JP4085124B2 - Method for producing reversible thermosensitive recording medium - Google Patents

Description

The present invention relates to a method for producing a reversible thermosensitive recording medium having writability that can be described with a writing instrument such as a ballpoint pen or a magic (registered trademark) ink pen.

  2. Description of the Related Art Conventionally, a card having a sign panel that can write the name of the card holder and the like with a writing instrument such as a ballpoint pen is known.

  Further, there is known a card having a rewrite display portion formed of a reversible thermosensitive recording layer capable of erasing / (re) writing image information or the like by applying heat to one side of the card or the like.

  A rewrite card provided with such a sign panel is also known.

  The rewrite card provided with this sign panel has a reversible thermosensitive recording layer in which the sign panel as described above is provided on one side of the base material, and the rewrite display part is provided in a layered manner on the opposite side of the surface. It has a structure.

  When displaying information on such a rewritable card, using a heating application means such as a thermal head, a rubber roll is pressed against the surface opposite to the surface to be printed, and heat is applied to the printing surface by the thermal head. Is done by that.

  In this printing, if the sign panel provided on the surface opposite to the printing surface has a step of about 10 μm, for example, the pressure unevenness of the thermal head on the printing surface opposite to the substrate having this step. As a result, there were darkness and fading in printing.

  For this reason, the edge part of the sign panel could not be provided so as to overlap with the inside of the reversible thermosensitive recording layer provided on the opposite surface to the substrate.

In addition, if the end of such a sign panel is provided in the rewrite display area provided on the opposite surface, the strength of pressing the rubber roll is adjusted during printing to prevent blurring of printing. As a result, the life of the rewritable card may be extremely reduced or the thermal head may be damaged due to the pressure applied during printing. For this reason, at present, there has not been obtained a rewrite card that effectively prevents blurring during printing and prolongs the card life.
JP-A-10-181268 JP-A-11-105476 JP-A-8-142521 JP 58-201651 A

SUMMARY OF THE INVENTION In view of the above-described problems of the prior art, an object of the present invention is to provide a method for producing a reversible thermosensitive recording medium having writing suitability that does not cause color unevenness and print fading during printing. Yes.

  In order to achieve this object, the present invention has the following features.

A method for producing a reversible thermosensitive recording medium according to the present invention includes:
A writable layer comprising a reversible thermosensitive recording layer on a substrate, and containing a porous material in at least a part of the outermost layer on the opposite surface of the substrate having the reversible thermosensitive recording layer. A method for producing a reversible thermosensitive recording medium comprising:
Perform each layer hot press constituting the reversible thermosensitive recording medium, the outermost layer having said writing layer performs roughening treatment, the surface roughening treatment, hot pressing via a roughened plate It is characterized by being performed at the same time.

Further, a method for producing a reversible thermosensitive recording medium according to the present invention includes:
A writable layer comprising a reversible thermosensitive recording layer on a substrate, and containing a porous material in at least a part of the outermost layer on the opposite surface of the substrate having the reversible thermosensitive recording layer. A method for producing a reversible thermosensitive recording medium comprising:
Perform each layer hot press constituting the reversible thermosensitive recording medium, the outermost layer having said writing layer performs roughening treatment, the surface roughening treatment, a heat press in the mirror plate is not roughened After performing, it is characterized by performing through the roughened board | plate material.

Further, a method for producing a reversible thermosensitive recording medium according to the present invention includes:
A porous ink is printed to form the writable layer.
In the method for producing a reversible thermosensitive recording medium according to the present invention,
Each layer constituting the reversible thermosensitive recording medium includes an IC circuit board layer on which an IC chip is mounted.

In the method for producing a reversible thermosensitive recording medium according to the present invention,
The plate material is a film made of a resin higher than a softening point of the outermost layer.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the manufacturing method of the reversible thermosensitive recording medium which has the possibility of generating coloring irregularity, printing blurring, etc. at the time of printing, and has writing suitability.

  The reversible thermosensitive recording medium having writability according to the present invention and the production method thereof will be described in order.

  The reversible thermosensitive recording medium having writability according to the present invention is a reversible thermosensitive recording medium having a reversible thermosensitive recording layer on a substrate, opposite to the substrate provided with the reversible thermosensitive recording layer. A writable layer is provided on at least a part of the outermost layer of the surface, and the outermost layer is provided substantially flush.

  First, the reversible thermosensitive recording layer constituting the reversible thermosensitive recording medium having such writability, the substrate having writability and the like will be described.

