JPS6331790A - Display material for thermal recording - Google Patents

Abstract

PURPOSE:To ensure that when the title material is used as a display sheet of an electronic blackboard, images written on the sheet can be recorded and images written on an ordinary paper can be recorded or displayed on the display sheet, by providing a colored member on one side of a laminar heat-sensitive member comprising a heat-sensitive material the transparency of which is reversible changed depending on temperature, and providing a laminar member of a fluoro resin on the other side. CONSTITUTION:The entire body of a laminar heat-sensitive member 2 having a heat-sensitive material the transparency of which is reversibly changed depending on temperature is once made transparent, and the member 2 is then partly opacified by a thermal head 4, whereby a white image is formed. when a colored member is disposed on the back side of the laminar heat-sensitive member provided with the white image, the image can be recognized as a white image, with the color of the colored member as a background. Alternatively, the entire body of the heat-sensitive member 2 is opacified, and then the member 2 is partly made transparent, whereby a transparent image is formed in a white surface. When the colored member 1 is disposed on the back side of the heat-sensitive member provided with the transparent image, the image can be recognized as an image of the color of the colored member, with the white ground as a background. In addition, characters or the like in each color can be and-written on a laminar member 3 of a fluoro resin provided on one side of the laminar heat-sensitive member 3, and the characters or the like can be erased by a cloth or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a heat-sensitive recording display member that performs recording and erasing by utilizing the reversible change in transparency of the heat-sensitive member due to temperature, and is particularly useful as a display sheet for an electronic blackboard.

Prior Art In a conventional electronic blackboard, an image written by hand on a display sheet (called a whiteboard sheet) is optically read by a photoelectric conversion means), and this read optical signal is converted into an electrical signal. The output is output from the printer attached to the electronic blackboard, and a printout is obtained. However, on the contrary, an electronic blackboard that has the function of displaying an image written on a normal sheet of paper on a display sheet, for example, has not yet been developed. There is a small idea of an electronic blackboard equipped with an inkjet device (Japanese Patent Application Laid-Open No. 61-47300), but it is not yet practical.

Purpose The purpose of the present invention is to write an image by hand on the surface of a display sheet, take out and record the image as a printer output, and in addition to the function of a conventional electronic blackboard, for example, an image recorded on a manuscript or a magnetic recording medium. Images etc. recorded in '
It is an object of the present invention to provide a heat-sensitive recording display body suitable for adding a function of displaying on a display sheet surface using a thermal signal.

Structure The heat-sensitive recording display of the present invention is mainly composed of a resin base material and an organic low-molecular substance dispersed in the resin base material, and has a heat-sensitive body whose transparency changes reversibly depending on the temperature. It is characterized by comprising a layered heat-sensitive member, a colored member provided on one surface of the layered heat-sensitive member, and a fluororesin layered member provided on the other surface of the layered heat-sensitive member.

The recording principle of the display body of the present invention utilizes the change in transparency of the heat sensitive body depending on the temperature, and this will be explained with reference to the drawings. In FIG. 1, the heat sensitive body is in a cloudy, opaque state at room temperature below To, for example. When this is heated to a temperature between Tl and T1, it becomes transparent, and even if it is returned to room temperature below T in this state, it remains transparent. Further heating to a temperature of 13 or higher results in a translucent state intermediate between maximum transparency and maximum opacity. Next, when this temperature is lowered, the liquid returns to its initial cloudy and opaque state without becoming transparent again. Furthermore, after heating this opaque state to a temperature between 'rox'ri,
When cooled to room temperature, ie, below 'reTo, the state can be between transparent and opaque. In addition, the above-mentioned material that became transparent at room temperature is heated again to a temperature of T or higher,
When returned to room temperature, it returns to its cloudy, opaque state. That is, it can take both opaque and transparent forms, as well as intermediate states, at room temperature.

Therefore, for example, after heating the entire layered heat-sensitive member having such a heat-sensitive body to a temperature between T1 and T, it is cooled to room temperature below To to make it transparent, and then it is partially heated to a temperature of 13 or higher using a thermal head or the like. By heating the area to make it opaque, a white image is formed and can be recognized.

On the other hand, after heating the entire layered heat-sensitive member to a temperature of 13 or more, returning it to room temperature below T0 and making it cloudy and opaque, heat the part with a thermal head etc. to a temperature between TI#T and remove the part. Transparent processing allows a transparent image to be formed on a white surface.

If a colored member is placed on the back side of a layered heat-sensitive member having such a transparent image, this image can be recognized as an image of the color of the colored member against a white background.

