JP4753585B2 - Repetitive recording medium writing instrument and writing method - Google Patents

Description

  The present invention relates to a writing instrument that writes on the surface of a recording medium that can be repeatedly used by heat, and more specifically, to the surface of a recording medium that can be used repeatedly, which controls both coloring and decoloring by heating at a temperature higher than room temperature. A coloring material that has a hysteresis property capable of maintaining a colored state and a decolored state at normal temperature and takes a decolored state in a temperature range higher than the color developing and decoloring temperature of the recording medium while maintaining a colored state at normal temperature. And a writing instrument for a recording medium that can be used repeatedly.

  Thermal pens are known as writing media on heat-recordable recording media, so-called reuse paper and thermal paper (Patent Documents 1 and 2). This thermal pen uses a heated nib and writes on reused paper or thermal paper with the heat, but it is difficult to use because the writing instrument itself is hot, and it is dangerous and requires special equipment. And had problems.

A recording medium that can be repeatedly used by heat is generally referred to as reuse paper, thermolite sheet, and the like, and is known per se (for example, Patent Document 3). In recent years, the market is expanding due to environmental problems and the like. In addition, the use of reuse paper or the like has been demanded not only for recording by an output device but also for writing on the surface thereof.
Conventionally, various attempts have been made in addition to the above-mentioned thermal pen as proposals for writing on reuse papers, etc., but they have not yet fully satisfied the requirements.
For example, in the case of using a so-called whiteboard marker or the like, the ink adhering to the surface is removed by dry method, so that there are cases where ink dusting occurs or cleaning is difficult. In addition, there are those that wipe off with special chemical fibers or the like, and those that require a large-scale device (Patent Document 4).
There is also a proposal that uses ink that softens with temperature and scrapes with a spatula during heating at the time of erasing, but it is similarly large and cannot be completely removed (Patent Document 5).
In order to improve this point, an ink using ink that can be erased with water has been proposed (Patent Document 6). However, because of the structure for washing with water, water is essential and the dry type is not possible.

On the other hand, there is a proposal that attempts chemical erasing instead of physical erasing as ink for writing.
Writing is performed using ink having the same thermal characteristics as a recording medium such as reuse paper, and since it can be erased under the same conditions as the recording image of the recording medium, it can be easily used. However, since the color development phenomenon is also the same, when the heating for the next recording that is used repeatedly is performed, the added ink portion also develops color, and in this case, there are subtle color differences and steps due to the ink thickness. There has been a problem that the handwriting of the colored additional ink is visible due to a change in the refractive index of the light beam (Patent Document 7).

  In addition, an ink has also been proposed that erases by melting and mixing an erasing component that has been blended separately from a coloring component at room temperature. In this case, there is no problem such that the handwritten ink of the colored ink is visible due to the change in the refractive index of the light beam, but once erased, the ink will never be restored and the so-called history is displayed again. The display was impossible (Patent Document 8 and Patent Document 9).

  On the other hand, as a thermochromic writing instrument, there is a proposal of a writing instrument in which a thermochromic ink giving a specific hysteresis characteristic is contained in a shaft tube as shown in Patent Document 9. However, in this proposal, there is no proposal for use as a so-called reuse paper. Moreover, it is used for writing on the surface of a reusable recording medium that controls both coloring and decoloring by heating at a temperature higher than room temperature. There was no suggestion regarding the history display or the history (Patent Document 10).

JP-A 63-9266 Japanese Patent Laid-Open No. 11-151890 JP-A-9-175030 JP 2004-130563 A JP-A-7-70502 JP 2003-1994 JP-A-1-138275 JP-A-9-165537 Japanese Patent Laid-Open No. 7-113055 JP-A-7-186588

  It is an object of the present invention to propose a writing instrument that writes on the surface of a reusable recording medium that controls both color development and decoloring by heating at a temperature higher than normal temperature. Regardless of whether the medium is colored or erased, the handwriting acts in the direction of erasing, and when necessary, the handwriting can be recolored by cooling to a set temperature lower than room temperature. The writing instrument etc. which is is proposed.

