JP2905998B2 - Heating and cooling discoloration set - 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 set. More specifically, an electric heating and cooling discoloration device set which is applied in combination with a thermochromic element having a thermochromic layer formed thereon, and which heats or cools the thermochromic layer to discolor, and which functions by applying a low voltage. About.

[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] The heating discoloring device of the present invention eliminates the risk of the conventional overheating or electric leakage, quickly raises the heating element to a desired heating temperature by applying a low voltage, and furthermore, the heating and discoloring device is affected by fluctuations in the outside air temperature. Construct a heating tool with a small variation in heat generation temperature, and provide a simple and safe energizing heating discoloring tool that discolors by directly contacting the thermochromic layer of the object or discoloring by blowing warm air etc. An object of the present invention is to provide a simple and portable energizing cooling discoloring device which is provided in combination with the energizing heating discoloring device. The conventional cooling / heating means, even if applicable in a specific place such as a home, can not immediately change the color of the thermochromic layer of the object, regardless of the place, when necessary, and has a discoloration point in a low temperature range. The function of the thermochromic element having the above was not able to 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 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, the surface is generated on the container surface. The thermochromic element tends to deteriorate due to a condensed layer, water droplets, or water leakage.

The cooling discoloring device of the present invention satisfies the immediate effect, the cooling durability, the convenience, and the like, and provides an energizing cooling discoloring device for easily and thermally discoloring the thermochromic layer at any time and at any place. In combination with the energizing heating and discoloring device, a heating and cooling discoloring device set that immediately expresses the function of heating and cooling when desired, and effectively expresses the thermochromic function of the thermochromic element. It is something to offer.

[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 present invention will be described with reference to the drawings. The discoloring tool set of the present invention includes an energizing heating discoloring tool 1 and an energizing cooling discoloring tool 11. The energizing heating discoloring device 1 heats the energizing heating element 7 housed and held in the casing 8 and heats the heat conductive member 6 arranged in contact with the heating element 7 to function. In this configuration, warm air is discharged from a discharge port at the end of the casing via a blowing means disposed at a position where the electric heating element 7 has a positive temperature coefficient of electric resistance in a temperature range of 25 ° C. to 70 ° C. It is a resistance heating element showing a value.
At 25 ° C (C) Ratio of volume resistivity at 25 ° C. and 70 ° C. (ρ70
/ Ρ25) is within the range of the following formula: 5 ≦ (ρ70 / ρ25) ≦ 400, generates heat by applying a voltage of 0.8 V to 40 V, and generates a heat saturation temperature of 25 ° C. to 70 ° C.
Thermistor is self-controlled to an arbitrary temperature within the above temperature range.

The energizing cooling discoloration tool 11 is a P-type semiconductor element 2
1 and an N-type semiconductor element 22 are alternately joined by metal pieces 23, and upper and lower surfaces are sandwiched by a thermally conductive insulating plate 24 to form a unit, and the casing accommodates and holds the thermoelectric conversion element 2 having the Peltier effect. 8, a radiator 3 connected to the heat-generating side B of the thermoelectric conversion element 2, and a heat-conductive member 6 connected to the heat-absorbing side A of the thermoelectric conversion element 2. 6 may function as a cold tip, or cool air may be discharged from a discharge port at the tip of the casing via a blowing means positioned behind the thermoelectric conversion element 2, and the radiator 3 has a thermal resistance value of 0.
It has a heat radiation function of 1-150 [° C / watt]
At an environmental temperature of 35 ° C., the heat-absorbing side A is configured to exhibit a temperature drop function of at least 3 ° C. or more with respect to each environmental temperature within the above range.

Further, the thermochromic layer 1 of the thermochromic element 12
21 shows a large hysteresis characteristic due to a temperature change, exhibits a colorless state and a colorless state, or exhibits an alternation between a colored state [1] and a colored state [2], and selectively stores and retains one of the two states in a normal temperature range. A requirement is a color changer set having the above-described configuration, which is colored with a color material containing a possible color memory thermochromic dye and applied in combination with the thermochromic element 12.

