JPH0639151A - Discoloration tool - Google Patents

Abstract

(57) [Abstract] [Purpose] A light-weight facility for changing the contact part to cold and heat by contacting a tip member with the thermochromic layer such as toys, learning materials, and writing boards having a thermochromic layer formed on the surface. Provide a color changing tool. A thermoelectric conversion element 2 having a Peltier effect is used as a cold heat source, and a heat transfer member 4 is provided on the heat absorption side of the thermoelectric conversion element 2.
The radiators 3 are closely arranged on the heat generation side, and are connected in series between the power supply battery 7 and the thermoelectric conversion element 2 via the resistor 6 so that they can be energized and operated. [Effect] It is possible to easily and easily discolor the thermochromic layer of the object immediately and at any time and in any place with respect to the cooling means using the conventional cold water or ice pieces as the cooling medium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color changing tool. More specifically, the present invention relates to a color-changing tool that causes the contact point to undergo cold-thermochromic change by bringing it into contact with the thermochromic layer of various thermochromic objects.

[0002]

2. Description of the Related Art Conventionally, as a means for discoloring a thermochromic layer of a thermochromic object, an electric heating tool equipped with a resistive heating element such as tungsten or nickel has been disclosed. An attempt to bring a color-changing material into contact and change the color of the contact portion is disclosed in Japanese Utility Model Application Laid-Open No. 62-139573. As described above, attempts for heating means for discoloring the thermochromic layer have been disclosed, but effective cooling means for discoloring the thermochromic layer with cold color have not yet been disclosed, and cold water, ice chips, etc. The application of the cold heat medium and the target thermochromic element were put in the refrigerator, and the color change operation by the cold air in the refrigerator was forced.

[0003]

Even if the cooling / heating means has applicability in a specific place such as a home, when necessary,
The thermochromic layer of the object could not be instantly discolored from any place, and the function of the thermochromic element having a discoloration point in the low temperature region could not be effectively exhibited. Further, the application of the cold heat medium has a limit in the cold heat duration, and it has been troublesome to prepare these media each time.
Further, in the case of a non-water resistant thermochromic element, not only the direct contact with the cooling / heating medium but also the indirect contacting operation in which the cooling / heating medium is accommodated in the container and applied to the container surface is generated. The thermochromic element tends to be deteriorated due to the dew condensation layer, water droplets, water leakage or the like.

The present invention solves the above-mentioned problems due to the application of the conventional cooling and heating means all at once, and satisfies the portability, immediate effect, cooling heat sustainability, convenience, etc., and easily at any time, in any place. An object of the present invention is to provide a discoloring tool that discolors a thermochromic layer with cold heat.

In particular, the thermochromic element of interest has a color-memory sensitizing thermochromic dye (which exhibits a large hysteresis characteristic due to temperature change and discolors, and has two color changing points, a low temperature side changing point and a high temperature side changing point. , A colored state and a colorless state, or a tautomerism between colored [1] and colored [2] is exhibited, and by applying cold heat below the low temperature side discoloration point or heat above the high temperature side discoloration point, a state different from the normal state appears. By applying in combination with a system provided with a thermochromic layer colored with a coloring material containing a coloring material containing a dye which has a function of being able to change and store the characteristics in an alternating manner at room temperature. The present invention intends to provide a color-changing tool that effectively develops the function of a color-memory thermosensitive dye to enable diversification of products and application and development in various fields.

[0006]

The color changing tool 1 of the present invention will be described with reference to the drawings. The present invention relates to a color-changing tool that causes a contact portion to undergo a thermochromic change by bringing it into contact with a thermochromic element on which a thermochromic layer is formed, in which a P-type semiconductor element 21 and an N-type semiconductor element 22 are alternately metal pieces 23. A thermochromic conversion element 2 having a Peltier effect having a structure in which the upper and lower surfaces are sandwiched by heat conductive insulating plates 24 and united with each other as a heat source. The heat transfer member 4 is closely attached, and the radiator 3 is closely attached to the heat generation side, and the color change tool 1 in which a power battery is connected in series to the thermoelectric conversion element 2 via a resistor is required. To do.
Furthermore, the thermochromic layer of the thermochromic element exhibits a large hysteresis characteristic due to a temperature change, and exhibits a mutual change between a colored state and a colorless state or a colored [1] and a colored [2] state. The color changing tool 1 that is applied in combination with a system that is colored with a color material containing a color-memory thermochromic dye capable of selectively storing and holding any of the states is required.