In order to solve the above-mentioned problems, the present invention includes a writing material for a recording medium and a writing method that can be used repeatedly according to the present invention, for example, by containing a colorant that erases in a temperature range equal to or higher than the color developing / erasing temperature of the recording medium. Was completed.
That is, the present invention
“ 1. The surface of a recording medium that can be used repeatedly can be controlled by heating at a temperature higher than room temperature, and has a hysteresis property that can maintain a color development state and a color erasure state at room temperature. While maintaining the color development state, with a writing instrument containing a coloring material that takes a color erasing state in a temperature range higher than the color erasing temperature of the recording medium, the surface of the recording medium that can be repeatedly used by heat is added and written, A writing method that can display repeated handwriting by heat.
2. The writing method according to claim 1, wherein both coloring and erasing are controlled by heating at a temperature higher than room temperature, and writing is performed on the surface of a reusable recording medium, and the coloring state and erasing state are maintained at room temperature. A writing instrument for a recording medium that can be used repeatedly, comprising a coloring material that has a hysteresis property and maintains a colored state at room temperature and takes a decolored state in a temperature range higher than the color developing and decoloring temperature of the recording medium. ".

According to the writing instrument, the following excellent effects can be achieved.
It is possible to write on the surface of a recording medium that can be repeatedly used by heat, and to erase well. In erasing, if the erasing is based on temperature, the history of the added items can be displayed by partially or entirely cooling. Furthermore, history display such as daily changes is possible by color coding.
If erasing is performed at a temperature lower than the lower of color development or decoloration of a reusable recording medium that controls both color development and decoloration by heating at a temperature higher than normal temperature, rewrite recording of the recording medium As it is, only the added record can be erased. At that time, a history display by cooling is also possible.
If necessary, after rewriting the rewrite record of the recording medium, if the part or the whole is cooled, the rewritten display displayed before the rewrite record is rewritten even after the rewrite display is rewritten. Can be reproduced.
If ink for writing instruments is made erasable even with water or rubbing, it can be completely erased just like conventional writing instruments that cannot be erased by heat. Also, even if dusting occurs during physical erasing, a synergistic effect can be expected, such as being inconspicuous and less likely to contaminate the surroundings.

It is well known that a colorless or light-colored electron-donating color-forming compound reacts with an electron-accepting compound to develop a color. Applying this principle, from the viewpoint of reducing environmental impact or from the viewpoint of convenience, the development of technology that makes color development and color erasure both thermally and reversible has been energetically performed. . For example, there is a thermochromic composition using a leuco dye which is an electron donating color developing compound and phenol which is an electron accepting compound.
The recording medium that can be used repeatedly and can be repeatedly used for controlling both color development and decoloring by heating at a temperature higher than room temperature has been researched and commercialized in various ways as its application technology. Control, color development and decoloring.
For example, an electron-accepting color selected from an electron-donating color-forming compound, a phosphonic acid compound having a long-chain aliphatic hydrocarbon group, an aliphatic carboxylic acid compound, and a phenol compound, as disclosed in Japanese Patent No. 2981558 By using a compound and a combination with an electron donating color developing compound, color development and decoloring can be easily performed by reversible recording by controlling heating and cooling, and a recording medium that stably holds them at room temperature Etc.
When such a recording medium is heated to the color development temperature range, both compounds melt and react to cause the color-forming compound to open and color, and by rapidly cooling it, the color development state can be maintained even at room temperature. Has been. When the colored composition is heated to a decoloring temperature range lower than the coloring temperature range, the long-chain alkyl group of the electron-accepting compound aggregates, and the electron-accepting compound becomes a single crystal, which It is presumed that they will separate and consequently lose color. That is, in the relationship between the electron-donating color-forming compound and the electron-accepting compound, the colored state is maintained by solidifying the two compounds while they are reacted, and the electron-accepting compound is thermally It is said that it separates and crystallizes under conditions to form a single crystal and maintain a decolored state.
That is, both the decoloring control and the coloring control are controlled by a temperature higher than room temperature, that is, “heating”.