[0010] Semiconductor, and, if necessary, substituted with an element such as Sr, Si single crystal, organic plastic (low-melting crystalline plastic blended with conductive fine powder such as graphite), etc. And a low temperature range (25 to 7). Is preferred. The heating element 7 has a disk shape, a band shape, a honeycomb shape, or any other appropriate shape depending on the purpose.

Next, the characteristics of the electric heating element 7 applied to the present invention will be described with reference to graphs shown in FIGS.

The energizing heating element 7 has a temperature of at least 25.degree.
Within the range of ° C., it is essential that the temperature coefficient of electric resistance shows a positive value, and that the increase in the resistance value with the temperature rise is steep (FIG. 8). By being abrupt within the range, the calorific value decreases sharply, enabling self-temperature control within the temperature range.

[0013] ) Is within the permissible range shown in FIG. 9 (the range of the line indicating the upper limit value and the lower limit value), and the ratio of the volume resistivity at 25 ° C. and 70 ° C. (ρ 70 / ρ 25) 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 7 which satisfies the heat generation property in the low temperature range (70 ° C. or less, preferably 50 ° C. or less) and the self-temperature controllability. Heating element 7
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. 10 is a graph showing the relationship between the stable temperature of the heating element due to a change in room temperature. The amount of heat generated by the heating element per unit time and the amount of heat radiation (per unit time) match. Heating element 7 that is stable at temperature and is applicable to the present invention
Has less influence of the ambient temperature than the metal-based heating element system and shows stable thermal characteristics. Figure 11 shows the energization time and Series sintered body [15.0 mmφ x thickness 1 mm, 2.5 Ω (2
5 ° C) as a heating element, and a wiring (0.1 mm
(Formed on a polyester film) was used as a metal-based heating element in a comparative test, and each was fixed to a brass plate of 30 mm square × 0.3 mm thick, and was obtained by applying a voltage of about 1 V.

It is effective to provide an electrode on the heating element 7 in terms of energization assembling process. Specifically, the opposite surface of the heating element 7 itself is sprayed with aluminum or plated with nickel, tin or the like. Or provided on the heat-conductive member 6 arranged in contact with the current-carrying heating element 7.

The heat conductive member 6 is not limited to a metal material, but may be a thin heat conductive rubber, plastic, ceramic or the like.

The electrodes may be provided on the opposite surface of the electric heating element 7, one electrode may be provided on the back of the electric heating element 7, and the counter electrode may be provided on the front of the heat conductive member 6 (conductive member).
The electrode is set so as to be able to conduct electricity to the power supply 9 via a conductive member such as a lead wire.

As the power supply 9, various kinds of batteries and commercial power are adjusted to a predetermined voltage (0.8 to 40V) and applied. Power supply 9
For example, a dry battery or the like can be detachably housed in the main body and used as an energizing heater, but can be configured to be energized by a power supply outside the system. The heating element 7
In a system in which warm air is discharged from a discharge port at the front end of the casing via a blowing means disposed behind, a radiating fin can be connected to the current-carrying heating element 7 to effectively exhibit a radiating effect. Without the heat radiation fins, a large number of plate-shaped energizing heating elements 7 can be appropriately combined and arranged, and the honeycomb-shaped energizing heating element 7 can be arranged at a position capable of warming. it can.

The blower mechanism can be put to practical use by attaching a fan 5 to the drive shaft of a general-purpose small motor 4 conventionally. The logarithm of the semiconductor element is 1 to 511 pairs, more practically 4
A system of ~ 127 pairs, preferably 4-31 pairs, 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 power source 9 for applying the voltage includes a color changing device 11.
Can be integrally accommodated and arranged in the casing 8 of the first embodiment, but can be separately provided via a cord or the like. As a power source, various batteries such as dry batteries and AC / D
It is also possible to connect a C converter and convert AC to DC for application.

