JP4416068B2 - THERMAL RECORDER, THERMAL RECORDING LAYER TRANSFER SHEET, THERMAL RECORDING LAYER LABELING LABEL AND RECORDING METHOD - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
In the present invention, a layer capable of thermal destruction recording using heat generated by photothermal conversion of a near infrared absorbing layer upon irradiation with a near infrared laser beam overlaps a layer capable of thermal color development recording with a thermal head or the like. The present invention relates to a composite thermosensitive recording layer capable of eliminating the influence on other layers during recording on each layer, and a thermosensitive recording medium provided with such a composite thermosensitive recording layer. In particular, the present invention relates to a thermal destructive recording using a heat generation by photothermal conversion of a near infrared absorbing layer upon irradiation of a near infrared laser beam or the like from the side of a layer capable of thermal recording, that is, a thermal head. The present invention relates to a heat-sensitive recording material of a type that performs heat-sensitive color-development recording.
The present invention also relates to a heat-sensitive recording layer transfer sheet suitable for applying such a composite heat-sensitive recording layer to an adherend such as a card, and a label for sticking a heat-sensitive recording layer.
Furthermore, the present invention also relates to a recording method for recording on the above-mentioned composite thermosensitive recording layer, thermosensitive recording material, thermosensitive recording layer transfer sheet, and thermosensitive recording layer sticking label.
[0002]
[Prior art]
In cards, when necessary, individual information or the like is printed to form a recording medium and provided to the client.
In this case, the card itself (which is not recorded with individual information), which is the basis of the ID card, is often a material that can hold information, but in addition, printing of information and the like is possible. In order to make it possible to do it immediately, printing is performed using a material whose hue and light reflectivity change depending on the energy applied during printing, or a material that accepts a coloring material given externally by printing. A planned area is often formed.
[0003]
For example, since a plastic card, which is a material of plastic, has embossability, the credit card number, the name of the contractor, the expiration date, and the like can be recorded by forming uneven characters.
In addition, an ink ribbon containing a sublimation dye can be used to output images such as characters and facial photographs to a card base or a specially laminated dye-accepting resin layer, or an ink-accepting layer. To sign a contractor.
[0004]
Alternatively, in the prepaid card for transportation, a thermochromic recording layer is formed on one side, and the usage details, collection fee, balance, etc. are printed each time, and a regular ticket The contents are also printed at the time of issuance on a similar heat-sensitive color-developing recording layer.
[0005]
By the way, it is rare that all the information is printed every time it is issued by preparing a completely blank card in the above-mentioned cards and information recording bodies other than the card.
This is because the printing means used at the time of issuance has limited performance. For example, recording using laser light enables fine recording, but the material is limited and only binary recording can be performed. According to the sublimation transfer method, a good color image can be obtained, but the processing speed is high. It is slow and is not suitable for recording on the entire surface. Further, according to the thermal recording, the processing speed is fast, but it is limited to monochrome binary recording.
[0006]
Therefore, in actual operation, the amount of information printed at the time of issuance is reduced as much as possible.
For example, in the case of credit cards and bank savings cards, the name of the issuing company or bank name, card name, surface pattern, item name such as “expiration date”, precautionary notes, etc. are printed using the normal printing method. When issuing, the information is recorded on the magnetic stripe, the card issuance number by embossed characters, the name of the contractor, and the expiration date are formed.
Or, in the case of commuter pass, print a background pattern designed with the railroad company mark on the front side, and a cautionary note etc. on the back side, and when issuing it, pass the name, age, boarding section of the purchaser on the front side Print the expiration date.
[0007]
However, if several types of information to be printed at the time of issuance are recorded by the same method, it is difficult for a person who intends forgery / alteration to prepare and record the recording means. For the purpose of increasing the performance, it is desirable to use a plurality of different recording means in combination and to record in the same area.
[0008]
Although there are various recording means to be selected, thermal recording is mainly performed by a thermal head in that printing can be performed at high speed according to information output when a card or the like is issued.
Typical materials that can be used for thermal recording with a thermal head are thermal coloring layers that use two-component thermal coloring agents such as leuco dyes and acidic developers, and thermal sensitivity that uses a metal film with a relatively low melting point. There is a destructive layer.
[0009]
However, when these two types of materials are stacked and recording is performed with a contact-type thermal head, heat is always transferred from the side in contact with the head, so it is impossible to record on each layer independently. For example, even when recording is performed on the lower layer, recording is performed on an undesired upper layer due to the influence of heat.
[0010]
[Problems to be solved by the invention]
Therefore, in the present invention, when two types of recording layers, both of which are thermally recorded, are used in an overlapping manner, it is an object to enable recording on each layer independently. To do.
[0011]
[Means for solving the problems]
The above problem is that two types of layers that are stacked one above the other, both capable of thermal recording, contact heating printing with a thermal head for the upper layer, and near-infrared absorbing layer for the lower layer It has been found that this problem can be solved by performing non-contact heating printing using heat generated by irradiating a low-power near-infrared laser beam.