In the above, as the thermoelectric conversion element 2 having the Peltier effect, the one generally used conventionally is effective. The thermoelectric conversion element 2 includes a metal piece 23 (electrode) formed by a couple of P-type deficient electron and N-type excess electron semiconductor elements.
Are alternately joined, and the upper and lower surfaces are sandwiched by a heat conductive insulating plate 24 such as alumina or ceramic to form a unit. When an electric current is passed from the N side terminal to the P side terminal, the Peltier effect is applied to the upper surface. Heat is absorbed and heat is generated on the lower surface (see FIGS. 4 and 5).

The P-type or N-type semiconductor element 2 described above
1, 22 are Bi ₂ Te ₃ , Bi ₂ Se ₃ , and Sb ₂ Te.
₃ etc. can be illustrated. The semiconductor device has a logarithm of 1 to 511
Pairs, more practically 4-127 pairs, preferably 4-31
Paired systems are effective.

The radiator 3 according to the present invention has a radiator fin made of a metal material, a mesh-shaped sheet material made of a metal material, a processed metal plate piece, and a heat-dissipating metal container. A radiator that is filled with a medium (containing an appropriate amount of polyhydric alcohols for imparting antifreeze and an appropriate amount of a rust inhibitor, etc.), glycerin, ethyl alcohol, ammonia water, etc. Etc. can be illustrated.

The voltage applied by the DC power supply for energizing the thermoelectric conversion element 2 is 0.1 to 50 V, and it is difficult to operate by the battery in a system of 0.1 V or less, and it is appropriate in a system of 50 V or more. It is necessary to increase the number of couples, and it is not suitable for general products such as fields such as toys, learning, writing materials, etc., and is unsuitable, and restricted to special applications. Usually, a combination with the thermoelectric conversion element 2 that functions by an applied voltage of 0.2 to 20 V is preferable.

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

The heat transfer member 4, which is brought into close contact with the insulating plate 24 (heat absorption side) of the thermoelectric conversion element 2, is not limited to a metal material, and is made of thin heat conductive rubber, plastic, ceramic material, or the like. It may be the body. Further, in the system in which the heat transfer member 4 is made of a metal material, the portion which becomes the contact tip to the thermochromic layer can be subjected to silicone resin processing or fluorine resin processing to impart lubricity.

Further, a porous body having continuous pores can be attached to the front end of the heat transfer member 4 made of a metal material, and the porous body can be impregnated with water or the like to impart a soft touch and a smooth coating property.

The temperature lowering function on the heat absorption side A in the above system has a lowering temperature 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. A falling temperature (preferably 10 to 25 ° C.) is developed. If the temperature falls below 3 ° C., the discoloring function cannot be sufficiently exerted even when the room temperature changes. on the other hand,
When the temperature falls below 40 ° C, water vapor freezes, which is not practical. In the discoloration tool of the present invention, the heat absorption side A can be converted to the heat generation side by switching the polarities to function as a heat discoloration tool.

Various forms of the discoloring tool 1 are effective, and examples thereof include a writing tool, a stamp, a toy element (for example, a doll toy comb, other makeup tools, etc.). Next, the thermosensitive color-changing material constituting the thermochromic layer of the thermochromic element applied in combination with the color-changing tool 1 of the present invention will be described.

A thermochromic material containing a conventionally known thermochromic dye, for example, liquid crystal, an electron-donating color-developing organic compound, a color developer of the compound and a medium for causing a color reaction between the both. Thermochromic material containing three components of a compound or a thermochromic material exhibiting a color-changing property in the form of fine particles of a resin solid solution of the components (for example, JP-B-51-35414, JP-B-51-44706, Japanese Patent Publication 52-77
No. 64, Japanese Patent Publication No. 1-29398, etc.). In the above, the color changes before and after a predetermined temperature (color change point) as a boundary, and only one specific state can exist in the normal temperature region of both states before and after the change. That is, the other state is maintained while the heat or cold required to develop that state is applied, but returns to the state exhibited in the normal temperature range when the application of the heat or cold is lost, so-called, It is a type that changes color by showing a small hysteresis width (ΔH) with respect to temperature-color density due to temperature change.