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. By changing the polarity, the heat absorption side A is changed to the heat generation side B.
The temperature of the heat generation side B is configured to be able to exhibit a temperature-raising characteristic of 3 ° C. to 60 ° C. (preferably 5 ° C. to 50 ° C.) when applied after conversion to the temperature range.

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, and examples thereof include writing instruments, handwriting erasing tools, stamps, toy elements (for example, combs for doll toys, other makeup tools, irons, etc.). ) And the like.

Next, a thermochromic material constituting the thermochromic layer 121 of the thermochromic element 12 applied in combination with the color changing device set 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. 14)

Further, Japanese Patent Application Laid-Open No.
The system described in Japanese Patent Publication No. 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. 15)

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. Then, the thermochromic layer 121 is formed on the surface of the support. Further, thermochromic elements 12 of various shapes obtained by kneading the above-mentioned microcapsule pigments in a thermoplastic and melt-molding them are effectively applied in combination with the color-changing tools 1 and 11 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, various display bodies, and other toy elements. The thermochromic layer 121 has a temperature of −10 ° C. to +
Those having a discoloration point in the range of 70 ° C. (preferably −5 ° C. to + 50 ° C.) are effective from a practical viewpoint.

[0039]

[Action] In the case of a current-carrying discoloration tool, by applying a voltage,
The current-carrying heating element 7 self-heats and rises in temperature, the resistance value rapidly increases, the temperature rise decreases, and the self-temperature control is stably performed at a temperature at which the amount of heat generation and the amount of heat radiation coincide. 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 rises slowly, the current-carrying heating element 7 of the present invention has a large current flow immediately after the current is applied, has a large temperature rise rate, and quickly rises to a predetermined temperature.

With respect to changes in room temperature, the current-carrying heating element 7 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 of a stable temperature of 39 ° C. and a difference of 7 ° C., the current-carrying heating element 7 applied to the present invention has
It shows a behavior in which the temperature change due to the ambient temperature is smaller than that of the metal heating element system.

The current-carrying heating element 7 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.

In the current-cooling and discoloring device 11, when a current is applied from the N-side terminal to the P-side terminal by applying a DC voltage (0.3 to 50 V), heat is absorbed on the upper surface and heat is generated on the lower surface by 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 (having a specific range of thermal resistance value), the temperature of the heat absorption side A is lowered and maintained in a desired range.

When the heating or cooling color changing device is applied to the thermochromic element 12 having the surface layer formed by the thermochromic layer 121, the color is changed in accordance with the color changing temperature.

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 FIG. 2) A heat-conductive member 6 having a pen tip protruding from an axis of a flat portion at a front end opening of a main body made of a plastic shaft cylinder 8.
And the back of the flat part with conductive adhesive Has a conductive plating layer formed thereon and has a resistance of 2Ω (2
5 ° C) Exothermic saturation temperature set at 45 ° C
And a 1.5V dry battery 2
The components were arranged in series, and were set so as to be able to conduct electricity through an electrode provided on the front surface of the flat part of the heat conductive member 6 and the conductive member, thereby forming the electrically conductive heating discoloration tool 1. The power switch unit is disposed at an appropriate position (not shown). The temperature of the pen tip of the energizing heating discoloring device 1 was raised to about 45 ° C. after 30 seconds at room temperature of 25 ° C. after energization.

[0047]

Embodiment 2 A heat transfer member [aluminum plate (60 mm × 30 mm ×
Thickness 1 mm)] and the back surface is appropriately spaced with a conductive adhesive. mφ × 1 mm thick, and a conductive heating layer with a conductive plating layer formed on both surfaces, and a resistance heating element having a resistance value of 2.5Ω (25 ° C.) and a heat generation saturation temperature of 45 ° C.]. A heating element (not shown) in which the electrode on the back of the heating element and the electrode on the surface of the heat transfer member are wired in parallel by a lead wire is set, and is set to be capable of conducting and generating heat by applying a voltage of 3 V. The heating discoloration tool 1 was configured.
In addition, on the bottom surface (the portion exposed on the surface) of the heat transfer member,
By applying a surface coating with a fluorine-based or silicon-based resin, lubricity during use can be imparted. Further, a reversible thermochromic display for confirming the heat generation temperature can be appropriately provided.