[0012]
In the first invention, at least a part of the substrate is At least the heat-sensitive destruction layer, the near-infrared absorbing layer, the transparent heat-insulating layer, and the heat-sensitive color-forming layer were laminated in order. The present invention relates to a thermal recording material that is laminated such that the thermal breakdown layer side of the composite thermal recording layer faces the substrate side. A second invention relates to the heat-sensitive recording material according to the first invention, wherein the composite heat-sensitive recording layer has a colored layer laminated on the opposite side of the heat-sensitive destruction layer to the near-infrared absorbing layer. A third invention relates to the heat-sensitive recording material according to the first or second invention, wherein the heat-sensitive color-forming layer contains a dye precursor that does not absorb in the near infrared region after color development. A fourth invention relates to a heat-sensitive recording material according to any one of the first to third inventions, wherein an adhesive layer is laminated on the exposed surface of the composite heat-sensitive recording layer. The fifth invention is: At least the heat-sensitive destruction layer, the near-infrared absorbing layer, the transparent heat-insulating layer, and the heat-sensitive color-forming layer were laminated in order. The present invention relates to a heat-sensitive recording layer transfer sheet in which the heat-sensitive color-developing layer side of the composite heat-sensitive recording layer is laminated on the peelable surface of the peelable substrate sheet. The sixth invention is: At least the heat-sensitive destruction layer, the near-infrared absorbing layer, the transparent heat-insulating layer, and the heat-sensitive color-forming layer were laminated in order. The present invention relates to a label for sticking a heat-sensitive recording layer in which the heat-sensitive color-developing layer side of a composite heat-sensitive recording layer is laminated on a transparent substrate sheet. The seventh invention At least the heat-sensitive destruction layer, the near-infrared absorbing layer, the transparent heat-insulating layer, and the heat-sensitive color-forming layer were laminated in order. The present invention relates to a label for sticking a heat-sensitive recording layer, comprising a composite heat-sensitive recording layer, and the transparent heat insulating layer being a transparent substrate sheet. The ninth invention is the one of the first to fourth inventions. Thermal recording material , Of the fifth invention Thermal recording layer transfer sheet, or Of the sixth or seventh invention The near-infrared absorbing layer of the label for sticking a heat-sensitive recording layer is irradiated with near-infrared laser light to generate heat by photothermal conversion, and the heat-sensitive destruction layer is recorded on the heat-sensitive destruction layer by the heat. The present invention relates to a recording method comprising performing thermal recording by bringing a heated recording means into contact with a color forming layer.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a composite thermosensitive recording layer 1 which is a characteristic part of the present invention. Basically, as shown in FIG. 1, from the bottom, a thermosensitive destruction layer 2 made of a metal thin film, etc. The outer absorptive layer 5, the transparent heat insulating layer 3 made of a transparent resin, and the like, and the two-component color former such as a leuco dye and an acid developer, and the heat-sensitive color developing layer 4 made of a resin and the like were laminated in order. Is.
The composite thermosensitive recording layer 1 is preferably used by being laminated on an adherend such as a card substrate so that the heat-sensitive destruction layer 2 side is in contact therewith.
[0014]
With respect to the above basic laminated structure, various layers can be laminated to improve the function. The addition of these layers will be described below with reference to FIGS. 2 and 3.
[0015]
As shown in FIG. 2, the composite thermosensitive recording layer 1 may have a colored layer 6 laminated on the bottom layer. Addition of the colored layer 6 increases the visibility of the recording formed by the fine apertures in the heat-sensitive destruction layer 2.
FIG. 2 shows a structure corresponding to a structure in which a colored layer 6 is added to the lowermost layer of the composite thermosensitive recording layer 1 shown in FIG.
As will be described later, the colored layer 6 may be a magnetic recording layer containing magnetic material powder.
[0016]
In FIG. 3, the structure which did not appear in the above description and was laminated | stacked by adding the protective layer 8 to the uppermost layer and adding the adhesive bond layer 7 to the lowest layer is shown.
The protective layer 8 and the adhesive layer 7 are laminated by adding only the protective layer 8 to the uppermost layer and laminating only the adhesive layer 7 on the lowermost layer for each structure as shown in FIGS. There may be a case where the layers are additionally laminated, or the protective layer 8 is laminated on the uppermost layer and the adhesive layer 7 is laminated on the lowermost layer.
[0017]
FIG. 4 shows a state in which the above-mentioned composite thermosensitive recording layer is laminated on a base material 12 such as a card base material as an adherend. In FIG. 4 (a), the composite heat sensitive shown in FIG. The recording layer 1 is laminated, and in FIG. 4B, the lowermost adhesive layer 7 of the composite thermosensitive recording layer 1 shown in FIG.
All of them merely exemplify the composite thermosensitive recording layer 1 that can be laminated, and any of the composite thermosensitive recording layers described so far can be laminated on the substrate 12.
[0018]
In the lamination of the composite thermosensitive recording layer 1 and the substrate 12, the composite thermosensitive recording layer 1 may be laminated on the entire surface of the substrate 12, or may be laminated on a part of the substrate 12. It may be laminated at one place on the material 12 or may be laminated at a plurality of places.
The composite thermosensitive recording layer 1 may be laminated only on one side of the base material 12, but may be laminated on both the front and back surfaces of the base material 12.