[Reversible thermosensitive recording medium with writability]
The reversible thermosensitive recording medium having writability according to the present invention has at least a substrate, a reversible thermosensitive recording layer, and a writable layer as shown in FIG. Further, as shown in FIG. 2 (a), as a base material, a laminate composed of two core films and an overlay film laminated on both surfaces of the core film is used, and between the core film and the overlay film. Has an adhesive layer 6.

  The surface (front surface) side overlay film is provided with a print 7 on which the reversible thermosensitive recording layer 2 is provided. Further, a protective layer is provided on the reversible thermosensitive recording layer 2. In the example shown in FIG. 2B, an IC circuit board layer 4 is provided between the layers of the core film, and a through-hole is provided in a portion of the core film that embeds the IC chip 5 therein. . Each layer used in such a reversible thermosensitive recording medium having writability according to the present invention will be described.

Reversible thermosensitive recording layer 2
The reversible thermosensitive recording layer 2 is a layer capable of reversibly recording and erasing information by heating with a heating means such as a thermal head. Such a reversible thermosensitive recording layer 2 is formed on the substrate 3 by drying after coating, or by using a transfer sheet or an adhesive sheet on which the reversible thermosensitive recording layer 2 is formed. Can be formed.

  The reversible thermosensitive recording layer 2 is composed of a leuco dye, a developer / developer, and a binder resin as main components and repeats color development / decoloration reversibly by heat. The leuco dye is usually referred to as a colorless to light-colored electron-donating dye precursor. Further, the developer / color reducing agent is referred to as an electron-accepting compound, which causes a reversible color change in the dye precursor due to a difference in cooling rate after heating, and has at least one aliphatic hydrocarbon group having 6 or more carbon atoms. A phenolic compound, a naphtholic compound, a phthalic acid compound, an acidic compound having a phenolic hydroxyl group and an amino group, an acidic compound having a naphtholic hydroxyl group and an amino group, or the like is used.

  Examples of the leuco dye contained in the reversible thermosensitive recording layer 2 include crystal violet lactone, 3-indolino-3-p-dimethylaminophenyl-6-dimethylaminophthalide, and 3-diethylamino-7-chlorofluorane. 2- (2-chlorophenylamine) -diethylaminofluorane, 2- (2-fluorophenylamino) -6-diethylaminofluorane, 2- (2-fluorophenylamino) -6-di-n-butylaminofluorine Oran, 3-diethylamino-7-cyclohexylaminofluorane, 3-diethylamino-5-methyl-7-t-butylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6- Methyl-7-p-butylanilinofluorane, 3-cyclohexylamino 6-chlorofluorane, 2-anilino-3-methyl-6- (N-ethyl-p-toluidino) -fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-7-cyclohexyl Examples include aminofluorane, 3-N-methylcyclohexylamino-6-methyl-7-anilinofluorane, and 3-N-ethylpentylamino-6-methyl-7-anilinofluorane.

  Here, the electron donating dye precursor as a normally colorless or light leuco dye may be used singly or in combination of two or more.

  Further, examples of the developer / subtractant contained as a main component in the reversible thermosensitive recording layer 2 include N- (p-hydroxyphenyl) -N′-n-octadecylthiourea and N- (p-hydroxyphenyl) -N ′. -N-octadecylurea, N- (p-hydroxyphenyl) -N'-n-octadecylthioamide, 4'-octadecananilide, 2-octadecylterephthalic acid, N-octadecyl (p-hydroxyphenyl) amide, N- (p -Hydroxybenzoyl) -N-octadecanoylamine, N- [3- (p-hydroxyphenyl) propiono] -N'-octadecanohydrazide, N-[(p-hydroxyphenyl) methyl] -n-octadecylamide N-[(p-hydroxyphenyl) methyl] -n-octadecylurea, N-[(p-hydroxyphenyl) me Til] -N′-n-octadecyloxamide and the like.