[0048]

Embodiment 3 A plastic body case 8 (outer diameter 3.5)
cmφ × 9.0cm in total length: split in the axial direction and configured to be assembled and assembled)
The heat generating mechanism section and the blower mechanism section are connected so as to be able to conduct electricity and are housed therein. At the center of the main body case 8, a grip section (with a built-in switch mechanism) is attached. Discharge member (diameter reduced toward the tip, 6mmφ
The other end is fitted with a member having an air suction hole at the other end to form the electrically heated and discolored tool 1 for toys.

The grip portion can have a built-in battery and can be connected to a power source outside the system via a cord.

[0050] (φ x thickness 1mm): Conductive plating layers are formed on both sides, and a resistance heating element with a resistance value of 2Ω (25 ° C) and a heating saturation temperature of 50 ° C) is electrically conductive to the upper and lower radiation fins. It was configured by attaching with an adhesive. The blower mechanism was configured such that a small motor 4 (output: 0.4 W, rotation speed: 4000 rpm) was built in a box, and a fan 5 was attached to an output shaft of the motor 4. The heat generating mechanism section and the blower mechanism section are wired in parallel, and are configured to be energized through a switch 10 and a power supply 9 of 4.5 V (three dry batteries of 1.5 V are arranged in series). The electric heating and heating discoloring device 1 was able to continuously discharge hot air of about 45 ° C. from the discharge port after 10 seconds of energization at room temperature of 25 ° C.

[0051]

Fourth Embodiment (See FIG. 6) A heat discoloring device 1 capable of forming a wide handwriting by attaching a heat conductive tip member 6 made of a metal material to the tip of the heating discoloring device of the first embodiment.

[0052]

Embodiment 5 A thermoelectric conversion element 2 (logarithm of semiconductor: 11) is provided in front of a casing 8 having a large number of heat radiating holes 83 on the side.
Pair) is attached, and a metallic heat transfer member having a writing tip shape is closely arranged on the insulating plate 24 on the heat absorbing side A, and the insulating plate 2 on the heat generating side B is disposed.
A radiator 3 (heat resistance value: 19 [° C./watt]) formed by winding an aluminum mesh sheet material around a radiating member made of an aluminum bar having a contact plane brings the contact plane into close contact. The thermoelectric conversion element 2 is connected to a DC power supply 9 (1.5 V dry battery) provided outside the system via a lead wire.

The cooling discoloring device 11 is used (at room temperature 18).
C) at a voltage of 1.0 V, a current of 0.7 A, a maximum temperature on the heat generation side of 32 ° C. (attainment time of about 3 minutes), and a minimum temperature of -3 on the heat absorption side.
° C (arrival time: about 3 minutes) and endothermic rising characteristics (11 ° C after 10 seconds). The color changing tool 11 can also function as a heating color changing tool by reversing the polarity of the applied current.

[0054]

Sixth Embodiment (See FIG. 3) The thermoelectric conversion element 2 (the number of pairs of semiconductors: 11 pairs) is attached to the front of a casing 8 having a large number of heat radiation holes 83 arranged on the side, and an insulating plate on the heat absorbing side A is mounted. 24, a metal heat transfer member 6 having a writing tip shape is closely arranged, and a heat radiator 3 having a large number of fins formed by die-casting of aluminum is continuously arranged on an insulating plate 24 on the heating side B. Inside
A 1.5 V dry battery is arranged, and is set so as to be able to conduct electricity through the thermoelectric conversion element 2 and a lead wire, and is turned on and off by a power switch 10 provided at a front portion of the casing.
The cooling discoloration tool 11 was configured. The DC power supply 9 is not limited to a system provided with a battery or the like, but may be a system connected to an AC / DC converter.