[0019]
When laminating the composite thermosensitive recording layer 1 on the base material 12, when the base material 12 is composed of a laminate of a plurality of sheets, other than simply mounting and fixing on the base material 12, In addition to the surface of the laminated body, it can be laminated between a plurality of sheets constituting the substrate. For example, as in a typical credit card or bank savings card, a laminate of four sheets of a transparent oversheet, two opaque core sheets, and a transparent oversheet, oversheet and core sheet You may laminate between.
[0020]
In the present invention, the composite thermosensitive recording layer 1 of various aspects described above is laminated on the base material 12 by sequentially laminating from the side in contact with the base material 12 by coating or the like (partially vapor deposition or the like). However, it is better to once form a laminate on which a composite thermosensitive recording layer is applied, which is laminated on a flexible substrate sheet separate from the substrate 12, and then laminate the formed laminate on the substrate 12. In terms of industrial convenience, there are two types of laminates, transfer sheets and labels.
[0021]
FIG. 5A and FIG. 5B show examples of such a transfer sheet 21 type, and FIG. 5A shows a peelable surface (see FIG. 5) of the peelable substrate sheet 22. In this case, the heat-sensitive color-developing layer 4, the transparent heat-insulating layer 3, the near-infrared absorbing layer 5, the heat-sensitive destruction layer 2, the colored layer 6, and the adhesive layer 7 are laminated in this order on the lower surface. It is.
Moreover, what is shown in FIG.5 (b) has the protective layer 8 laminated | stacked on the peelable surface of the peelable base material sheet 21 first, and others are the same as what is shown to Fig.5 (a). It is.
After any of the transfer sheets is placed on the substrate 12 as the adherend with the adhesive layer 7 side as the adherend side, the transfer sheet is heated and / or pressurized from the upper surface side of the peelable substrate sheet 21 and adhered. The composite thermosensitive recording layer is transferred onto the substrate 12 by peeling the peelable substrate sheet 21.
[0022]
In the above, as the composite heat-sensitive recording layer, any of the above-described materials other than those described above may be provided on the peelable surface of the peelable substrate sheet.
The adhesive layer 7 is preferably laminated for industrial reasons, but an adhesive can be applied at the time of transfer, or an adhesive layer is previously laminated on the adherend. In some cases, it can be omitted.
With respect to peeling between the peelable substrate sheet and the layer to be transferred in the structure of the transfer sheet, various layers can be interposed. For example, when the peelability between the base sheet and the composite thermosensitive recording layer is poor, a peelable layer is laminated on the base sheet to give the peelability. This peelable layer remains on the base sheet side during transfer.
[0023]
On the most peelable substrate sheet side of the composite thermosensitive recording layer 1, a release layer for facilitating peeling from the substrate sheet 21 or the peelable layer may be laminated, and due to the presence of the release layer, When the release layer is interposed between the release layer and the base sheet of the transfer sheet, the adhesion between the release layer and the release layer is appropriately maintained, and at the time of transfer, It is intended to make the gaps peel off smoothly. When the protective layer 8 is laminated, the protective layer 8 can also contain a release agent, and can also serve as the protective layer 8 and the release layer.
[0024]
FIG. 6 shows an example of the type of label, and the one shown in FIG. 6A is formed on the lower surface of the transparent base sheet 32 on the thermosensitive coloring layer 4, the transparent heat insulating layer 3, and the near infrared absorptivity. This is a label 31 made of a laminate in which the layer 5, the heat-sensitive destruction layer 2, the colored layer 6, and the adhesive layer 7 are laminated in order downward.
The label 31 is placed on the substrate 12 as an adherend with the adhesive layer 7 side as the adherend side, and is heated and / or pressurized from the upper surface side of the transparent substrate sheet 32 to be bonded. A composite thermosensitive recording layer is laminated on the material 12.
In the label 31, the composite thermosensitive recording layer laminated on the lower surface of the transparent base sheet 32 may be any of those described so far.
[0025]
By the way, in the label 31 described with reference to FIG. 6A, since the transparent base sheet 32 is the uppermost layer, when the thermosensitive coloring layer 4 is colored by contact with the thermal head, the sensitivity is reduced. As the transparent base sheet 32, a very thin object of 6 μm or less is preferably used.
In the label shown in FIG. 6 (b), the transparent heat insulating layer 3 in FIG. 6 (a) is replaced with the transparent base sheet 32, and the protective layer 8 may be laminated in this way as necessary. You can omit it. In this case, since the transparent substrate sheet 32 is not in the uppermost layer, the recording sensitivity to the thermosensitive coloring layer 4 is not lowered.
[0026]
The transparent base sheet 32 in the label 31 can be laminated in a lower layer.
The transparent substrate sheet 32 can be laminated on the upper surface or the lower surface on which the heat-sensitive destruction layer 2 and the light absorbing layer 5 are laminated. Avoid laminating a transparent substrate sheet between the heat-sensitive destruction layer 2 and the near-infrared absorbing layer 5.
When the heat-sensitive destruction layer 2 is accompanied by the colored layer 6, the transparent substrate sheet 32 may be laminated between the heat-sensitive destruction layer 2 and the colored layer 6. From the viewpoint of properties, it is preferable not to laminate between the heat-sensitive destruction layer 2 and the colored layer 6, and therefore, it is preferable that the layer is laminated on the upper surface or the lower surface where the heat-sensitive destruction layer 2 and the colored layer 6 are laminated. When the composite thermosensitive recording layer in the label 31 is accompanied by the adhesive layer 7 on the lowermost surface, the transparent base sheet 32 can be laminated immediately above the adhesive layer 7.