Furthermore, the below-mentioned color developing / subtracting agents can be used.
N-pentacosyl (p-hydroxyphenyl) amide, N-hexacosyl (p-hydroxyphenyl) amide, N-heptacosyl (p-hydroxyphenyl) amide, N-octacosyl (p-hydroxyphenyl) amide, N-nonacosyl (p- Hydroxyphenyl) amide, N-triacontyl (p-hydroxyphenyl) amide, N-hentriacontyl (p-hydroxyphenyl) amide, N-dotriacontyl (p-hydroxyphenyl) amide, N-tetratriacontyl (p-hydroxy) Amide compounds such as phenyl) amide;

  N- (p-hydroxybenzoyl) -N- hexacosanoylamine, N- (p-hydroxybenzoyl) -N- heptacosanoylamine, N- (p-hydroxybenzoyl) -N- octacosanoylamine, N- (P-hydroxybenzoyl) -N-nonacosanoylamine, N- (p-hydroxybenzoyl) -N- triacontanoylamine, N- (p-hydroxybenzoyl) -N-hentriacontanoylamine, N- ( diacylamine compounds such as p-hydroxybenzoyl) -N-dotriacontanoylamine, N- (p-hydroxybenzoyl) -N-tetratriacontanoylamine,

  N- [3- (p-hydroxyphenyl) propiono] -N′-hexacosanohydrazide, N- [3- (p-hydroxyphenyl) propiono] -N′-heptacosanohydrazide, N- [3- ( p-hydroxyphenyl) propiono] -N'-octacosanohydrazide, N- [3- (p-hydroxyphenyl) propiono] -N'-nonacosanohydrazide, N- [3- (p-hydroxyphenyl) propiono] -N'-Triacontanohydrazide, N- [3- (p-hydroxyphenyl) propiono] -N'-Hentriacontanohydrazide, N- [3- (p-hydroxyphenyl) propiono] -N'-do Diacylhydrazine compounds such as triacontanohydrazide, N- [3- (p-hydroxyphenyl) propiono] -N′-tetratriacontanohydrazide,

  N-[(p-hydroxyphenyl) methyl] -n-pentacosylamide, N-[(p-hydroxyphenyl) methyl] -n-hexacosylamide, N-[(p-hydroxyphenyl) methyl]- n-heptacosylamide, N-[(p-hydroxyphenyl) methyl] -n-octacosylamide, N-[(p-hydroxyphenyl) methyl] -n-nonacosylamide, N-[(p-hydroxyphenyl) ) Methyl] -n-triacontylamide, N-[(p-hydroxyphenyl) methyl] -n-hentriacontylamide, N-[(p-hydroxyphenyl) methyl] -n-dotriacontylamide, Amide compounds such as N-[(p-hydroxyphenyl) methyl] -n-tetratriacontylamide,

  N-[(p-hydroxyphenyl) methyl] -N'-n-pentacosylurea, N-[(p-hydroxyphenyl) methyl] -N'-n-hexacosylurea, N-[(p-hydroxyphenyl) methyl ] -N'-n-heptacosyl urea, N-[(p-hydroxyphenyl) methyl] -N'-n-octacosyl urea, N-[(p-hydroxyphenyl) methyl] -N'-n-nonacosyl urea, N-[(p-hydroxyphenyl) methyl] -N'-n-triacontylurea, N-[(p-hydroxyphenyl) methyl] -N'-n-hentriacontylurea, N-[(p-hydroxyphenyl ) Urea compounds such as methyl] -N′-n-dotriacontylurea, N-[(p-hydroxyphenyl) methyl] -N′-n-tetratriacontylurea,

  N-[(p-hydroxyphenyl) methyl] -N'-n-pentacosyloxamide, N-[(p-hydroxyphenyl) methyl] -N'-n-hexacosyloxamide, N-[( p-hydroxyphenyl) methyl] -N'-n-heptacosyloxamide, N-[(p-hydroxyphenyl) methyl] -N'-n-octacosyloxamide, N-[(p-hydroxyphenyl) ) Methyl] -N'-n-nonacosyloxamide, N-[(p-hydroxyphenyl) methyl] -N'-n-triacontyloxamide, N-[(p-hydroxyphenyl) methyl] -N '-n-Hentriacontyloxamide, N-[(p-hydroxyphenyl) methyl] -N'-n-Dotriacontyloxamide, N-[(p-hydroxyphenyl) methyl] -N'-n -Oxalic acid diamide compounds such as tetratriacontyl oxamide.

  Furthermore, the compound shown with the following chemical formula can be mentioned.

  In the above formula, a is an integer of 1 to 3, X is any group selected from —CONH—, —NHCO—, —CONHCO—, —CONHNHCO—, or —NHCOCONH—, and b is It is an integer of 10 or more.

  In the formula [2-1] or [2-2], n is an integer of 10 or more.

  The developing / subtracting colorant used may be used singly or in combination of two or more.