On the other hand, the writing instrument for a recording medium that can be used repeatedly according to the present invention is based on, for example, a temperature change comprising at least (a) an electron-donating color-forming compound, (b) an electron-accepting compound, and (c) a reaction temperature regulator. It contains a coloring material obtained by pulverizing a mixture having hysteresis characteristics or storing it in a microcapsule. Mainly, the color is selected by the component (a), the color density is selected by the component (b), and the color temperature is determined by the component (c).
Such a color material is a color material having hysteresis characteristics due to temperature change, and depending on the temperature history, depending on whether the temperature is changed from the high temperature side to the normal temperature, or from the low temperature side to the normal temperature, the coloration mode and the color disappearance at normal temperature (20 ° C.). It is a color material that can take both modes of the embodiment.
Referring to FIG. 1, the coloring material can be colored by cooling to t1 and can maintain the colored state even at room temperature due to its hysteresis if it returns to room temperature as it is. That is, if the entire writing tool is cooled to t1 in advance, when writing with a writing tool containing the coloring material, colored handwriting can be obtained on the surface of the recording medium that can be repeatedly used by heat.
The handwriting can have various colors depending on the type of color material.
Then, the color material in the handwriting is heated, and when it reaches t4, it is in a decolored state. Due to the hysteresis property, the decolored state can be maintained even at room temperature.

Here, as described above, the recording medium that can be repeatedly used by heat develops color (t8) at a temperature higher than room temperature (see FIG. 2) and decolorizes (t6 to t7). In other words, if the erasing temperature of the medium (t6 in FIG. 2) is higher than the handwriting erasing temperature (t4 in FIG. 1), the handwriting can be erased simultaneously when erasing the medium display.
It should be noted that the recording medium controls both color development and decoloration by “heating”, but the color material used in the writing instrument of the present invention is erased by “heating”. In other words, the writing ink acts only in the erasing direction in both the coloring and erasing control operations of the recording medium, so that even more favorable erasability can be obtained.

  When t4 is higher than normal temperature and lower than the erasing start temperature t5 of the recording medium, only the handwritten handwriting can be erased many times without changing the display recorded on the medium. It can be used repeatedly for the purpose of erasing. Even in this case, the handwriting is suitably erased simultaneously by heating (t6 to t7) when erasing the display on the recording medium.

By the way, as described above, the erasing method can be executed even for an erasable color material that performs an irreversible reaction having no hysteresis property as conventionally used. Rather, the writing instrument containing the coloring material is a writing instrument specialized for use only in such an erasing method.
However, with a writing instrument containing an irreversible color material that can be erased, once erased, the character cannot be reproduced.
Even for writing instruments that contain reversible color materials, the recordings on the recording medium and the additional handwriting are also heated in the case of handwriting with the same reactive color material used for the recording medium. Since it disappears at the same time and colors at the same time by control, it is not possible to reproduce only the handwritten handwriting as it was.
If the temperature condition of color development / decoloration has a difference between the recording medium and the writing instrument, it is possible to make a difference in their color development / decoloration properties, but it has the same color development / decoloration control concept. Since they are the same, it is impossible to control the color development with only the writing ink.
Therefore, when the color material on the recording medium and the color material on the handwriting are colored simultaneously by re-recording on the recording medium, the ink is erased at first glance because it is composed of the same color tone. Although it appears to have been applied, a subtle difference in refractive index occurs due to the effect of the coating thickness and the third component, which is essential for writing instruments, and color differences that inevitably occur even though they have the same color tone. As a result, it is expected that the handwritten handwriting will come out, and there has been a problem in that extra shading is produced in the second and subsequent display on the recording medium.
Unlike the history display effect of the present invention, this phenomenon is different from the gist of the present invention in which handwriting can be actively reproduced.

  According to the writing instrument for a recording medium that can be used repeatedly according to the present invention, the handwriting once heat-erased is further erased in any process of heating color development and heat-erasing on the recording medium thereafter. Therefore, the re-recording display property of the recording medium is not affected.

  Here, it has been described that the handwriting written by the recording medium writing instrument of the present invention that can be used repeatedly is erased by heating to t4. However, there are applications where you want to reproduce the erased handwriting. In that case, if the medium itself is cooled to t1, the handwriting can be reproduced, and the reproduction handwriting is maintained even when it is returned to room temperature due to the hysteresis property. The At this time, the recorded image recorded on the recording medium itself is not affected at all. This is because the recording medium controls both the coloring and erasing processes at a temperature higher than room temperature (t5 to t8).