[0027]
The heat-sensitive color-forming layer 4 is mainly composed of an electron-donating dye precursor and an electron-accepting compound that react with each other by melting and reacting by heating, and these are dispersed in a resin binder.
[0028]
As the electron-donating dye precursor, those used as this type of heat-sensitive recording material as a leuco dye can be used, and those that respectively color yellow, magenta, and cyan are selected for color reproduction.
Specifically, a leuco compound of a dye such as triphenylmethane, fluorane, phenothiazine, auramine, spiropyran, or indinophthalide is preferably used.
When a dye precursor that does not absorb in the near infrared region after color development is used and solid printing (= color uniformly and uniformly), the lower layer is apparently hidden, but reading with an infrared barcode reader, etc. Allows the machine to read the underlying information.
[0029]
The electron-accepting compound is used as a developer in combination with the above-mentioned electron-donating dye precursor, and has heat resistance enough to withstand the heat when pasted on an adherend by heating and pressing. In the thermal recording with a thermal head or the like, one that reacts with high sensitivity is selected.
[0030]
Specifically, phenolic substances such as bisphenol A, octylsulfonic acid, nonylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, octadecylphosphonic acid, or eicosylphosphonic acid, α -Organic acids such as hydroxyoctanoic acid, α-hydroxydecanoic acid, α-hydroxytetradecanoic acid, or α-hydroxyoctadecanoic acid, metal complex compounds, thiodiphenylurea, or quinones Is preferably used.
[0031]
Examples of the resin binder for dispersing the electron-donating dye precursor and the electron-accepting compound include polyvinyl alcohol, starch, modified starch, methylcellulose, hydroxyethylcellulose, gelatin, casein, alkylene / maleic anhydride copolymer, and polyvinylpyrrolidone. , Water-soluble resins such as acrylamide-based water-soluble resins, styrene / butadiene copolymer emulsions, urea resins, melamine resins, amide resins, or polyurethane resins.
[0032]
In addition to the above, various additives can be added to the thermosensitive coloring layer 4, and examples of the additive include a sensitizer, an anti-fading agent, and a pigment.
Examples of the sensitizer include 1-hydroxy-2-naphthoic acid phenyl, p-benzylbiphenyl, stearic acid amide, behenic acid amide, methylenebisstearic acid amide, dibenzyl oxalate, tolylbiphenyl ether, and aliphatic amides. Is mentioned.
Examples of the anti-fading agent include analogs of color developers blocked with hydroxyl groups, organometallic salts such as zinc salts, hindered phenols, and the like.
As the pigment, pigments that are not concealable, have a high oil absorption, have a high pH, and are inactive with respect to dyes are required. If it is a white pigment, there exists an effect which scatters visible light and near-infrared light around, accelerate | stimulates near-infrared light absorption to a light absorber, and raises a heat_generation | fever effect. Specific examples of the pigment include calcium carbonate, aluminum hydroxide, silicate, zeolite, silica, kaolin, clay, and urea formalin resin.
[0033]
The transparent heat insulating layer 3 is composed of a transparent resin, and preferably a pigment dispersed in the transparent resin. These are those that do not interfere with the color development of the thermosensitive color-developing layer and that do not have a concealing property.
The transparent heat-insulating layer 3 is preferably thicker for the purpose of thermally blocking between the near-infrared absorbing layer and the heat-sensitive color-developing layer, but when applied to a card or the like, it is determined as an adherend. The upper limit of the thickness is exceeded, so that it is not suitable for the clearance set in the reader, etc., it is preferable that the thickness is thin. In practice, the thickness is preferably 1 to 3 μm.
[0034]
Transparent resins include polyvinyl alcohol, starch, modified starch, methylcellulose, hydroxyethylcellulose, gelatin, casein, alkylene / maleic anhydride copolymer, polyvinylpyrrolidone, acrylamide water-soluble resin, styrene / butadiene copolymer emulsion, urea resin , Melamine resin, amide resin, or polyurethane resin.
Examples of the pigment include calcium carbonate, aluminum hydroxide, silicate, zeolite, silica, kaolin, clay, and urea formalin resin.
[0035]
The near-infrared absorptive layer 5 contains a light absorber for converting near-infrared light into heat in the resin binder, and is located in the lower layer of the thermosensitive color-developing layer 4. In order not to hinder the visibility of the recording on the layer 4, it is desirable that it be colorless or light even if colored.
[0036]
Examples of the light absorber constituting the near-infrared absorbing layer 5 include phthalocyanine-based, naphthalocyanine-based, bisthiourea-based compounds, squarylium-based, azurenium-based, triphenylamine-based, trisazo-based, diphenylmethane-based, and triphenylmethane. Quinone, naphthoquinone, anthraquinone, azo, immonium, diimmonium, metal complex, metal sulfide and thiourea compound, or phosphorus compound and copper compound, etc. Use two or more.