Recording and erasing on the layered heat-sensitive member as described above can be repeated at least about 10 times.

Furthermore, by providing a layered member of fluororesin on one side of this layered heat-sensitive member, it is possible to hand-write letters, images, etc. in various colors on this member using an oil-based pen, etc. You can delete it with etc.

As described above, the heat-sensitive recording display of the present invention comprises a layered heat-sensitive member provided with a colored member on one side and a layered member of fluorine-based resin on the other side.

Here, the layered heat-sensitive member may be formed by forming the heat-sensitive member as a film on the support member, or may be formed in the form of a sheet without using the support member, and the layered member made of fluororesin may be formed by forming the heat-sensitive member as a film on the support member. It may be formed as a film on top, or it may be formed into a sheet without using a support member. Note that it is preferable that the layered member made of fluorine resin is transparent or semitransparent.

Further, the colored member may be one in which a colored layer is formed on the support member, or the support member itself may be colored, and may be in the form of a film, sheet, or board.

Therefore, the heat-sensitive recording display of the present invention can have the following configuration, but is not limited thereto.

1) A sheet-like or board-like colored member is applied to one side of a layered heat-sensitive member formed by forming a heat-sensitive member in a sheet-like form, and a sheet-like member made of a fluorine-based resin is applied to the other side, or a fluorine-based member is applied to the sheet-like support member. A structure in which sheet-like members each formed with a resin film are arranged separately.

2) In 1) above, a sheet-like colored member is used as the colored member, and each member is bonded with an adhesive or the like to be integrated.

3) A structure in which a fluorine-based resin film is formed on one surface of a layered heat-sensitive member formed by forming a heat-sensitive member in the form of a sheet, and a colored member is separately disposed on the other surface of the heat-sensitive member.

4) A structure in which a colored layer is formed on one surface of a layered heat-sensitive member formed by forming a heat-sensitive member in the form of a sheet, and a sheet-like member of fluorine-based resin is separately arranged on the other surface of the heat-sensitive member. .

5) A structure in which a colored layer film is formed on one surface of a layered heat-sensitive member formed by forming a heat-sensitive member in a sheet shape, and a fluorine-based resin film is formed on the other surface.

6) In 1) to 5) above, instead of the layered heat-sensitive member formed by forming the heat-sensitive member in the form of a sheet, a layered heat-sensitive recording member formed by forming a film of the heat-sensitive member on a sheet-like transparent support is used. composition.

7) A layered heat-sensitive member formed by forming a heat-sensitive body into a sheet, with a sheet-like member of fluorine-based resin integrated with adhesive or the like on one side, and a colored member arranged separately on the other side. composition.

8) A sheet-like colored member is integrated with an adhesive or the like on one side of a layered heat-sensitive member formed by forming a heat-sensitive member in a sheet-like form, and a sheet-like member of fluorine emulsion resin is placed separately on the other side. composition.

9) In 7) and 8) above, instead of the layered heat-sensitive member formed by forming the heat-sensitive member in the form of a sheet, a layered heat-sensitive member formed by forming a film of the heat-sensitive member on a sheet-like transparent support is used. composition.

10) A structure in which a heat-sensitive body film is formed on a sheet-like member of fluorine-based resin, and a colored member is separately arranged on the film surface side.

11) A structure in which a heat sensitive film is formed on a sheet-shaped colored member, and a fluorine-based resin sheet-shaped member is separately arranged on the film surface side.

12) A structure in which a heat sensitive film is formed on a sheet-like colored member, and a fluorine-based resin film is formed on the film.

13) Structure G in which a heat-sensitive film is formed on a sheet-like member of fluorine-based resin, and a colored layer is formed on the film As described above, the heat-sensitive recording display of the present invention includes a layered heat-sensitive member,
The colored member and the fluororesin layered member may be configured separately or integrally.

Next, an example of the heat-sensitive recording display body of the present invention will be explained with reference to the drawings.

2, 3, 4, and 5 are diagrams showing examples of different embodiments of the heat-sensitive recording display body of the present invention, respectively. In each figure, 1 is a colored member, and 2 is a layered heat-sensitive member. , 31d: a layered member made of fluororesin, and 4 indicates a thermal head.

