiating container 31 made of an aluminum barrel 6 (diameter 15 mmΦ, total length 10 cm) with about 5 cc of water (heat storage medium 32) is provided. It is inserted and attached closely to the insulating plate 24 on the heating side B.

[0047]

[Embodiment 2] (not shown) A pen point-shaped heat-conductive tip member 41 is provided on the insulating plate 24 on the heat absorption side A of the thermoelectric conversion element 2 (semiconductor logarithm: 11 pairs) attached to the holding member 51. The heat dissipator 3 (heat resistance value: 19) is formed by winding an aluminum mesh sheet material on an aluminum bar having a contact plane on the insulating plate 24 on the heat generation side B. [℃
/ Watt] are connected to each other with the contact planes in close contact with each other and inserted into the shaft body 6 (a number of heat dissipation holes are provided on the peripheral wall).
Via the DC power supply unit 9 (1.5 V dry battery) provided outside the system to constitute a cooling discoloration device. The shaft barrel 6
The heating element of the first embodiment is attached to the other end of the heat discoloration device.

[0048]

Embodiment 3 (not shown) In the color changing tool of Embodiment 2, a radiator 3 having a large number of fins formed by die-casting aluminum is connected to an insulating plate 24 on the heat generation side of the thermoelectric conversion element 2. The configuration is the same as that of the second embodiment except that two 1.5 V dry batteries are provided at the rear position of the radiator 3 and assembled so as to be able to conduct electricity through the lead wire 11. A discoloring tool 1 that can be used for both purposes was obtained. The DC power supply is not limited to a system provided with a battery or the like, but may be a system connected to an AC / DC converter.

Application Example 1 (see FIGS. 1 and 2) Using the color changing device 1 of Example 1, a color memory thermosensitive color changing dye [black ← → colorless, low temperature side color change point (t 1)] on a white sheet material
15 ° C., high-temperature side discoloration point (t 4) 35 ° C.]. The heat-transferable tip member 4 is applied to the thermochromic element 12 (showing white at room temperature) having the thermochromic layer 121 formed on the entire surface.
1 (cooling side) in contact with the handwriting, the white color of the writing portion changed color, and a black handwriting (thermochromic image 122) appeared. The handwriting was stored and stored at room temperature of 17 ° C. to 30 ° C. (see FIG. 1). When the black handwriting portion was written by contacting the heat conductive tip member 4 (heating side: the writing tip portion is heated to about 40 ° C.) of the color changing tool 1 of Example 1 with the handwriting portion, Black handwriting could be erased (see Fig. 2)

Application Example 2 The heat-discoloring element 12 of Application Example 1 (however, the entire surface is kept black at room temperature) is heated to the tip of the discoloring tool 1 of Example 1 (writing tip at about 40 ° C.). Was heated), and a white handwriting appeared when writing was performed. The handwriting was stored at room temperature of 17 ° C to 30 ° C. The white handwriting portion is cooled to the cooling-side tip of the color changing tool 1 of the first embodiment (the front end face of the heat-conductive tip member 41 is cooled to about 6 ° C.)
Abutting the handwriting, the white handwriting can be erased,
The entire surface was restored to a black sheet. The aspect changes of Application Example 1 and Application Example 2 were repeatedly reproduced.

Application Example 3 A picture book for an infant having a configuration in which answer elements are hidden by a reversible thermochromic layer (a banana pattern and characters are printed and formed with yellow non-color-changing ink, and the non-color-changing layer is covered with A reversible thermochromic layer having a discoloration point, exhibiting a green color below 40 ° C., and erasing at 40 ° C. or more is overprinted.) Then, the layer was erased and a non-discolored layer appeared, and the answer was determined. After a while, the non-color-changing layer was restored to the concealed state by the thermochromic layer colored green.

[0052]

The heating and cooling discoloring device of the present invention is applied in combination with a thermochromic element provided with a thermochromic layer, and can easily discolor the thermochromic layer by heating or cooling.

On the side of the heating element, the energized heating element can be quickly heated by applying a low voltage, and the temperature can be raised to a predetermined temperature to change the color of the thermochromic layer. There is no danger of overheating because the temperature is self-controlled to the exothermic saturation temperature in the low temperature range. Furthermore, since the heating system is an energized heating system by applying a low voltage, there is no danger due to electric leakage, and it is not necessary to cover the heater unit to prevent the danger. it can.

