JPH0678031B2 - Repeat recording method - Google Patents

Description

Detailed Description of the Invention

 Purpose of the invention

[Industrial applications]

The present invention relates to a repetitive recording method capable of temporary recording and free rewriting. The repetitive recording method of the present invention is used to display the number of times a train or bus coupon has been used, a telephone card balance, a medical ticket receipt number, a credit card monthly total, a cash card balance, etc., a word processor, a personal computer, etc. Suitable for temporary output material.

[Prior art]

Conventionally, as a recording technique, there are many methods such as thermal recording, ink jet recording, electrostatic recording, and wire dot recording. The recording material used for these is a thermal recording paper or plain paper, and when a plain paper is applied to thermal recording, a transfer ribbon is used. All of these recording methods are irreversible, it is difficult to correct misprints, and it is impossible to use the same recording material many times. However, it is often the case that it is desired to perform repeated recording by erasing existing recordings and making new recordings on the same recording material. On the other hand, as a material utilizing reversible change, there is a material called a temperature indicating material. These mainly use metal salts such as mercury and copper, which utilize the crystal modification accompanying the temperature change, or those which utilize the opening and closing ring reaction of the leuco dye by the combination of leuco dye and electron donor-acceptor, Widely known. Although a reversible heat-sensitive method that uses a thermal hysteresis curve during color development and erasing has already been proposed, a heat-retaining heat source is required in the device to store images for a long time after color development, and the device is large. Will turn into. There are also reversible materials that utilize the acquisition and removal of water of crystallization, and typical examples thereof include cobalt chloride.
This is different from the above-mentioned temperature-indicating material, and it takes time for the crystal water to be dissociated and discolored for recording, and then it takes time to absorb the crystal water and return to the initial state. A reversible thermosensitive recording material using this is also proposed, but since it does not return to the initial state within about one day,
It cannot be reused or corrected until the next day. Japanese Examined Patent Publication No. 50-5097 discloses reversible recording material by water absorption / dehydration, which is provided as a brush-writing colored paper, and it is provided for practicing writing brushes, and its water retention time is as short as 4 to 5 minutes. Not a material. As described above, with the conventional recording material, only one print can be obtained, and it is not possible to repeat recording on the same material.

[Problems to be Solved by the Invention]

An object of the present invention is to provide a recording technique capable of recording and erasing, and capable of changing the record and correcting an input error on the same recording material. Structure of the invention

[Means for solving problems]

The repetitive recording method of the present invention is a method of repetitive recording on the same recording material, showing a temperature indicating property of developing a color at a specific temperature, reversibly absorbing and releasing water of crystallization, and in a state of absorbing and releasing. A recording material is formed by applying a thermochromic material that develops and erases color onto a support,
Recording or erasing is performed by partially heating the recording material or supplying water to develop or erase the color. A typical temperature indicating material is a complex compound of hexamethylenetetramine and a salt of cobalt or nickel, and specific examples thereof are as follows. Hexamethylenetetramine-cobalt chloride complex 10-hydrate Hexamethylenetetramine-cobalt bromide complex 10-hydrate Hexamethylenetetramine-cobalt iodide complex 10-hydrate Hexamethylenetetramine-nickel chloride complex 10-hydrate Hexamethylenetetramine-nickel bromide complex Hexamethylenetetramine-cobalt nitrate complex 10-hydrate Hexamethylenetetramine-cobalt sulfate complex 10-hydrate Hexamethylenetetramine-nickel nitrate complex 10-hydrate Hexamethylenetetramine-nickel sulfate complex 10-hydrate In addition, the following substances are also shown It is useful as a material. Dipyridine Cobalt Sulfate Decahydrate Iron Ammonium Permanganate Hexahydrate Cobalt Phosphate Octahydrate

[Action]