  The binder resin contained in the reversible thermosensitive recording layer 2 includes starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, acrylic acid amide / acrylic acid. Water-soluble polymers such as ester copolymers, acrylic acid amide / acrylic acid ester / methacrylic acid terpolymers, styrene / maleic anhydride copolymer alkali salts, ethylene / maleic anhydride copolymer alkali salts And latex such as polyvinyl acetate, polyurethane, polyacrylate, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, ethylene / vinyl acetate copolymer, etc. In particular, the reversible thermosensitive recording layer 2 having excellent dispersibility of the electron-donating dye precursor (leuco dye) and the electron-accepting compound (developing color reducing agent) and excellent rewriting durability can be obtained. A resin obtained by esterifying acrylic acid or methacrylic acid with a vinyl chloride / vinyl acetate / vinyl alcohol copolymer can be used as a resin that is made ultraviolet or electron beam curable by introducing a double bond into the molecule. These resins can be used alone or in admixture of two or more.

  On the other hand, in the reversible thermosensitive recording layer, it is sufficient that rapid cooling occurs after heating in order to perform color development, and it is sufficient that the cooling rate after heating is slow in order to perform decoloring. For example, when heated for a relatively long time with an appropriate heat source (thermal head, heat roll, heat stamp, high frequency heating, radiant heat from an electric heater, hot air, etc.), not only the reversible thermosensitive recording layer 2 but also the substrate 3 etc. are heated. As a result, the cooling rate is slowed down and the phase is separated (decolored state). On the other hand, after heating by an appropriate method, a colored state can be developed by rapidly cooling by pressing a low-temperature metal block or the like.

  Further, when heating is performed for a very short time using a thermal head, a hot plate or the like, cooling (solidification) starts immediately after the completion of heating, so that a colored state can be developed. Therefore, even if the same heating temperature and / or the same heat source are used, the coloring state and the decoloring state can be arbitrarily expressed by controlling the cooling rate. The reversible thermosensitive recording layer 2 using this kind of material is usually formed to a thickness of about 3 to 15 μm.

Writable layer 1
The writable layer 1 used in the present invention is provided on at least a part of the outermost layer 10 on the opposite surface to the reversible thermosensitive recording layer 2 and the substrate 3 described above. The writable layer 1 is prepared by surface treatment of a plastic film, or a porous ink is applied on the outermost layer, or an adhesive sheet or transfer sheet having a porous ink layer is used as a base. It can be provided by adhesion or transfer onto the material. The writable layer 1 can also be formed by appropriately combining these methods.

Examples of the method for applying the porous ink include a printing method. As the ink used in this printing method, commercially available inks containing porous materials such as silica (SiO ₂ ), alumina (Al ₂ O ₃ ), and combinations thereof can be used. Screen ink product name “SS7GK sign 611 white” manufactured by Co., Ltd., screen ink product name “SS writing medium” manufactured by Toyo Ink Manufacturing Co., Ltd., and the like can be used.

  Further, in the present invention, as will be described later, the roughened mirror plate or the roughened surface of the surface-roughened plate material 15 is brought into contact with the writable layer 1 and hot-pressed, whereby heat fusion or the like is performed. Even after the treatment, a good writable layer 1 can be provided. The same method as described above can be used for roughening the mirror plate 21.

  As the plate material 15 having the roughened surface, the surface of the plastic film was roughened by sand blasting or a known method such as acid, alkali, organic solvent or the like by chemical etching. Things can be used.

  The writable layer 1 formed in the present invention has an Ra value determined based on JIS B 0601, preferably in the range of 0.3 to 10 μm, and particularly preferably in the range of 0.4 to 2 μm.

Base material 3
As the base material 3 used in the present invention, a film made of the following materials or a laminate thereof is used.

Chlorine-containing polymer; polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, vinyl chloride-acrylate copolymer, Polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer, etc.
Polyester resin: Polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), or a condensed ester resin of an acid component such as terephthalic acid or isophthalic acid and an alcohol component such as ethylene glycol or cyclohexanedimethanol (for example, PETG: yeast) Man Chemical's trademark), etc.
Biodegradable plastic resins; polylactic acid resins, natural polymer resins composed of starch and modified polyvinyl alcohol, etc., microorganism-produced resins composed of β-hydroxybutyric acid and β-hydroxyvaleric acid, and the like.

  Further examples include synthetic resin films such as polyacetate, polystyrene (PS), epoxy resin, polyvinyl chloride (PVC) and polycarbonate (PC), polyamide resin, acrylic resin, silicone resin, and synthetic paper. They may be combined or may be a laminate of these materials. The thickness of these base materials 3 may usually be about 10 to 50 μm.