[0037]
The heat-sensitive destruction layer 2 generates heat by the photothermal conversion effect in the non-absorbing layer 5 by irradiation with near-infrared laser light or the like, and a portion to which the heat is transferred melts or evaporates, so that the colored layer or the like The color of the ground becomes visible.
Specifically, the thermal breakdown layer 2 is a layer of a metal thin film having a relatively low melting point such as Te, Sn, In, Bi, Pb, Zn, or Al, or an alloy of these metals, or these It may be a thin film made of a compound containing a metal, such as Te-C.
[0038]
The thin film made of these materials is formed by vacuum deposition, sputtering, plating, or the like. The thickness of the thin film is 10 nm to 1 μm, more preferably 50 to 100 nm, although it depends on the material so that the destruction by heat occurs sufficiently.
An anchor layer may be laminated on the upper and lower sides of the thermal breakdown layer 2. By laminating the anchor layer, the adhesion strength between the layers sandwiching the anchor layer is improved, and the thermal breakdown layer 2 is smoothly broken due to melting or the like, and the printing sensitivity is improved. The anchor layer is formed of, for example, a polyester resin, a vinyl chloride / vinyl acetate copolymer, a thermoplastic resin such as a polyvinyl chloride resin, or a thermosetting resin such as a polyurethane resin, and the thickness is preferably about 1 μm.
[0039]
The protective layer 8 is laminated as necessary, and by the protective layer 8 being laminated on the outermost surface, the surface of the composite thermosensitive recording layer on the adherend such as a card is rubbed during use, It prevents wear or thermal deformation when receiving heat, etc., has chemical resistance, water resistance, wear resistance, etc. and has transparency to allow the lower layer to be seen through. It is preferable to have it.
[0040]
The protective layer 8 is composed of the above-described binder resin, and for the purpose of enhancing the surface wear resistance, chemical resistance, stain resistance, etc., a thermosetting resin or an ionizing radiation plug curable resin. (UV curable magnetic recording layer or electron beam curable resin) may be used, and the thickness is about 0.1 to 10 μm.
An anchor layer may be interposed between the phases in order to ensure adhesion between the protective layer 8 and the lower layer (for example, a thermosensitive coloring layer).
[0041]
The colored layer 6 is laminated on the lower layer of the heat-sensitive destruction layer 2 and can be seen from the opening portion generated by the recording of the heat-sensitive destruction layer 2, so that a sufficient contrast with the hue of the heat-sensitive destruction layer 2 can be obtained. A dye or pigment colorant is used and a toned coating composition or ink composition is used, and roll coating, gravure coating, or knife edge coating, which are known coating methods, or It is formed by gravure printing or offset printing which is a known printing method.
[0042]
For this purpose, the coating composition or ink composition is usually a binder used in these preparations, and a colorant, solvent or dispersant consisting of pigments and / or dyes, and other additives usually added to the coating composition or ink composition. It is obtained by blending and kneading the product.
[0043]
Examples of binders for coating compositions or ink compositions include cellulose derivatives such as ethyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate propionate, or cellulose acetate, styrene resins such as polystyrene or poly-α-methylstyrene, and styrene copolymer resins. Acrylic resin such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, or polybutyl acrylate, or a methacrylic resin alone or copolymer, rosin, rosin modified phenolic resin, or rosin ester resin such as polymerized rosin , Polyvinyl acetate resin, coumarone resin, vinyl toluene resin, vinyl chloride resin, polyester resin, polyurethane resin, or butyral resin.
[0044]
The colored layer 6 may be a magnetic recording layer containing magnetic material powder. This is because the magnetic material powder is generally brown that is nearly black.
As magnetic material powder, γ-Fe ₂ O _Three Co-deposited-Fe ₂ O _Three , Fe _Three O _Four , CrO ₂ , Fe, Fe-Cr, Fe-Co, Co-Cr, Co-Ni, Mn-Al, Ba ferrite, Sr ferrite or the like can be used.
[0045]
When the colored layer 6 is a magnetic recording layer containing magnetic material powder, the binder includes butyral resin, vinyl chloride / vinyl acetate copolymer, polyurethane resin, polyester resin, cellulosic resin, acrylic resin, or styrene / A maleic acid copolymer resin can be used. Nitrile rubber or urethane elastomer is added as necessary.
[0046]
Formation of the magnetic recording layer as the colored layer 6 includes the above magnetic material powder and binder, solvent or dispersant, surfactant, silane coupling agent, plasticizer, wax, silicone oil, carbon, etc. The coating composition or ink composition obtained by adding and dispersing the above pigment or the like is used for gravure coating, roll coating, knife edge coating, or the like, so as to have a thickness of 1 to 100 μm, more preferably 5 to 20 μm.
[0047]
The adhesive layer 7 is formed by using an adhesive that is excellent in adhesiveness with the composite thermosensitive recording layer 1 in the present invention and selected in consideration of the adhesiveness with the substrate 12 of an adherend such as a card.
Specific examples of adhesives include vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, acrylic resins, polyester resins, polyurethane resins, polyamide resins, and rubber-modified products. These can be selected and used as appropriate, and these can be used alone or in a mixed system of two or more, and further added with a hard resin, a plasticizer, and other additives as necessary. can do.