On the cooling element side, the function of a thermochromic element having a discoloration point in a low temperature range can be effectively exhibited, and it can be compared with conventional cooling means using cold water, ice chips or the like as a cooling medium. It satisfies the convenience of instantaneously and easily discoloring the thermochromic layer of the object at any time and in any place, applicability to a non-waterproof object, and portability.

Moreover, the applied voltage is low (50 V or less).
And it can function effectively, and there is no danger such as electric leakage.
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 (discolored with a large hysteresis characteristic due to temperature change, and has two discoloration points, a low-temperature side discoloration point and a high-temperature side discoloration point). , Colored and colorless or colored [1]
And a color [2], and can be changed to a state different from the normal state by applying cold heat below the low-temperature side discoloration point or heat above the high-temperature side discoloration point. A dye having a function capable of being retained) by applying in combination with a system having a thermochromic layer colored with a coloring material containing a color material, thereby effectively exhibiting the function of the color memory thermochromic pigment. This enables diversification of products and application development to various fields.

[0057]

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a use state of an embodiment of the heating and cooling discoloring device of the present invention.

FIG. 2 is an explanatory view showing another use state of one embodiment of the heating and cooling discoloring device of the present invention.

FIG. 3 is a longitudinal sectional view of one embodiment of the heating and cooling discoloring device of the present invention.

FIG. 4 is a graph showing characteristics of temperature and resistance of a heating element applied to the present invention.

FIG. 5 is a graph showing an allowable range of volume resistivity at each temperature of a heating element applied to the present invention.

FIG. 6 is a graph showing a stable temperature of a heating element according to a change in room temperature.

FIG. 7 is a graph showing a relationship between an energizing time and a heating temperature of a heating element.

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 diagram of a color change characteristic due to a temperature change of a thermochromic dye.

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 Heating and cooling 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 Heatsink 4 Heat-conductive tip member 41 Heat-conductive tip member 5 Holding member 51 Holding Member 6 Shaft barrel 7 Lead wire cover member 8 Electric heating element 9 Power supply 10 Switch 11 Lead wire 12 Thermochromic element 121 Thermochromic layer 122 Thermochromic image

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification symbol FI B41K 1/00 B41K 1/00 Z (58) Field surveyed (Int.Cl. ⁷ , DB name) A63H 3/52 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 (3)

(57) [Claims] A thermochromic element provided with a thermochromic layer that changes color due to a temperature change, wherein the thermochromic element is a current-carrying color changing tool having a function of both heating and cooling for changing the color of the thermochromic layer. A heating element at one end and a cooling element at the other end,
The heating element includes at least an energizing heating element and a heat-conductive tip member arranged in contact with the energizing heating element, and the energizing heating element has an electrical resistance at least in a temperature range of 25 ° C to 70 ° C. (B) a volume resistivity (ρ25) at 25 ° C. of 9.8 × 10 ⁻³ Ω · cm to 2.97 × 10 ⁵ Ω · cm;
(C) Ratio of volume resistivity at 25 ° C. and 70 ° C. (ρ70
/ Ρ25) satisfies each requirement that the following expression 5 ≦ (ρ70 / ρ25) ≦ 400, generates heat by applying a voltage of 0.8 V to 50 V, and has a heat generation saturation temperature of 25 ° C. to 70 ° C. The cooling element consists of a P-type semiconductor element and an N-type semiconductor element alternately joined by metal pieces, and a heat conductive insulating plate on both upper and lower surfaces. A thermoelectric conversion element having a Peltier effect in a unitized configuration, a heat conductive 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 At least, at an environmental temperature of 10 ° C. to 35 ° C. by application of a DC voltage, the heat absorbing side has an environmental temperature within the above range,
A heating / cooling discoloring device configured to exhibit a temperature lowering function of at least 3 ° C. or higher. 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 heating according to claim 1, wherein the heating is performed in combination with the thermochromic element, which is colored with a color material containing a color-memorizing thermochromic pigment capable of selectively storing and holding one of the two states. , Cooling discoloration equipment. 3. The discoloring device according to claim 1, wherein the radiator in the cooling element comprises a heat-radiating container and water or a heat storage medium mainly composed of water contained in the container.