FIG. 2 shows a heat-sensitive recording and display body of the present invention in which a colored member 11, a layered heat-sensitive member 2, and a fluorine-based resin layered member 3 are arranged separately, and FIG. This figure shows a heat-sensitive recording display body of the present invention in which a layered member 3 of resin is integrated by adhesion or film formation by coating. In addition, FIG. 4 shows the layered heat-sensitive member 2.
A heat-sensitive recording and display body of the present invention is shown in which a layered member 1 of a fluorine-based resin and a fluorine-based resin are integrated by adhesion or film formation by coating, and a colored member 3 is arranged separately. This figure shows a heat-sensitive recording display of the present invention in which the member 2 is integrated by adhesion or film formation by coating, and the fluororesin layered member 1 is arranged separately.

In order to improve adhesion and facilitate handling, various films, sheets, glass plates, etc. may be inserted between each member, or each member may be laminated thereon.

An image is recorded on the layered heat-sensitive member by the thermal head 4,
When displaying it, the thermal head 4 is placed on the layered heat-sensitive material.
However, in cases where direct contact between the thermal head 4 and the layered heat-sensitive member 2 is not possible, as in the case of the heat-sensitive recording display shown in FIG. It is desirable to make contact with the surface or the surface with better thermal conductivity. Therefore, for example, if the thickness of the fluorine-based resin layered member 3 is smaller than the thickness of the colored member, recording is performed by bringing the thermal head 4 into contact with the surface of the fluorine-based resin layered member as shown in FIG. This is desirable.

Next, methods and materials used for forming the layered heat-sensitive member, the colored member, and the fluororesin layered member will be described.

The layered heat-sensitive member can be formed as a film on a support member or formed into a sheet shape, for example, by the method described below.

1) A method in which a resin base material and an organic low-molecular substance are dissolved in a solvent, the solution is applied onto a support member, and the solvent is evaporated to form a film or a 7-plate shape.

2) Dissolve the resin base material in a solvent that dissolves only the resin base material, crush or disperse organic low-molecular substances therein using various methods, apply this onto a support member, and evaporate the solvent to form a film. Or make it into a sheet.

3) A method of heat-melting and mixing a resin base material and an organic low-molecular substance without using a solvent, forming the mixture into a film or sheet, and cooling it.

In this case, various solvents can be used depending on the type of organic low molecular substance and resin base material. Examples include organic solvents such as dihydrofuran, methyl ethyl ketone, methyl isobutyl ketone, chloroform, carbon tetrachloride, ethanol, toluene, and benzene.

In addition, in the layered heat-sensitive member formed in this way, the organic low-molecular substance exists in a dispersed state as fine particles in the resin base material. The resin base material used for the layered heat-sensitive member holds the organic low-molecular substance uniformly dispersed. In addition to forming a film or sheet,
This is a material that affects transparency at maximum transparency. Therefore, the resin base material is preferably a resin that has good transparency, is mechanically stable, and has good film-forming properties. Such resins include polyvinyl chloride; vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, and vinyl chloride acrylate copolymer. Vinyl chloride copolymers such as polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer; polyester; polyamide;
Examples include polyacrylate, polymethacrylate, acrylate-methacrylate copolymer, and silicone. These may be used alone or in combination of two or more.

On the other hand, organic low-molecular substances are at a temperature of T~T as shown in Figure 1.

The melting point 3 can be selected as appropriate depending on the
It is preferably about 0 to 200 C, especially about 50 to 150 C. Such organic low-molecular substances include alkanols; alkanediols; halogen alkanols or halogen alkanediols; alkylamines; alkanes; alkenes; alkynes; halogen alkanes; halogen alkenes, halogen alkynes; cycloalkanes; ; Saturated or unsaturated mono- or dicarboxylic acids or their esters, amides, or ammonium salts; Saturated or unsaturated halogenated fatty acids or their esters, amides, or ammonium salts; Allylcarboxylic acids or their esters, amides, or ammonium salts; ; halogen allylcarboxylic acids or their esters, amides, or ammonium salts; thioalcohols; thiocarboxylic acids or their esters, amines, or ammonium salts; carboxylic acid esters of thioalcohols, and the like. These may be used alone or in a mixture of two or more. The number of carbon atoms in these compounds is 10
-60, preferably 10-38, especially 10-30. The alcohol group moiety in the ester may be saturated or unsaturated, and may be substituted with halogen. In any case, organic low-molecular substances contain at least one of oxygen, nitrogen, sulfur, and halogen in the molecule, such as -O
H.

-0OOH, -○ONH, -00OR, -NH-, -N
H,, -8-.

A compound containing -5-S-, -O-, halogen, etc. is preferable.