When using a material that develops color upon removal of water of crystallization,
A negative pattern image is obtained by applying moisture to a recording material which has been heated in advance to develop color on the entire surface by applying a method such as wire dot printing using an inkjet or a water-containing ribbon. To change or correct this image, partially heat it with a heating element such as a thermal head or a heating pen to release the water of crystallization, cause color development and return to the initial state. A new image can be obtained by supplying water by dot printing, inkjet, etc. In addition to the above, infrared light and laser light can also be used as the heat source. Similarly, it is possible to obtain a positive image. In this case, a positive image can be obtained by spraying water vapor using a humidifier or coating water with a watering roller to make the decolored state the original state, and by causing the heat source to develop color. To be The correction may be performed by erasing the color by supplying the water. In the water supply method as described above, the drying rate may be inappropriate depending on the type of recording material and the use conditions. For example, there is a problem in that the water containing crystal water is too slow to dry and takes a long time to develop heat, and the material such as a brush-colored paper is too fast to dry and it is difficult to temporarily store records. Occurs. As a countermeasure against this, it is recommended to mix an appropriate organic solvent to adjust the volatility to obtain a desired drying rate. Any organic solvent can be used as long as it does not damage the recording material.

Example 1 A commercially available temperature indicating material "Oriental Thermal Color OF-60" (Oriental Giken) formed by coating a complex of a salt of hexamethylenetetramine and cobalt on a support was used as a recording material. This temperature indicating material is a semi-irreversible type, which develops a color when heated to a constant temperature and retains the color even when the temperature returns to the original temperature, but exhibits a property of disappearing when water is supplied. The semi-irreversible temperature indicating material has high storage stability of the record when used as a recording material and is easy to erase,
It is suitable for use in the present invention. After heating this recording material to 70 ° C to develop color over the entire surface,
After returning to room temperature, water was supplied by the following means. B) Inkjet printer b) Printing was performed using a wire dot printer with a ribbon made of cotton cloth sufficiently moistened by a humidifier, or c) a transfer type thermal printer with a ribbon made of cotton cloth similar to the above b. By the above method, a white image pattern in a blue background was obtained. This image was still visible after 2 days. Heat was supplied to the above recorded image by the following means to partially erase the recorded image. D) Direct recording type thermal printer e) Laser printer f) Infrared light It was possible to selectively recolor any part of the image by the above water supply method. Furthermore, it was possible to re-record the selectively recolored portion using the above-mentioned thermal printing method, and it was possible to correct the recording.

Example 2 In Example 1, comparison was performed using the following three types of liquids supplied by an inkjet printer. B) Water b) Water: Methyl alcohol = 2: 1 c) Water: Ethylene glycol = 2: 1 As a result, (b) was used for faster color development with a laser printer, and (c) was used. The storability of the recorded image was good.

Example 3 The temperature indicating material used in Example 1 was whitened on the front surface using a humidifier, and then an image was formed by the methods of the above d), e) and f) to obtain a positive image. This positive image has been found to be suitable as a modifiable display material because it can be partially erased and rerecorded by heating. It has been found that the image recorded by the above method has a high contrast and therefore can be used as a base paper for copying, and when the recorded image needs to be stored, a copy can be made. EFFECTS OF THE INVENTION By using the method of the present invention, it is possible to record on the same recording material and erase it, and it is possible to change the recording and correct an input error on the recording material. That is, repetitive recording is realized by separately supplying moisture or a mixture of water and an organic solvent and heat from the outside.

Claims (3)

[Claims] 1. A method of repetitive recording on the same recording material, which exhibits a temperature indicating property of developing a color at a specific temperature, reversibly absorbs and releases water of crystallization, and develops a color and a color in the absorbed and released state, respectively. Recording or erasing by forming a recording material by applying a decolorizable temperature-indicating material on a support and partially heating or supplying water to develop or decolor the recording material. A method characterized by. 2. The repetitive recording method according to claim 1, wherein a complex of hexamethylenetetramine and a salt of cobalt or nickel having water of crystallization is used as the temperature indicating material. 3. The repetitive recording method according to claim 1, wherein partial heating is carried out by a thermal head or a hot pen, and water is supplied by an ink jet means or a combination of a bon containing water and a wire dot printer. .