  As an example of such a laminated body, as shown in FIG. 2A and the like, a core film 13 in which two white polyvinyl chloride resin films (for example, a thickness of 280 μm) are laminated, and the front and back surfaces of the core film 13 are used. And a laminated film of a transparent polyvinyl chloride resin film or the like that has been printed as an overlay film (for example, a thickness of 100 μm), a core film in which two white PETG films (for example, a thickness of 280 μm) are laminated, and this core film A laminate of printed transparent PETG as an overlay film (for example, 100 μm thickness) on both the front and back surfaces of the above, a laminate of an overlay film on either the front surface (front surface) side or back surface of the core film, or one side Etc. Polyethylene terephthalate (PET) can also be used as the overlay film.

  Also, a core film in which two similar white polyvinyl chloride resin films having the surface printed thereon are laminated, and a transparent polyvinyl chloride resin film similar to the above laminated on the front and back surfaces of the core film as an overlay film Also, a core film obtained by laminating two similar white PETG films having the surface printed or the like, and a laminate of the same transparent PETG as an overlay film on the front and back surfaces of the core film, the surface of the core film ( Examples include those obtained by laminating an overlay film on the front side) or the back side or on one side.

IC chip circuit board layer 4
The reversible thermosensitive recording medium having writability according to the present invention preferably has an IC chip circuit board layer 4. For example, as shown in FIG. 2B, for example, an IC chip is embedded in a base material layer and the embedded IC chip 5 and the IC chip circuit board layer 4 are electrically connected via bumps or the like. It may be.

  Further, the reversible thermosensitive recording medium having writability according to the present invention may have an adhesive layer 6 and the like described below as shown in FIGS. 2 (a) and 2 (b).

Adhesive layer 6
The adhesive layer 6 is not particularly limited as long as it is provided between arbitrary layers when the base material 3 is a laminate, particularly a film layer with poor adhesion, and can sufficiently bond the layers when subjected to hot pressing or the like. Examples of the resin forming the adhesive layer 6 include polyester resins, alkyd resins, vinyl resins, polyurethane resins or mixed resins thereof, and films made of hot melt resins.

Protective layer 8
The protective layer 8 can be provided on the reversible thermosensitive recording layer 2. Such a protective layer 8 is not particularly limited as long as it is normally used as the protective layer 8, but in the present invention, it can be composed of an ultraviolet curable resin. In addition, silica or the like may be contained, and if necessary, a dispersant, a surfactant such as fluorine, a conductive agent, a filler, a lubricant such as silicone, an antioxidant, and a light stabilizer. , UV absorbers, color development stabilizers, decolorization accelerators, and the like may be included.

Other recording layers The reversible thermosensitive recording medium having writability according to the present invention may be provided with other reversible recording layers 2 and irreversible recording layers. Examples of such other reversible recording layers include magnetic recording layers described below. Examples of the irreversible recording layer include a layer in which the known printing 7 is provided in a layered form.

Examples of the magnetic recording layer include those generally used as a magnetic recording layer in conventional magnetic recording media. For example, Ba-ferrite, Sr-ferrite, Co-coated γ-Fe ₂ O ₃ , γ-Fe ₂ O ₃ , acicular iron powder, CrO ₂ having a particle size of 10 μm or less, preferably 0.01 to 5 μm as a magnetic material. Etc., and polyester resins, alkyd resins, vinyl resins, polyurethane resins or mixed resins generally used as binder resins can be used.

  The magnetic recording layer 14 may contain other additives. Examples of other additives include antistatic agents, surfactants, dispersants, plasticizers, and lubricants. The thickness of the magnetic recording layer is about 5 to 20 μm.

  By laminating such layers as described above, the reversible thermosensitive recording medium having the writing property according to the present invention can be obtained. A known method is employed as the lamination method.

Example of lamination of reversible thermosensitive recording medium As another example of lamination of reversible thermosensitive recording medium, a writable layer (formed on a part or the whole surface) 1 / overlay film 14 / adhesive layer 6 / core film 13 / adhesive layer 6 / Overlay film 14 / Reversible thermosensitive recording layer 2 / Protective layer 8, Writable layer (formed on a part or the whole surface) 1 / Overlay film 14 / Adhesive layer 6 / Core film 13 / Circuit on which an IC chip is mounted Examples of the layer structure include substrate layer 4 / core film 13 / adhesive layer 6 / reversible thermosensitive recording layer 2 / protective layer 8 and the like.