[0055]

Seventh Embodiment (Refer to FIGS. 4 and 5) A small DC motor 4 is mounted on an upper front surface inside a casing 8 having an appearance similar to that of an electric iron, with the output shaft side downward, and a fan directly connected to the output shaft. The radiator 3, which is configured to be able to supply air to the periphery by the rotation of the radiator 5 and has a large number of fins radially formed in the centripetal direction and erected on the periphery of the aluminum disc, places the fins around the fan 5. The thermoelectric conversion element 2 is mounted on the lower surface of the disk.
The heat-generating side B of the (semiconductor logarithm: 17 pairs) is closely attached to the heat-absorbing side A of the element 2, and a heat-conductive member 6 made of an aluminum circular thin plate (about 3 cm in diameter) is fixedly provided on the heat-absorbing side A. , And is exposed from the lower surface of the casing 8.

A plurality of intake holes 81 for the fan 5 are provided on the lower surface of the casing 8 at appropriate intervals, and an exhaust hole 82 is provided on a front side surface of the casing 8. . A handle is attached to the upper part of the casing 8, a switch 10 is provided, and the switch is connected to a power source 9 (two 1.5V batteries are arranged in parallel) provided at the rear of the casing 8, and the motor 4 and the thermoelectric conversion element are connected. 2 is operably connected to the power supply 9.

In operation (room temperature 23 ° C.), a voltage of 0.
8 V, current 1.3 A, maximum temperature on the heat-generating side 52 ° C. (arrival time about 2 minutes), minimum temperature on the heat-absorbing side 8 ° C. (arrival time about 3 minutes), thermal resistance of the radiator 3: 29.0 [° C./watt ], Heat-rise characteristics (32 ° C. after 10 seconds) and endothermic rise characteristics (13 ° C. after 30 seconds). The heat conductive member 6 includes:
A stamp can be constructed by detachably mounting a magnetized imprint plate provided with an appropriate imprint.

[0058]

[Embodiment 8] A power battery (1. 6) is placed on one side of a plastic casing 8 having a general outer shape of 6 cm in length, 5 cm in width and 2 cm in height.
5V dry battery) and accommodated on the other side to allow air to be supplied by rotation of a fan 5 directly connected to a small DC motor 4 fixedly disposed, and a radiator 3 (aluminum material) disposed on the side of the drive element ) Is air-cooled. A radiator plate is attached to a base end of the radiator 3, and the radiator plate is a thermoelectric conversion element 2.
(The logarithm of the semiconductor: 17) is closely and fixed to the heat generation side B, and the heat transfer side 6 of the element 2 is closely and fixed to the heat absorption side A made of an aluminum plate to expose the surface.

An exhaust hole 82 is provided on the side of the casing 8.
The casing 8 on the side where the heat conductive member 6 is provided is provided with an intake hole 81. The color changing tool 11 has the following characteristics. At the time of use (room temperature 23 ° C.), the voltage is 0.8 V, the current is 1.3 A, and the maximum temperature on the heat generation side is 29.
° C (attainment time about 2 minutes), heat-absorbing side minimum temperature 4 ° C (attainment time 3 seconds), thermal resistance value of radiator 3: 10.0 [° C / watt], heat-absorption rising characteristic (13 ° C after 20 seconds) Indicated.