  For reproduction by cooling the handwriting, it is easy to reproduce the handwriting by putting the medium itself into the refrigerator as a whole and reproducing the whole handwriting or partially or entirely by cold spraying.

A suitable temperature for t1 is preferably 5 ° C. or less, and more preferably 0 ° C. or less so that handwriting is not easily reproduced by mistake. It is more preferably −10 ° C. or lower and further −20 ° C. or lower from the balance between the indoor environment temperature in winter and the ease of handwriting reproduction.
A preferable temperature of t4 is preferably 40 ° C. or higher so that the handwriting is not easily erased by mistake. Considering the indoor environment temperature in summer, the ease of erasing handwriting, and the setting of the erasing temperature of a reusable recording medium, 50 ° C. or higher, more preferably 60 ° C. or higher is more preferable.
The normal temperature used in the present invention refers to the environmental temperature when a reusable recording medium is used, and varies depending on the summer and winter, indoors and outdoors, factories and offices, etc. .

In the writing instrument containing the coloring material of the present invention, it is possible to erase the color by heating after writing, and if necessary, the erased handwriting can be reproduced by cooling as described above. .
Here, it is more preferable that a writing history effect can be obtained by writing for the second time with a color different from the color tone written for the first time and repeating writing and erasing with a different color until the nth time.
For example, after getting red handwriting on the first day with the first ink, erase the handwriting by heating, pink handwriting on the second day, orange handwriting on the third day, etc. If the handwriting of n color tones is obtained, all the color tones will be lost by heating, but all the tones can be displayed at the same time by cooling. The history effect can be obtained.
Furthermore, if a difference is provided in the temperature setting of t1-t4 of the color material in each ink, a use has the possibility of further expanding.
In addition, each color tone is not only a change from colored to colorless (decolored), but also from a normal color material or a combination of two thermochromic color materials (coloration). This is also included in the present invention. This is because it is effective when used for a colored recording medium.

  Embodiments of the present invention will be described below.

The writing instrument for a recording medium that can be repeatedly used by the heat of the present invention includes, for example, a coloring material comprising at least (a) an electron donating color developing compound, (b) an electron accepting compound, and (c) a reaction temperature regulator. contains.
As such a coloring material, the compositions described in JP-B-4-17154, JP-A-7-33997, JP-A-7-179777 and the like can be applied. Such a color material exhibits a hysteresis characteristic in the relationship between temperature and color density and changes color, that is, when the temperature is increased from the lower temperature side than the color change temperature range, and conversely, the temperature is increased from the higher temperature side than the color change temperature range. The phenomenon of discoloration follows a different path from the case of descending. This point will be described again with reference to FIG.

  In FIG. 1, a change in color density due to a temperature change proceeds along an arrow. The point A (temperature t1) in the graph is a point where the color is completely colored at a temperature below this point, and the point B (temperature t3) is substantially discolored (decolored) in the process of increasing the temperature. C point (temperature t4) is a point where the color is completely erased at a temperature higher than this, and the temperature range between the t1 and t4 is a discoloration temperature range. Both the hue and the second hue can coexist by the path, and the temperature range between t2 and t3, which is a region having a large difference in color density, is substantially the discoloration temperature range, that is, the first hue or the second hue is maintained. It is a two-color holding temperature range. In the present invention, a color material is used in which the normal temperature range is included in the color change temperature range between t1 and t4, or preferably in the substantial color change temperature range between t2 and t3.

  The colorant is preferably a microcapsule pigment containing essential components. The microencapsulation is prepared by a known method, that is, an interfacial polymerization method, an interfacial polycondensation method, an in situ polymerization method, a submerged curing coating method, a phase separation method from an aqueous solution, a spray drying method, or a combination thereof. Is done. In the microcapsule pigment system, there is a risk of clogging the pen body as a writing instrument or dispersion instability over time as the particle size increases, and the particle size is 10 μm or less, more preferably 5 μm or less, most preferably. 3 μm or less is preferable.