[Method for producing reversible thermosensitive recording medium having writability]
Next, a method for producing a reversible thermosensitive recording medium having writability according to the present invention will be described. The method for producing a reversible thermosensitive recording medium having writability according to the present invention includes a roughening process.

Roughening process The method for producing a reversible thermosensitive recording medium having writability according to the present invention is formed by appropriately laminating each of the layers as described above, and the writability is improved by the roughening process. It is possible to produce a reversible thermosensitive recording medium.

  In the present invention, preferably, first, a porous ink such as white ink for forming the writable layer 1 is printed to form the writable layer 1, and then the writable layer 1 is simultaneously applied to the card bonding. By performing the roughening process, a reversible thermosensitive recording medium having writing properties can be obtained. The color of the porous ink is not limited to the color.

  By such a method for producing a reversible thermosensitive recording medium having writability according to the present invention, a reversible thermosensitive recording medium having excellent writing suitability can be obtained.

  In the present invention, if the above method is adopted, the writing layer 1 is formed in a multi-faceted manner by a printing method as compared with a method in which a sign panel is transferred and provided on a single surface after card removal processing. A writable layer can be added.

  In the present invention, a method of simultaneously performing the hot pressing step through the roughened mirror plate or the roughened plate material 15 is employed for such a roughening step.

  In the present invention, the surface of the reversible thermosensitive recording medium on which the writable layer 1 is formed after the hot pressing using a non-roughened specular plate is roughened by the roughening treatment as described above. Processing steps can also be applied.

  Furthermore, in this invention, after finishing the roughening process performed simultaneously with hot press, the roughening process by a roughening process can also be given.

  When the roughening process is performed simultaneously with the hot pressing process via the roughened plate 15, the softening point of the roughened plate 15 is the reversible thermosensitive recording medium to be processed into the writable layer 1. This is higher than the softening point of the outermost layer 10. Such a difference in softening point is preferably about 20 ° C. or more.

The suitably applied hot pressing step and simultaneous roughening processing steps in the present invention, usually, 10 to 70 kg / cm ^2, preferably to a pressure of 15~50kg / cm ^2, 100~170 ℃, preferably The reaction is usually performed in the range of 110 to 150 ° C., for example, by holding for less than 1 hour, preferably about 1 to 50 minutes. The heating temperature in the hot pressing step is determined and selected based on the substrate used and the like. The holding time is merely an example, and is not particularly limited in the present invention.

  For example, when a laminate such as a transparent polyvinyl chloride film / white polyvinyl chloride film / white polyvinyl chloride film / transparent polyvinyl chloride film is used, the surface roughening process (heat press process) The heating temperature is preferably about 130 to 150 ° C. When a laminate such as transparent PETG / white PETG / white PETG / transparent PETG is used, the heating temperature during the roughening process is 110 to 130. It may be about ° C.

  If the pressure or heating temperature at the time of hot pressing exceeds the above range, the Ra value of the obtained reversible thermosensitive recording medium having writability may become too low, and the writing ability may be lowered. If the pressure or heating temperature at the time of hot pressing is less than the above range, it is not preferable because the bonding cannot be performed with sufficient strength.

  Such a hot pressing step may be performed by other means, but the pressure and temperature conditions at the time of heat fusion are performed in the same manner as described above. The hot pressing conditions when the roughening process is not performed simultaneously with the hot pressing are performed in the same manner as described above.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not construed as being limited based on these examples.

Example 1
1-1 Sign Panel (Writing Layer 1) Printing As a backside overlay film, white porous screen ink (Toyo Co., Ltd., trade name: Lumirror # 125E / 28G, 125 μm thick white PET film) Ink Manufacturing Co., Ltd., trade name SS7GK Sign 611 White) was printed by screen printing and dried at 80 ° C. for 15 minutes to form a sign panel portion having a width of 10 mm × length of 38 mm and a thickness of about 7 μm. In this embodiment, it is also possible to print with multiple impositions for a desired imposition, for example, 6 rows 3 columns = 18 impositions. In this case, if the size of the back substrate is, for example, length 430 mm × width 350 mm, 18 faces can be attached.

1-2 Preparatory printing of base material In the film where the sign panel is formed in 1-1 above, UV curable offset ink (manufactured by T & K TOKA Co., Ltd.) is applied to the area that does not overlap the sign panel on the same side as the sign panel. Characters and the like were printed using Best Cure UV161 Black S), and further, UV-curable offset OP ink (UV Calton Prica OP Varnish manufactured by The Inktech Co., Ltd.) was used to protect this printing. At this time, printing was performed avoiding the sign panel.