Application Example 1 (See FIGS. 1 and 7) Using the cooling discoloring device 11 of the sixth embodiment, a color-memorizing thermochromic dye [black →→ colorless, low-temperature discoloration point (t1)] is applied to a white sheet material. When the thermochromic element 12 (having a white color at room temperature) having a thermochromic layer 121 formed on the entire surface with a coloring material containing a color change point (15 ° C., high-temperature side color change point (t4) 35 ° C.) is written, The white color of the portion changed color, and a black handwriting (thermochromic image 122) appeared. The handwriting was stored at room temperature of 17 ° C to 30 ° C. When the black handwriting portion was written using the heating discoloring device 1 of Example 4 (the writing tip was heated to about 40 ° C.), the black handwriting could be erased. (See Fig. 7)

Application Example 2 The thermochromic element 12 (approximately 40) of Example 1 is applied to the thermochromic element 12 of Application Example 1 (however, the entire surface is kept black at room temperature).
When the writing tip was heated to (° C.), a white handwriting appeared. The handwriting is 17 ° C ~
The data was stored at room temperature of 30 ° C. When the white handwriting was written using the cooling discoloration tool 11 of Example 7 (the front end surface of the heat conductive member 6 was cooled to about 6 ° C.), the white handwriting could be erased and the entire surface was black. I was able to restore the 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 a yellow non-color-changing ink, and the non-color-changing layer is covered and heated to 40 ° C. The reversible thermochromic layer, which has a discoloration point, exhibits a green color at less than 40 ° C., and loses color at 40 ° C. or more, is overprinted.) When writing on the thermochromic layer, the layer was decolorized and a non-discolorable layer appeared,
The answer was determined. After a while, the non-discoloring layer becomes
The opaque state was restored by the thermochromic layer colored green.

Application Example 4 Clothes for a doll having a thermochromic layer 121 colored with a color material containing a color-memorizing thermochromic pigment (a light blue solid fabric with a yellow, pale green floral pattern (non-color-changing layer)) Is formed, and the entire surface including the non-discoloring layer is red-> colorless (t1:
(15 ° C., t 4: 32 ° C.), and the thermochromic layer 121 is changed so that the red clothes can be seen in the normal temperature range.
After applying the (heating condition) and ironing, the contact area was immediately erased in color, and a floral pattern was revealed on a light blue ground by applying an anron on the entire surface, and the above aspect was stored in a normal temperature range. Retained and visualized. The exposed floral pattern could be erased using the cooling discoloring tool 11 of Example 7 (the front end face of the heat conductive member 6 was cooled to about 6 ° C.).

Application Example 5 A discoloration point at 35 ° C., a black color at less than 35 ° C.,
Above ° C, warm air is blown onto the stuffed bear, which is formed with a flocked fabric colored with a thermochromic material that changes reversibly to white, using the energizing heating discoloring tool 1 of Example 3 above. As a result, the sprayed portion turned white, and the entire surface could be changed to a white bear having a white appearance. The white bear returned to the state of a black bear in a normal temperature range, and was transformed into a white bear by blowing hot air again, and could be enjoyed repeatedly.

[0065]

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

In the heating discoloring device, the energized heating element is quickly heated by applying a low voltage, and the temperature is raised to a predetermined temperature, so that the thermochromic layer can be discolored. 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. In addition, various commercially available batteries can be used as a power source, and the battery pack satisfies the practicality as a portable and portable energizing and heating discoloring tool in which a dry battery or the like is detachably mounted.

Among the above-mentioned heating discoloring devices, those in which warm air is discharged from the discharge port can discolor the desired portion of the target thermochromic element in a non-contact state. With the heating tool of the above, it is possible to effectively change the color of thermochromic elements that do not satisfy the convenience of use, such as doll's hair, clothes, uneven materials, and objects that are easily deformed by writing pressure.

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

Moreover, the applied voltage is low (less than 50 V).
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.

[0071]

[Brief description of the drawings]

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

FIG. 2 is a longitudinal sectional view of one embodiment of a heat discoloration device.

FIG. 3 is an explanatory longitudinal sectional view of one embodiment of the cooling discoloration tool.

FIG. 4 is a longitudinal sectional view of another embodiment of the cooling discoloration tool.