A suitable temperature for t1 is preferably 5 ° C. or less, and more preferably 0 ° C. or less so that handwriting is not easily reproduced by mistake. It is more preferably −10 ° C. or lower and further −20 ° C. or lower from the balance between the indoor environment temperature in winter and the ease of handwriting reproduction.
A preferable temperature of t4 is preferably 40 ° C. or higher so that the handwriting is not easily erased by mistake. Considering the indoor environment temperature in summer, the ease of erasing handwriting, and the setting of the erasing temperature of a reusable recording medium, 50 ° C. or higher, more preferably 60 ° C. or higher is more preferable.
As the color material in such a more preferable temperature range, the color materials described in Japanese Patent Application Nos. 2003-319039, 2004-21611, 2004-119869, and the like can be used.

  The ink for a writing instrument used in the present invention can be appropriately designed according to the form of the writing instrument to be used as long as an appropriate amount of the above coloring material is blended. Disperse coloring materials in various aqueous and oil-based solvents, etc., if necessary, sticking agent to writing surface, viscosity modifier, shear thinning agent, antiseptic, rust inhibitor, lubricant, etc. Can be obtained.

  As the writing instrument, various writing instruments such as a writing instrument having a capillary ink path such as a ballpoint pen and a felt pen containing the ink can be used. Other examples include a solid core hardened by a shaping material such as wax.

  From the viewpoint of protecting the surface of a reusable recording medium, a felt pen or a solid core having a writing tip that does not damage the surface is preferable.

Furthermore, the demand for reuse paper is increasing for FA applications, etc. From the viewpoint of the number of processes for line workers, there are many processes for removing and installing caps during writing, and processes for knocking with knock-type writing instruments. Therefore, a writing instrument that can be used without any operation is desired. Therefore, a solid core that can be used as it is without a problem such as drying at the tip of writing is suitable for such applications.
In the case of a solid core, although it depends on the selection of the shaping material, it is preferable because it can be applied thickly and the color developability is good. In addition, when a water-soluble material such as an aqueous gel is used, it has a good cleaning performance even when attempting complete removal with water.
However, in the case of a solid core, the handwriting has the property that it is difficult to dry or solidify or does not, so care must be taken during the second and subsequent thermal recordings. For example, in the case of using a thermal head, it is necessary to devise measures for protecting the thermal head so that it does not come into direct contact when the head passes, such as covering with a clear sheet in advance.

  During the first and second thermal recording, a fixed format recording is performed on a reuse paper with a thermal printer, and then writing is performed with the writing instrument of the present invention. It can be used satisfactorily for applications such as writing and erasing handwriting several times.

  If the writing instrument is a so-called permanent type that can obtain a highly rub-resistant handwriting as an ink, the thermal head is hardly damaged and is good. The ink composition in that case is mainly a solvent system, and it seems to be a cap type due to the problem of drying at the tip of writing, but it seems to be used.

  The color tone at the time of erasing the writing color material is preferably transparent. A colored type can also be used as long as it is a color similar to the base color of the recording medium. This is because there are few white recording media that can be used repeatedly, and if the color is similar to that of the base, it is considered that even an ink that is not completely decolored is not noticeable.

  As the recording medium that can be repeatedly used by the heat used in the present invention, those described above can be used. There are a colored type in which a coloring material such as a so-called leuco dye is arranged in a matrix polymer, and a transparent cloudy type by a difference in refractive index utilizing a difference in crystal structure.

  As a recording medium that can be repeatedly used by heat used in the present invention, even if it is a plain paper base, electrophotographic printing is performed on the plain paper with a heat erasable or reversible toner by a laser printer, a copy machine, or the like. It is also possible to add to reusable media. It can be used in the same manner even when it is recorded by an ink jet recording method or the like.