  Printing was performed on the surface (front surface) side overlay film with UV offset ink (manufactured by Toyo Ink Co., Ltd., trade name “FD Carton P”). Next, a reversible thermosensitive recording material having the following composition was applied onto the overlay film so as to cover the printed layer, dried, and irradiated with ultraviolet rays to form a reversible thermosensitive recording layer having a dry film thickness of 5 μm.

・ Leuco dye: (3-diethylamino-6-methyl-7-anilinofluorane: manufactured by Yamamoto Kasei Co., Ltd., trade name “ODB”) 5 parts by weight ・ Developing color reducing agent: N- (p-hydroxyphenyl)- N′-n-octadecylurea 15 parts by weight Binder resin: Thermoplastic resin (resin obtained by ester-polymerizing acrylic acid to vinyl chloride-vinyl acetate-vinyl alcohol copolymer, solid content 30%) 66 parts by weight Light Polymerization initiator: (Ciba Specialty Chemicals Co., Ltd .: trade name Darocur 184) 2 parts by weight Solvent (MEK (methyl ethyl ketone): toluene = 1: 1 (weight ratio) 114 parts by weight

Next, a paint having the following composition is applied on the reversible thermosensitive recording layer, dried at 100 ° C. for 2 minutes, and irradiated with ultraviolet rays (160 W / cm, 30 m / min, 1 pass) to protect a dry film thickness of 3 μm. A layer was formed.
・ Ultraviolet curable paint (Dainippon Ink Chemical Co., Ltd., trade name “Unidic C3-374” 20 parts by weight) ・ Silica (Mizusawa Scientific Co., Ltd., trade name “Mizukasil P-603”) 1 part by weight・ Solvent (MEK: toluene = 1: 1 (weight ratio) 20 parts by weight

1-3 Including (Hot press)
As shown in FIG. 3, a core film composed of two PETG films (Diafix PG-W, manufactured by Mitsubishi Plastics) having a thickness of 200 μm between the front surface side overlay film and the back surface side overlay film described above. A 100 μm thick hot melt adhesive film (sheet-like hot melt adhesive Aron Melt PES-111 manufactured by Toa Gosei Co., Ltd.) is sandwiched, and one surface is rough so as not to impair the writing ability of the sign panel. Roughened PET sheet (T-100, manufactured by Mitsubishi Polyester Film Co., Ltd., thickness 188μm, Ra value of roughened surface is about 0.6μm) Roughened surface is relative to writable layer 1 Placed on the writable layer 1 so that the mirror plate and cushion paper (thickness of about 1 mm × 3 sheets) overlap, and set between the hot press hot platen 32 to reduce the surrounding atmosphere, pressurized to 13kg / cm ² After heating at 125 ° C. for 15 minutes, cooling and bonding, and punching into ID-1 type size specified in JIS X6301, the reversible thermosensitive recording medium of this example was manufactured and manufactured Evaluation was performed using a reversible thermosensitive recording medium. The results are shown in Table 1.

  In addition to this example, a film made of a resin with a higher softening point than a highly oil-absorbing ink having writing suitability is roughened using sand, or the mirror plate is directly etched and used. The writable layer 1 can also be provided by roughening at least a part of the outermost layer 10.

Example 2
An antenna circuit is formed on the film, and an IC module (IC chip circuit board layer) on which an IC chip is mounted is interposed between a core film having a through hole at a position corresponding to the IC chip and another core film. A reversible thermosensitive recording medium was produced in the same manner as in Example 1 except that the evaluation was performed and evaluated. The results are shown in Table 1.

Comparative Example 1
A reversible thermosensitive recording medium was produced in the same manner as in Example 1 except that it was hot-pressed using a mirror-finished plate whose surface was not roughened without interposing a roughened film. Evaluation was performed. The results are shown in Table 1.

Comparative Example 2
Use a backside overlay film that does not form a sign panel, hot press using a mirror-finished surface plate without a roughened film, and reversibly after hot pressing A reversible thermosensitive recording medium was produced in the same manner as in Example 1 except that a sign panel having a thickness of 12 μm was formed on the opposite surface of the thermosensitive recording layer from the sign panel forming ink used in Example 1. Evaluation was carried out using. The results are shown in Table 1.