FIG. 5 is an explanatory cross-sectional view of the cooling discoloration tool of FIG. 4 taken along line AA.

FIG. 6 is a partially longitudinal explanatory view of another embodiment of the heating discoloring device.

FIG. 7 is an explanatory diagram of a state in which handwriting formed by a cooling discoloring tool is erased using the heating discoloring tool of FIG. 6;

FIG. 8 is a graph showing characteristics of temperature and resistance of a heating element applied to the present invention.

FIG. 9 is a graph showing an allowable range of volume resistivity at each temperature of a heating element applied to the present invention.

FIG. 10 is a graph showing a stable temperature of a heating element according to a change in room temperature.

FIG. 11 is a graph showing a relationship between an energizing time and a heating temperature of a heating element.

FIG. 12 is a perspective view of a thermoelectric conversion element applied to the cooling discoloration device of the present invention.

FIG. 13 is an explanatory diagram of the structure and operation of a thermoelectric conversion element applied to the cooling discoloration device of the present invention.

FIG. 14 is an explanatory graph of a color change characteristic of a thermochromic dye due to a temperature change.

FIG. 15 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 Heat discoloration tool 11 Cool discoloration tool 2 Thermoelectric conversion element 21 P-type semiconductor element 22 N-type semiconductor element 23 Metal piece 24 Insulating plate A Heat absorption side B Heat generation side 3 Heatsink 4 Motor 5 Fan 6 Heat conductive member 7 Electric heating element 8 Casing 81 Intake hole 82 Exhaust hole 83 Heat release hole 9 Power supply 10 Switch 12 Thermochromic element 121 Thermochromic layer 122 Thermochromic image

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-109986 (JP, A) JP-A-6-7549 (JP, A) JP-A-5-318914 (JP, A) 50100 (JP, U) (58) Fields investigated (Int. Cl. ⁶ , DB name) A63H 33/22 A63H 3/52 A63H 9/00 A63H 30/02 B43K 8/00

Claims (2)

(57) [Reference number] P910430-1 [Claims] 1. A heating and cooling discoloring device set for discoloring the thermochromic layer, wherein the thermochromic element is provided with a thermochromic element discolored by a temperature change, wherein the heating discoloring device is housed in a casing. The held energizing heating element is caused to generate heat, and a heat conductive member disposed in contact with the heating element is heated to function, or hot air is discharged from a discharge port at a tip end of the casing via a blowing means arranged behind the energizing heating element. Wherein the current-carrying heating element is a resistance heating element having a positive temperature coefficient of electrical resistance at least in a temperature range of 25 ° C. to 70 ° C .; Volume resistivity (ρ
twenty five) Is the ratio of volume resistivity (ρ70 / ρ25) at
Satisfies each requirement of being within the range of 5 ≦ (ρ70 / ρ25) ≦ 400, generates heat by applying a voltage of 0.8V to 40V, and has an exothermic saturation temperature of any temperature within a temperature range of 25 ° C to 70 ° C. The cooling discoloration device is a unit in which a P-type semiconductor element and an N-type semiconductor element are alternately joined by metal pieces, and both upper and lower surfaces are sandwiched by a thermally conductive insulating plate. A casing for accommodating and holding a thermoelectric conversion element having a Peltier effect having a simplified configuration, a radiator connected to a heat generation side of the thermoelectric conversion element, and a heat conductive member connected to a heat absorption side of the thermoelectric conversion element At least, the heat conductive member may function as a cold end, or a configuration in which cool air is discharged from a discharge port at a front end of the casing via a blowing unit positioned behind the thermoelectric conversion element, Serial radiator, heat resistance 0.1
It has a heat radiation function of up to 150 [° C / watt] and 10 ° C to 3
A heating / cooling discoloration tool set, wherein the heat-absorbing side is configured to exhibit a temperature drop function of at least 3 ° C. or more with respect to each environmental temperature within the above-mentioned range at an environmental temperature of 5 ° C. 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 set.