[0048]
The base material 12 can be comprised with a plastic film, paper, a nonwoven fabric, or metal foil, or those composites. Among these, plastic films such as polyester resin films and polyvinyl chloride resin films are suitable in terms of tensile strength, flexibility, smoothness, and the like.
In the case of a thick card substrate 12, for example, in the case of a general credit card or bank savings card, four sheets of a transparent oversheet, two opaque core sheets, and a transparent oversheet You may comprise the base material 12 with the laminated body of.
The substrate 12 may be provided with a magnetic recording layer or an electromagnetic information storage means such as an IC module, and the printing on the thermal recording medium is stored in the storage means or used. You may carry out based on the information updated each time.
[0049]
In the present invention, the peelable substrate sheet 22 used when the composite thermosensitive recording layer 1 is in the form of a transfer sheet is heat resistant such as a polyethylene terephthalate resin film, a polypropylene resin film, a polycarbonate film, or a polyamide resin film. A resin film is used, and if necessary, a silicone resin coating film or a wax-containing coating film is laminated to provide the surface with peelability.
[0050]
In the present invention, as the transparent base sheet 32 when the composite thermosensitive recording layer 1 is used in the label format, the heat-resistant resin film mentioned as the material of the peelable base sheet 22 is specially used. It is preferable to use an anchor agent laminated on the upper surface or / and the lower surface of the transparent base sheet 32 as needed.
[0051]
The composite heat-sensitive recording layer 1, the heat-sensitive recording member 11, the heat-sensitive recording layer transfer sheet 21 or the heat-sensitive recording layer sticking label 31 of the present invention is recorded and used by the method shown in FIG.
In FIG. 7, from the thermal recording body 11 as shown in FIG. 4B, that is, from the base material 12 side, the colored layer 6, the thermal breakdown layer 2, the near infrared absorbing layer 5, and the transparent heat insulating layer 3. , And a heat-sensitive color-developing layer 4 are sequentially laminated, and the protective layer 8 is omitted.
[0052]
As depicted on the left side in FIG. 7, the laser light 41 emitted from the laser light source is condensed and irradiated onto the necessary portion 43 of the near-infrared absorbing layer 5 using the lens 42, and the condensing unit 5a. The metal thin film of the heat-sensitive destruction layer 2 is melted and removed from the position adjacent to the light condensing part 5a by the generated heat, and the hole part 2a is generated to generate heat in a non-contact manner. Destruction records are made.
In the example of FIG. 7, since the colored layer 6 is present in the lower layer of the aperture 2a, when viewed from above, the color of the colored layer 6 and the color of the material of the heat-sensitive destruction layer 2 as viewed from the aperture 2a. Due to the contrast, the visibility of the aperture 2a is increased.
[0053]
In recording on the heat-sensitive destruction layer 2 by the near infrared laser light, the near infrared laser light 41 is condensed on the near infrared absorbing layer and used. When passing through the thermosensitive coloring layer 4, the near infrared laser light 41 is not absorbed and no heat is generated, so that the thermosensitive coloring layer 4 is not colored.
Further, even if heat is generated at the light collecting portion 5a of the near infrared absorbing layer 5, a large amount of heat is transmitted from the lower layer to the heat-sensitive color forming layer 4 because there is a transparent heat insulating layer between the heat-sensitive color forming layer 4 and the heat-sensitive color forming layer 4. Again, the thermosensitive coloring layer 4 does not develop color.
[0054]
Further, as depicted on the right side of FIG. 7, when the thermal head 51 is brought into contact with the heat-sensitive color forming layer 4 and heated, the color developing components in the heat-sensitive color developing layer 4 are melted by heat at the contact portion. Thus, the color developing portion 4a is generated, that is, thermal recording is performed by the heated recording means.
In recording on the thermosensitive coloring layer 4 by this thermal head, heat is brought from the thermal head 51. The influence of this heat on the thermal destructive layer 2 is the transparent heat insulating layer 3 under the thermosensitive coloring layer 4. Is prevented. In this case, the lower near-infrared absorbing layer 5 also functions as a heat insulating layer in relation to the thermal head.
[0055]
Therefore, non-contact type thermal destruction recording by near infrared laser light and contact type thermal color recording by thermal head can be performed independently, and non-contact type recording is solid (uniform and uniform). Unless done, both records appear to overlap.
In addition, when contact recording is performed in a solid state, the non-contact recording is covered, so in particular, when the contact recording is a dark color system, the lower contact non-contact recording is concealed regardless of the colored hue of the lower layer. Can do.
In the above, the non-contact type recording and the contact type recording may be performed either before or after. In addition, the thermal breakdown layer can be configured to be able to record by irradiating a laser beam from below, but when it is used by being attached to the substrate 12 of the adherend, the laser is applied from the same side where thermal recording is performed. It is better to perform non-contact thermal breakdown recording with light or the like.
[0056]
As described above, even when the thermal breakdown record of the lower layer is not visually visible, it is possible to perform reading using infrared rays. If a material is selected as the upper heat-sensitive color-developing layer 4 so that the lower layer is visually concealed after color development and does not absorb in the near-infrared region, the recording of the lower heat-sensitive destruction layer 2 is recorded in the near-infrared region. It is because it can be read by.