Results As shown in Table 1, the reversible thermosensitive recording media of Examples 1 and 2 and Comparative Example 2 had good writing ability, whereas the reversible thermosensitive recording media of Comparative Example 1 Had no writing ability for ballpoint pens.
Further, when printing was performed on the reversible thermosensitive recording layer of the reversible thermosensitive recording medium shown in each example and each comparative example using a thermal head, the reversible thermosensitive recording of Example 1, Example 2 and Comparative Example 1 was performed. In the medium, no print fading occurred, whereas in the reversible thermosensitive recording medium of Comparative Example 2, print fading occurred at the position of the reversible thermosensitive recording layer corresponding to the edge of the sign panel.

  Thus, according to the invention of the reversible thermosensitive recording medium having writability according to the present invention, the reversible thermosensitive recording layer 2 (rewrite display portion) is provided on the front surface of the substrate 3, and the opposite surface is provided on the opposite surface. Since the writable layer 1 is provided substantially flush, there is no pressure difference of the thermal head due to the level difference between the writable layer 1 and the uppermost layer surface, so that the reversible thermosensitive recording layer 2 does not cause printing unevenness and fading. . In addition, if the reversible thermosensitive recording medium having writability according to the present invention is used for an ID card or the like, there is no need to increase the pressure of the thermal head in order to prevent uneven printing or fading, so that the reversible feeling is long and has little contamination. A thermal recording medium is obtained.

  By applying such a reversible thermosensitive recording medium having writability to a card, even if the print surface and the end of the writable layer 1 are provided in the normal direction of the card surface, When erased, the end portion of the writable layer 1 has substantially no step, printing unevenness and blurring do not occur, and the outermost layer 10 provided with the writable layer 1 is an outermost layer. Since it is provided at any position of 10 without being restricted, it is possible to write the name of the person, a code and the like, and the thermal head is difficult to get dirty with a long life, and scratches are less likely to occur on the card during printing. Therefore, the reversible thermosensitive recording medium having writability according to the present invention can be used as a clean card with few scratches over a long period of time.

  Such a reversible thermosensitive recording medium having writability according to the present invention is particularly suitable for cards used for a long period of time such as IC cards and commuter passes.

It is a figure which shows an example of the laminated constitution of the reversible thermosensitive recording medium which has the writability concerning this invention. It is a figure which shows another example of the layer structure of the reversible thermosensitive recording medium which has writing property based on this invention, (a) shows the layer structure example of the card | curd obtained in Example 1, (b) These show the layer structural example of the card | curd obtained in Example 2. FIG. It is a figure which shows the manufacturing method of the reversible thermosensitive recording medium which has the writing property based on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Writable layer 2 Reversible thermosensitive recording layer 3 Base material 4 IC chip circuit board layer 5 IC chip 6 Adhesive layer 7 Printing 8 Protective layer 10 Outermost layer 13 Core film 14 Overlay film 15 Roughened board | plate material 21 Mirror surface board 31 Buffer Material (cushion)
32 Hot plate

Claims (5)

A writable layer comprising a reversible thermosensitive recording layer on a substrate, and containing a porous material in at least a part of the outermost layer on the opposite surface of the substrate having the reversible thermosensitive recording layer. A method for producing a reversible thermosensitive recording medium comprising:
Perform each layer hot press constituting the reversible thermosensitive recording medium, the outermost layer having said writing layer performs roughening treatment, the surface roughening treatment, hot pressing via a roughened plate A method for producing a reversible thermosensitive recording medium, which is performed simultaneously. A writable layer comprising a reversible thermosensitive recording layer on a substrate, and containing a porous material in at least a part of the outermost layer on the opposite surface of the substrate having the reversible thermosensitive recording layer. A method for producing a reversible thermosensitive recording medium comprising:
Perform each layer hot press constituting the reversible thermosensitive recording medium, the outermost layer having said writing layer performs roughening treatment, the surface roughening treatment, a heat press in the mirror plate is not roughened And a method for producing a reversible thermosensitive recording medium, which is performed through a roughened plate material. The method for producing a reversible thermosensitive recording medium according to claim 1 or 2, wherein the writable layer is formed by printing porous ink. The reversible thermosensitive recording medium according to any one of claims 1 to 3, wherein each layer constituting the reversible thermosensitive recording medium includes an IC circuit board layer on which an IC chip is mounted. Method. The method for producing a reversible thermosensitive recording medium according to any one of claims 1 to 4 , wherein the plate material is a film made of a resin higher than a softening point of the outermost layer.

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