More specifically, these compounds include higher fatty acids such as lauric acid, dodecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, behenic acid, nonadecanoic acid, arachidic acid, and oleic acid; methyl stearate, tetrastearate, etc. 2-decyl-esters of higher fatty acids such as octadecyl stearate, octadecyl lafinate, tetradecyl valmitate, and tocosyl behenate; 0sd (ss
-0-OtsHss, 0tsHss-8-
OnHu t○tsHsy-8-OtsHyr +
OtzHm-8-CtxHa +01eHs9
-8-OleHs + OtlHB-8-8-
011Hg.

H8 CH.

? H.

H8 H3 Hs There are ethers and thioethers such as

The weight ratio of the organic low-molecular substance to the resin base material in the layered heat-sensitive member is preferably about 10.5 to 1:16. If the ratio of the resin base material is less than this, it will be difficult to form a film that retains the organic low molecular weight substance in the resin base material, whereas if it is higher than this, the amount of the organic low molecular weight substance will be small and the film will become opaque. It becomes difficult to

The colored member is a supporting member, such as a layered heat-sensitive member, or paper, plastic film, glass plate,
It can be made by coating it on a metal plate, or by kneading a colored pigment or dye with a binder and forming it into a sheet. Here, known coloring pigments or dyes can be used. Further, as the coloring member, commercially available products such as color coated paper for printing can be used as they are.

A fluorine-based resin layered member can be made by 1) melting the fluorine-based resin and molding it into a sheet, or 2) coating the fluorine-based resin on a layered heat-sensitive member, a plastic film, a glass plate, etc. Can be done. In addition,
When a layered heat-sensitive member is formed on a sheet-like member made of a fluorine-based resin, surface treatment such as corona discharge may be performed to improve the adhesion of the fluorine-based resin sheet.Here, as the fluorine-based resin, polytetra Examples include fluoroethylene, polychlorotrifluoroethylene, and tetrafluoroethylene-hexafluoroftetrapyrene copolymer.

Next, an example of the use of the display body of the present invention will be explained using an electronic blackboard. FIG. 6 is a schematic diagram of an electronic blackboard using the display body of the present invention as a display sheet, and this electronic blackboard, like the conventional one, has a sheet 6 having one writing display surface wrapped around a box 5. A take-up roll (not shown) and its drive mechanism (not shown) are used to optically read the image written on the take-up roll on the take-up roll. The electronic blackboard is equipped with a photoelectric conversion means (not shown) for converting the electric signal into a photoelectric signal, and a printer 7 for printing out the electric signal. 8 and a thermal head 4 for printing photoelectrically converted image information on a sheet 6.

Note that 9 (shown as a dotted line because it is on the back side) is a heating roll for erasing held at a temperature higher than T1 to T in Figure 1 or 'rs, and 1o is a sheet feeder for moving the display surface. ,
Operation button 11 for instructing writing of a manuscript on a sheet, etc.
is the opening for inserting and removing originals and also for taking out the hubby.

The present invention will be explained below using a decorative example. Note that both "part" and "part" are based on weight.

Example 5 parts of nistearic acid and 75 parts of tetrahydrofuran were mixed together, dissolved uniformly, and applied to one side of a 75 μm thick polyester film with a wire spar, dried at 150C to form a 15 μm thick film. A heat-sensitive film was provided. This heat-sensitive film was white. Furthermore, on top of that, the thickness is 12
μm fluorine-based resin film (Aflex 5 manufactured by Asahi Glass Co., Ltd.)
12N) was laminated using an acrylic emulsion. Next, 10 parts of carbon black and 80 parts of methyl ethyl ketone were mixed together, uniformly dispersed using a ball mill, applied to the other side of the polyester film using a wire bar, dried at 150C, and colored to a thickness of 10 μm. A layer was provided to obtain a heat-sensitive recording display of the present invention.

Next, the entire display body was heated to 65C and then cooled to air temperature, so that the heat-sensitive film became transparent and the display body became black. When printing was performed at 150 C using a thermal head on the fluororesin film surface of this display, a clear white image with a black background was formed.

Next, after heating the entire heat-sensitive coating surface of this display at 55 ci, and cooling it to room temperature, the white image area becomes transparent.
Then, when printing was performed using a thermal head in the same manner as above, a clear white image was formed against a black background.

Even after repeating this operation more than 1,000 times, a similar image could be formed.