[0057]
As a preferable example of reading using near infrared rays, the lower heat-sensitive destruction layer 2 is subjected to non-contact recording such as a fine bar code, password and ID number with a semiconductor laser or the like, and the upper heat-sensitive coloring layer. If the contact recording is performed in a solid state in 4, the non-contact recording can be read only by a reader using a near infrared light source.
In addition, if the recording is performed on the lower heat-sensitive destruction layer 2 after the solid recording is performed on the upper heat-sensitive color-developing layer 4, the recorded content cannot be seen even in the non-contact recording. It is more preferable in terms of ensuring security.
[0058]
【Example】
Example 1
A heat-sensitive recording material 11 having a layer configuration almost the same as that shown in FIG. 4B was produced as follows.
A polyethylene terephthalate resin film (E-20, manufactured by Toray Industries, Inc.) having a thickness of 188 μm is prepared as the substrate 12, and the colored layer 6, the heat-sensitive destruction layer 2, the near-infrared absorbing layer 5, the transparent heat-insulating layer 3, and the heat-sensitive layer. Each layer of the color forming layer 4 and the protective layer 8 was laminated in order as follows. However, the thermal breakdown layer 2 was formed by a vacuum vapor deposition method, and the other layers were formed by a gravure printing method. The thickness of each layer is the thickness after drying.
[0059]
The colored layer 6 was formed to a thickness of 2 μm using black ink using a polyester-based resin containing carbon black as a binder.
As the heat-sensitive destruction layer 2, an anchor layer having a thickness of 0.5 μm was formed on the colored layer 6 by using an anchor coating agent having a vinyl chloride / vinyl acetate copolymer as a binder, and an Sn layer having a thickness of 80 nm was formed. A thin film was formed.
The near-infrared absorptive layer 5 is formed by using a near-infrared light absorbing material (product of ICI, product number: S110510) mixed with a 10% aqueous solution of polyvinyl alcohol resin and an isocyanate curing agent, and has a thickness of 2 μm. did.
The transparent heat insulating layer 3 was formed using a 10% aqueous solution of polyvinyl alcohol resin and had a thickness of 2 μm.
The thermosensitive coloring layer 4 comprises 3-diethylamino-7-chlorofluorane, which is a red coloring dye, and 3,3-dichlorophenthiourea, which is a developer, as coloring components, which are 10% of the polyvinyl alcohol resin. It formed using the composition disperse | distributed in aqueous solution, and was 5 micrometers in thickness. The composition was prepared using a sand mill so that the average particle diameters of the dye and the developer were 0.3 μm so as not to disturb the transmittance of visible light and near infrared light.
The protective layer 8 was formed using a urethane acrylate-based ultraviolet curable resin so as to have a thickness of 4 μm.
[0060]
When a semiconductor laser beam having a wavelength of 780 nm was used for the obtained heat-sensitive recording material, the position of the objective lens was adjusted so that the focal point was in the middle of the thickness of the near-infrared absorbing layer 5. In contrast, the lower colored layer 6 is black, and the non-opening portion is composed of the Sn metallic color of the heat-sensitive destruction layer 2 so that good recording with contrast can be performed. No change occurred.
Further, when recording was performed on the heat-sensitive color-developing layer 4 using a thermal head, good red printing could be performed, and the lower thermal-sensitive destruction layer 2 did not change due to the recording performed using the thermal head. .
[0061]
(Example 2)
The coloring component in the composition used for forming the thermosensitive coloring layer 4 is 3- (N-ethyl-N acylamino) -6-methyl-7-anilinofluorane) which is a black coloring dye. A thermosensitive recording material was produced in the same manner as in Example 1 except that the colorant was changed to bisphenol A, which is a colorant.
[0062]
As in the case of Example 1, the obtained thermosensitive recording material could be recorded on the thermosensitive destruction layer 2 and the thermosensitive coloring layer 4 without causing an influence on the other layer.
Further, when a bar code was recorded on the heat-sensitive destruction layer 2 and solid color was printed on the heat-sensitive color-developing layer 4, the bar code was completely concealed visually. When an infrared barcode reader was used in this state, an apparently hidden barcode could be read.