Further, Japanese Patent Laid-Open No. 60-
A system described in Japanese Patent No. 264285, which is colored with a thermochromic material containing a color-memory thermochromic dye that exhibits large hysteresis characteristics and is discolored, is effective. The dye exhibits a large hysteresis width (ΔH) and changes color. That is, the shape of the curve plotting the change of the coloring density due to the temperature change is the case where the temperature is increased from the lower temperature side than the color change temperature range and the other is the temperature is decreased from the higher temperature side than the color change temperature range. It is a type that changes color by following a significantly different route.

The above-mentioned thermochromic dye and color-memory thermochromic dye are usually encapsulated in microcapsules and dispersed in a medium containing a binder to obtain a color material in the form of ink, paint or paint. Applied to form a thermochromic layer on the surface of the support. Further, thermochromic elements of various shapes obtained by kneading the above-mentioned microcapsule pigment in thermoplastics and melt-molding are effectively applied in combination with the color changing tool 1 of the present invention. The thermochromic element is a thermochromic sheet, a thermochromic linear body, a thermochromic molded product having an uneven surface, or a thermochromic layer formed of the thermochromic material described above on the surface layer. Including all. Examples include writing boards, teaching materials, learning materials, picture books, and other toy elements.

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

[0020]

Operation: By applying a DC voltage (0.1 to 50 V), N
When a current is passed from the side terminal to the P side terminal, heat is absorbed on the upper surface and heat is generated on the lower surface due to the Peltier effect, and the heat is transferred to the heat conductive insulating plates 24 on both upper and lower surfaces to form a heat absorbing side A and a heat generating side B (FIG.
(See FIG. 5).

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

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

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

In the application of the color-changing tool 1 of the present invention, in the system in which the thermo-color-changing layer is formed of a color material containing a thermosensitive dye exhibiting a thermo-color-changing characteristic having a small hysteresis width (ΔH), the color-changing point is used as a boundary before and after the color-changing point. Discoloration occurs, and of both states before and after the change, one specific state exists in the normal temperature range, and the other state is the normal temperature range when the heat or cold heat required to develop that state is eliminated. Return to.

On the other hand, the thermochromic layer formed of a color material containing a color-memory thermochromic dye has a cold temperature lower than the low temperature side color changing point,
Alternatively, by applying heat above the high-temperature side discoloration point, the colors change each other in an aspect different from the normal state, and even if the application of cold heat or heat required to develop that state is eliminated, that state is stored and retained at room temperature. Then, the memory-retained aspect changes its color to the original state by the thermal means opposite to that required for the development of the state, and retains it in the normal temperature range.

[0026]

EXAMPLE A first example will be described (see FIGS. 1 and 2).
The thermoelectric conversion element 2 (the number of pairs of semiconductors: 11 pairs) is attached to the front portion of the shaft body 5 having a large number of heat dissipation holes 51 on its side portion, and the metal plate of the writing tip shape is attached to the insulating plate 24 on the heat absorption side A. The heat member 4 is closely arranged, and the insulating plate 24 on the heat generating side B has a thickness of 1 mm × 8.
Center part 1 of aluminum plate piece with a width of 170 mm and a length of 170 mm
The radiator 3 is bent in a "U" shape with a width of 0 mm as a base surface, and the base surface is closely arranged (heat conductive grease is applied to maintain the closeness). The thermoelectric conversion element 2 is connected to a dry battery 7 (1.5 V) via a lead wire 8, and its circuit is configured to be energized and operable via a resistor 6 (about 0.3 Ω).

The second embodiment is shown in FIG. The color changing tool 1 is configured with the power source housing 9 as a separate body, and other configurations are the same as in the first embodiment.

At the room temperature of 25 ° C., the temperature of the writing tip of the color-changing tool 1 was about 0 ° C. 20 seconds after the start of energization and −7 ° C. after 60 seconds.