This display body is set as sheet 6 in Fig. 6 on the electronic blackboard shown in Fig. 6 with the fluorine-based resin film side facing up, the printed original is inserted through the original insertion slot, and the image is photoelectrically converted. When the printer output was printed and recorded on a display body using a thermal head, a clear white image with a black background was formed on one display body. When this image was photoelectrically converted using another photoelectric conversion means on the winding roll and printed as a printer output using an attached printer, a clear printed image was obtained.

Furthermore, the upper surface of the white image of the display (fluorine resin film surface)
When I drew on it with a commercially available red oil-based whiteboard pen, a clear red image was formed in that area. This red image could be wiped cleanly with a cloth.

Example 2 The same heat-sensitive film forming solution as in Example 1 was used except that vinylidene chloride-acrylonitrile copolymer was used instead of the vinyl chloride-vinyl acetate copolymer in the heat-sensitive film forming solution, and a 75 μm thick film was prepared. on polyester film,
A heat-sensitive film having a thickness of 20 μm was formed in the same manner as in Example 1.

This film was white.

A 25 μm thick fluorine-based resin film (
A heat-sensitive recording display of the present invention was obtained by superimposing sheets of AFLEX #25N (manufactured by Asahi Glass Co., Ltd.) and a black cup-coated paper on the side opposite to the heat-sensitive film surface.

Next, using this display body, printing was performed in the same manner as in Example 1 except that the thermal head was brought into direct contact with the heat-sensitive film. A clear image was obtained.

Further, when this image was printed using a printer in the same manner as in Example 1, a clear copy image was obtained.

Furthermore, when a red oil-based pen was used to draw on the surface of the fluororesin film on a white image, a clear red image could be drawn, and the image could be erased cleanly by wiping it with a cloth.

Example 3 The same heat-sensitive film forming solution as in Example 1 was used except that a polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.) was used instead of the vinyl chloride-vinyl acetate copolymer in the heat-sensitive film forming solution, and the thickness was A heat-sensitive film having a thickness of 15 μm was formed on a polyester film having a thickness of 75 μm in the same manner as in Example 1. This film was white. Then, a fluorine-based resin film (Aflex 16N, manufactured by Asahi Glass Co., Ltd.) having a thickness of 6 μm was deposited on the surface opposite to the heat-sensitive film using an acrylic emulsion.

Next, a black color coated paper is fixed to the box 5 in FIG. 6, and the sheet obtained above is assembled as the sheet 6 in FIG. 6 so that the heat-sensitive film surface faces the black color sheet surface. When a printed document was recorded using a thermal head in the same manner as in Example 1, a clear white image on a black background was obtained.

When this image was photoelectrically converted on a winding roll and printed out by a printer, a clear copy image was formed.

In addition, when drawing with a red oil-based pen on the fluorine-based resin film surface on a white image, a clear red image could be drawn.
Also, this image could be erased cleanly by wiping it with a cloth.

Effects As described above, the heat-sensitive recording display of the present invention can be reversibly recorded and erased, and especially when used as a display sheet for an electronic blackboard, images written on the sheet can be outputted from a printer as in the conventional case. In addition to the functions of taking out and recording, it also has the function of recording and displaying images written on ordinary paper on a display sheet, making it extremely practical. Of course, since the display body of the present invention has the above-mentioned heat-sensitive recording function, it can receive image information from a storage device such as a facsimile or floppy disk and form an image, or it can be used with a thermoben equipped with a heater or the like. It is also possible to draw.

[Brief explanation of the drawing]

Fig. 1 is an explanatory diagram of the recording principle in the heat sensitive body of the heat sensitive recording display body of the present invention, Figs. 2 to 5 are diagrams of the structure and state of use of this display body, and Fig. 6 is a schematic diagram of an electronic blackboard using this display body. It is a diagram. 1... Colored member 2... Layered heat-sensitive member 3...
・Fluorine-based resin finish 1 Layered member 4... Thermal head 5... Box body 6°°° Heat sensitive recording display body 7... Printer 8... Photoelectric conversion means 9... Heat for dissipation 7 -A'10...Operation button 11...Insertion and ejection port Patent applicant Ricoh Co., Ltd. - ゝ-:, jH'jijj'Mini・F10

Claims (1)

[Claims] 1. A layered heat-sensitive member having a heat-sensitive member whose main components are a resin base material and an organic low-molecular substance dispersed in the resin base material, and whose transparency changes reversibly depending on the temperature, and this layered heat-sensitive member. A heat-sensitive recording display body comprising a colored member provided on one surface of a heat-sensitive member and a layered member of a fluorine-based resin provided on the other surface of the layered heat-sensitive member.