[0063]
【The invention's effect】
According to the first aspect of the present invention, since the heat-sensitive destruction layer and the heat-sensitive color-developing layer are separated by the transparent heat-insulating layer, the influence on other layers can be avoided when recording on both layers. Recording is possible, and since the near-infrared absorbing layer is interposed between the heat-sensitive destruction layer and the transparent heat-insulating layer, the near-infrared absorbing layer converts light into heat and transmits it to the heat-sensitive destruction layer. Composite thermal recording layer capable of non-contact thermal breakdown recording on the thermal breakdown layer However, the thermal recording material is laminated on at least a part of the base material, with the thermal breakdown layer side facing the base material side. Can provide. According to the invention of claim 2, in addition to the effect of the invention of claim 1, since the colored layer is laminated on the side opposite to the transparent heat-insulating layer of the heat-sensitive destruction layer, when recording is made on the heat-sensitive destruction layer Since the colored layer can be seen through the aperture, visibility can be increased by contrasting the hue with the heat-sensitive destruction layer. Thermal recording material Can provide. According to the invention of claim 3, in addition to the effect of the invention of claim 1 or 2, the heat-sensitive color-developing layer is uniformly and uniformly colored, the lower layer is apparently concealed, and the lower layer information is read by near infrared rays. Is possible Thermal recording material Can provide. According to the invention of claim 4, in addition to the effects of the invention of any one of claims 1 to 3, since the adhesive layer is laminated on the exposed surface on the heat-sensitive destruction layer side of the composite thermosensitive recording layer, Easy to apply to the adherend Thermal recording material Can provide. Of claim 5 According to the invention, It has the same effect as the composite thermosensitive recording phase layer in claim 1 described above. The composite thermosensitive recording layer is laminated on the peelable surface of the transfer sheet, and a transfer sheet that can be easily applied by transfer to various adherends can be provided. Claim 6 According to the invention, It has the same effect as the composite thermosensitive recording phase layer in claim 1 described above. A composite thermosensitive recording layer is laminated on a transparent substrate sheet, and a label that can be easily applied by sticking to various adherends can be provided. Claim 7 According to the invention, A composite thermosensitive recording layer having the same effect as the composite thermosensitive recording phase layer in claim 1 is provided, and the transparent heat insulating layer is replaced with a transparent base sheet. Since it has a structure, it is the same as that of the invention of claim 6 of It is possible to provide a label that has an effect and does not cause a decrease in sensitivity of the thermosensitive coloring layer. Claim 8 According to the invention, any one of claims 1 to 4 Thermal recording material , Claim 5 Thermal recording layer transfer sheet, or Claim 6 or 7 By using the heat-sensitive destruction layer of the heat-sensitive recording layer label, non-contact-type heat-sensitive destruction recording with a laser beam, and contact-type heat-sensitive recording with a thermal head, the superimposed heat-sensitive color-developing layer and heat-sensitive destruction It is possible to provide a recording method capable of performing recording on each of the layers without affecting the other recording layers.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a composite thermosensitive recording layer.
FIG. 2 is a cross-sectional view of a composite thermosensitive recording layer with a colored layer.
FIG. 3 is a cross-sectional view of a composite thermosensitive recording layer with a protective layer and an adhesive layer.
FIG. 4 is a cross-sectional view of a heat-sensitive recording material.
FIG. 5 is a cross-sectional view of a heat-sensitive recording layer transfer sheet.
FIG. 6 is a cross-sectional view of a label for sticking a heat-sensitive recording layer.
FIG. 7 is a cross-sectional view showing a state of recording on a thermal recording medium.
[Explanation of symbols]
1 Composite thermal recording layer
2 Thermal breakdown layer
3 Transparent thermal insulation layer
4 Thermosensitive coloring layer
5 Near-infrared absorbing layer
6 Colored layer
7 Adhesive layer
8 Protective layer
11 Thermal recording material
12 Substrate (Substrate)
21 Thermal recording layer transfer sheet
22 Peelable substrate sheet
31 Sheet for thermal recording layer sticking
32 Transparent substrate sheet
41 Near-infrared laser light
42 lenses
51 thermal head

Claims (8)

At least a part of the heat-sensitive destruction layer, a near-infrared absorbing layer, a transparent heat-insulating layer, and a heat-sensitive color-developing layer are laminated in order on at least a part of the substrate. A heat-sensitive recording material, characterized by being laminated facing the substrate side.   2. The heat-sensitive recording material according to claim 1, wherein the composite heat-sensitive recording layer has a colored layer laminated on the opposite side of the heat-sensitive destruction layer to the near-infrared absorbing layer.   3. The heat-sensitive recording material according to claim 1, wherein the heat-sensitive coloring layer contains a dye precursor that does not absorb in the near infrared region after color development.   The heat-sensitive recording material according to claim 1, wherein an adhesive layer is laminated on the exposed surface of the composite heat-sensitive recording layer. At least the heat- sensitive color-developing layer side of the composite heat-sensitive recording layer in which the heat- sensitive destruction layer, the near-infrared absorbing layer, the transparent heat-insulating layer, and the heat-sensitive color-forming layer are sequentially laminated is peelable of the peelable substrate sheet A heat-sensitive recording layer transfer sheet, which is laminated on a surface. At least the heat- sensitive color-forming layer side of the composite heat-sensitive recording layer in which the heat- sensitive destruction layer, the near-infrared absorbing layer, the transparent heat-insulating layer, and the heat-sensitive color-forming layer are sequentially laminated is laminated on the transparent substrate sheet. A label for sticking a heat-sensitive recording layer. At least a heat-sensitive destruction layer, a near-infrared-absorbing layer, a transparent heat-insulating layer, and a heat-sensitive color-forming layer are each provided with a composite heat-sensitive recording layer, and the transparent heat-insulating layer is a transparent base sheet. A label for sticking a heat-sensitive recording layer. The heat-sensitive recording material according to any one of claims 1 to 4, with respect to the near infrared absorbing layer of the heat-sensitive recording layer transfer sheet or claim 6 or 7 thermosensitive recording layer sticking label according of claim 5, wherein, Irradiate near-infrared laser light to generate heat by light-to-heat conversion, perform heat-sensitive destruction recording on the heat-sensitive destruction layer by the heat, and heat recording by bringing heated recording means into contact with the heat-sensitive color-developing layer A recording method comprising:

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