  Furthermore, writing in the present invention includes writing by a machine such as an ink jet recording method.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1
(Writing instrument)
A reversible thermochromic pigment (t1: 2 ° C., t2: 6 ° C., t3: 37 ° C., t4: 44 ° C., average particle size: 2) in which a thermosensitive color-changing color memory composition is encapsulated in a microcapsule as a colorant A reversible thermochromic ink consisting of 30 parts (5 μm, color change from dark green to colorless), 5 parts of a moisturizing agent, 0.7 part of a fungicide, and 64.3 parts of water was prepared.
Thereafter, the ink is cooled to 2 ° C. or lower in advance to develop a reversible thermochromic pigment, and then impregnated into a fiber bunched ink occlusion body covered with a synthetic resin film at room temperature (20 ° C.). It is stored in a writing cylinder with a polyester fiber resin pen at the tip, and the fiber-focused ink occlusion body and the pen body are assembled in contact to complete a water-based marker that can be used repeatedly. did.
(recoding media)
As a reusable recording medium, a recording medium having a thermoreversible recording layer on a plastic sheet in which a leuco dye or the like that controls both coloring and decoloring by heating at a temperature higher than normal temperature is held in a matrix polymer. The recording medium used was one that performed color recording at about 110 ° C./rapid cooling and erased recording at about 60 ° C./slow cooling.
(Written)
When writing and writing on the recording medium using the writing instrument, writing was successful. In addition, the handwriting shows dark green color when cooled to 2 ° C. or lower, becomes colorless at 44 ° C. or higher, and the dark green handwriting is memorized and visualized in the temperature range of 6 ° C. to 37 ° C. due to hysteresis. In addition, a colorless handwriting, that is, an invisible handwriting could be stored and retained. In addition, the part in the said Example shows a mass part, and the following examples are also the same.

Example 2
(Writing instrument)
A reversible thermochromic pigment (t1: 3 ° C, t2: 6 ° C, t3: 38 ° C) in which a thermosensitive color-change color memory composition is encapsulated in a microcapsule using the reversible thermochromic ink in Example 1 as a colorant. T4: 45 ° C., average particle size: 2.5 μm, color change from blue to colorless) Reversible thermochromic ink comprising 20 parts, 5 parts moisturizing agent, 0.7 part antibacterial material, and 74.3 parts water. In the same manner as in Example 1, a water-based marker as a recording medium writing tool that can be used repeatedly was completed.
(Written)
When writing and writing on the recording medium used in Example 1 using the writing instrument, writing was successful. In addition, the handwriting shows a dark green color when cooled to 3 ° C or lower, becomes colorless at 45 ° C or higher, and makes the dark green handwriting memorized and visualized in the temperature range of 6 ° C to 38 ° C due to hysteresis. In addition, a colorless handwriting, that is, an invisible handwriting could be stored and retained.

The writing instrument and writing method of the present invention have the following industrial applicability.
The present invention is applicable to a writing instrument that can be satisfactorily written on the surface of a recording medium that can be repeatedly used by heat and can be erased satisfactorily.
In erasing, if the erasing is based on temperature, the history of the added items can be displayed by partially or entirely cooling. Furthermore, history display such as daily changes is possible by color coding.
If erasing is performed at a temperature lower than the lower of color development or decoloration of a reusable recording medium that controls both color development and decoloration by heating at a temperature higher than normal temperature, rewrite recording of the recording medium As it is, only the added record can be erased. At that time, a history display by cooling is also possible.
If necessary, after rewriting the rewrite record of the recording medium, if the part or the whole is cooled, the rewritten display displayed before the rewrite record is rewritten even after the rewrite display is rewritten. Can be reproduced.
If ink for writing instruments is made erasable even with water or rubbing, it can be completely erased just like conventional writing instruments that cannot be erased by heat. Also, even if dusting occurs during physical erasing, a synergistic effect can be expected, such as being inconspicuous and less likely to contaminate the surroundings.

It is explanatory drawing which shows the thermal discoloration behavior of the coloring material used for this invention. It is explanatory drawing which shows the thermal discoloration behavior of the recording medium which can be recorded by heat.

Claims (2)

  The surface of the reusable recording medium that controls both coloring and erasing by heating at a temperature higher than room temperature has a hysteresis property that can maintain the coloring and erasing states at room temperature. Repeated by heat on the surface of the recording medium that can be repeatedly used by heating, writing and writing with a writing instrument containing a coloring material that takes on a color erasing state in a temperature range higher than the color erasing temperature of the recording medium while maintaining Writing method that can display handwriting. The writing method according to claim 1, wherein both coloring and erasing are controlled by heating at a temperature higher than room temperature, and writing is performed on the surface of a reusable recording medium, and the coloring state and erasing state are maintained at room temperature. A writing instrument for a recording medium that can be used repeatedly, comprising a coloring material that has a hysteresis property and maintains a colored state at room temperature and takes a decolored state in a temperature range higher than the color developing and decoloring temperature of the recording medium.

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