Using the above-mentioned color changing tool 1 (for cold heat), a white sheet material is heated by a color material containing a color-memory thermosensitive dye [black ← → colorless (low temperature side color changing point 15 ° C., high temperature side color changing point 35 ° C.) When writing was made on a thermochromic element having a color-changing layer formed on the entire surface (which exhibits white at room temperature), the white color of the written portion was discolored, and black handwriting was revealed. The handwriting is 17 ℃
It was kept in memory at room temperature of -30 ° C. 3 sheets of the above
When heated to 5 ° C or higher, the black handwriting disappears, and the entire surface is repeatedly used as a white writing surface for practical use.

In the discoloring tool 1, in the system to which the resistor 6 is not applied, the time in which the writing tip is kept at a temperature of 8 ° C. or less is 105 minutes, but in the system to which the resistor 6 is applied. In particular, a temperature of 8 ° C. or lower could be maintained for about 180 minutes. Further, when the resistor 6 having a resistance value of about 1Ω was applied, the temperature at the tip of the writing could not be effectively lowered.

[0031]

INDUSTRIAL APPLICABILITY The color-changing tool of the present invention is applied in combination with a thermochromic element provided with a thermochromic layer, and in particular, effectively exhibits the color-changing function of a thermochromic element having a color-changing point in a low temperature range. It is a cold heat discoloration tool that can be used to quickly and easily discolor the heat discoloration layer of an object at any time, in any place, as compared with conventional cold heat means using cold water, ice chips, etc. Satisfies convenience, applicability to non-water resistant objects, portability, etc. Moreover, the applied voltage can be effectively operated at a low voltage, and there is no danger of leakage. Functions can be made permanent by replacing batteries such as dry cells. Furthermore, the interposition of the resistor allows the output current of the power supply battery to be appropriately reduced to effectively function, and the battery life can be extended. Furthermore, since the amount of heat generated by the thermoelectric conversion element is small, even if the heat dissipation capacity of the radiator is small, it can function effectively, a radiator with a small capacity can be applied, and a compact and easy-to-use color changing tool is constructed. can do. As described above, the color changing tool of the present invention can be easily applied with cold heat, and can be combined with various thermochromic elements having a structure in which a thermochromic layer having a color changing point in a low temperature region is provided. In particular, the target thermochromic element is a color memory memorizing thermochromic dye (which exhibits large hysteresis characteristics due to temperature changes and changes color, has two color changing points, a low temperature side changing point and a high temperature side changing point, and is in a colored state. And a colorless state or a tautomerism between colored [1] and colored [2], and by applying cold heat below the low-temperature side discoloration point or heat above the high-temperature side discoloration point, a state different from the normal state can be obtained. , The function of the color-memory thermosensitive color-changing dye by applying in combination with a system provided with a thermochromic layer colored with a coloring material containing a colorant containing a function capable of retaining and storing such an aspect at room temperature. Can be effectively expressed to enable diversification of products and application and development in various fields.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view of an embodiment of a color changing tool of the present invention.

FIG. 2 is a circuit diagram of the color changing tool of FIG.

FIG. 3 is a vertical cross-sectional view of another embodiment of the color changing tool of the present invention.

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

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

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Color change tool 2 Thermoelectric conversion element 21 P-type semiconductor element 22 N-type semiconductor element 23 Metal piece 24 Insulation plate A Heat absorption side B Heat generation side 3 Radiator 4 Heat transfer member 5 Shaft barrel 6 Resistor 7 Power supply battery 8 Lead wire 9 Power supply Housing 10 switches

Claims (2)

[Claims] 1. In a color-changing tool which causes a contact portion to be thermochromic by contacting it with a thermochromic element on which a thermochromic layer is formed, P-type semiconductor elements and N-type semiconductor elements are alternately joined by metal pieces. A thermochromic conversion element having a Peltier effect having a structure in which both upper and lower surfaces are sandwiched by heat conductive insulating plates is used as a heat source, and a heat transfer member is closely attached to the heat absorption side of the thermoelectric conversion element. A heat dissipator is closely assembled to the heat generating side, and a power supply battery is connected in series to the thermoelectric conversion element via a resistor. 2. The thermochromic layer of the thermochromic element exhibits a large hysteresis characteristic due to a temperature change, and exhibits a metamorphosis between a colored state and a colorless state or a colored [1] and a colored [2] state, and a room temperature range. 2. The discoloration according to claim 1, wherein the discoloration is applied with a color material containing a color-memory thermochromic dye capable of selectively storing and holding one of the two states, and is applied in combination with the thermochromic element. Ingredient