JP2019104195A - Marking sheet, marked marking sheet, and method for manufacturing marking sheet - Google Patents

Abstract

To provide a marking sheet having good abrasion resistance and peeling resistance, a marked marking sheet, and a method for manufacturing a marking sheet.SOLUTION: There is provided a marking sheet 11 in which a transparent resin layer 14 is laminated on a resin substrate 12 provided with a heat-sensitive color-developing layer 13 by melting, wherein the heat-sensitive color-developing layer 13 contains a developer having an electron-donating property, a dye reacting with the developer and changed from colorless to have a color, and a binder resin holding adhesion with the resin substrate 12, and a glass transition point of the binder resin is within 30°C at a low temperature side compared to melting points of resins contained in the resin substrate 12 and the transparent resin layer 14.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a marking sheet for marking characters, figures and the like on a sheet, a marked marking sheet, and a method of manufacturing the marking sheet.

  In recent years, for example, various cards such as IC cards are widely used, and a marking technology is known as a means for forming information etc. displayed on these cards clearly including anti-counterfeit. The abrasion resistance and peel resistance of a card or the like by such marking are desired.

  Conventionally, as a marking technology for cards and the like, those described in the following patent documents and the like are known. Patent Document 1 relates to a thermal print recording medium and the like, and a transfer foil is formed by sequentially laminating a transfer substrate, a peeling layer, a light diffraction layer, a transparent reflection layer, and an adhesive layer on the entire surface of a white card substrate. The thermal printing layer and the offset printing layer are formed on the release layer through the primer layer, and the OP layer is formed by the OP ink etc. to prevent rubbing, scraping and staining on the offset printing layer. In the case of a ticket, a magnetic recording layer is formed on the opposite surface of a card substrate, and it is described that desired items are printed on a thermal printing layer by a thermal printer.

  Further, in Patent Document 2, a reversible thermosensitive coloring layer, a light absorption / heat conversion layer, an adhesive layer, and a resin layer (laminate film) are sequentially provided on one surface of a support for a noncontact recording and rewriting medium. It is described that the laser recording is performed on the reversible thermosensitive coloring layer from the resin layer side.

JP, 2002-364065, A JP, 2009-233600, A

  However, the thermal printing recording medium of Patent Document 1 has a problem that the thin film coating technology in which the OP layer is formed of OP ink etc. has a problem that the thermal printing layer is easily scraped off and forged because the abrasion resistance of the thermal printing layer is not sufficiently ensured. is there. Further, in the medium of Patent Document 2, the resistance to peeling is not sufficiently secured in the formation of the resin layer through the adhesive layer, the adhesive layer is easily peeled off and forged, and the adhesive material is dealt with foaming during recording. However, resin fusion is considered as a means for improving scratch resistance and peeling resistance, for example, but it can not be adopted because the thermosensitive coloring layer develops color when heated.

  Then, this invention was made in view of the said subject, and an object of this invention is to provide the manufacturing method of the sheet for marking which has favorable abrasion resistance and peeling resistance, the marked marking sheet, and the sheet for marking.

  In order to solve the above problems, in the invention of claim 1, a thermosensitive coloring layer is provided on a resin substrate, and a transparent resin layer is fused on the side of the resin substrate on which the thermosensitive coloring layer is provided. The heat-sensitive color-forming layer is a color developing agent having an electron donating property, a dye which reacts with the color developing agent to change color from colorless to colored, and adhesion to the resin base material. A binder resin that retains the properties is contained, and the glass transition point of the binder resin is within 30 ° C. on the low temperature side as compared to the melting point of the resin contained in the resin base material and the transparent resin layer.

In the invention according to claims 2 to 4, the melting point of the color developer is higher than the melting point of the resin contained in the resin base material and the transparent resin layer,
"The thermosensitive coloring layer contains a light-to-heat conversion material that absorbs laser light and converts it into heat,"
"The transparent resin layer contains a coloring material that changes color by generating heat by absorbing laser light."

  In the invention of claim 5, the transparent resin layer is fused and laminated on the resin substrate provided with the thermosensitive coloring layer, and the thermosensitive coloring layer is a developer having an electron donating property, A dye that reacts with a developer to change color from colorless to colored, and a binder resin that retains adhesion with the resin base material are contained, and the glass transition point of the binder resin is the resin base material and the transparent resin layer. A marking sheet marked on a marking sheet having a temperature within 30 ° C. on the low temperature side as compared to the melting point of the resin contained in the first color, and the first thermosensitive coloring layer is colored according to thermal stimulation. It is assumed that the information section is marked.

In the sixth to eighth aspects of the present invention, "the melting point of the color developer contained in the thermosensitive coloring layer to which the first information portion is marked is higher than the melting point of the resin contained in the resin base material and the transparent resin layer "High" configuration,
"The thermosensitive coloring layer contains a photothermal conversion material which absorbs laser light and converts it into heat, and the first information portion is marked by laser light",
"The transparent resin layer contains a coloring material that changes color by generating heat by absorbing laser light, and the second information portion is marked by the laser light on the transparent resin layer".

  In the invention according to claim 9, a method for producing a sheet for marking comprising a resin base, a thermosensitive coloring layer and a transparent resin layer, wherein the color developing agent having an electron donating property on the resin base And a dye that reacts with the color developer to change color from colorless to colored, and a binder resin that maintains adhesion with the resin base material, and the glass transition point of the binder resin is the resin base material and the above. A step of applying a thermosensitive coloring layer which is within 30 ° C. on the low temperature side as compared to the melting point of the resin contained in the transparent resin layer, and a surface side provided with the thermosensitive coloring layer on the resin substrate And a step of fusing the transparent resin layer at a temperature equal to or higher than the melting point of the resin contained in the resin base material and the transparent resin layer.

According to the invention of claim 10, "the melting point of the developer is higher than the melting point of the resin contained in the resin base and the transparent resin layer".
"The thermosensitive coloring layer contains a photothermal conversion material which absorbs laser light and converts it into heat",
"The transparent resin layer contains a coloring material that changes color by generating heat by absorbing laser light."

  According to the invention of claim 1, regarding the marking sheet, the transparent resin layer is fused and laminated on the resin base material provided with the thermosensitive coloring layer, and the thermosensitive coloring layer has an electron donating property. And a binder resin that maintains adhesion with the resin base material, and the glass transition point of the binder resin is When the transparent resin layer is fused at 30 ° C. or less as compared to the melting point of the resin contained in the resin base material and the transparent resin layer, the flow at the time of fusing of the binder resin is suppressed It is possible to inhibit the reaction between the dye and the developer, thereby suppressing color formation, and improving the abrasion resistance of the heat-sensitive color forming layer and the peeling resistance of the transparent resin layer by fusing the resin materials together. Can be .

  According to the invention of claim 2, 6 and 10, color development is carried out at the time of fusion of the transparent resin layer by setting the melting point of the color developing agent higher than the melting point of the resin contained in the resin base material and the transparent resin layer. The agent does not melt, and the color development can be further suppressed.

  According to the invention of claims 3, 7 and 11, the photothermal conversion material efficiently converts the laser light into heat by incorporating the photothermal conversion material that absorbs the laser light and converts it into heat. As a result of being able to record at a low laser output to convert, the load on the sheet can be reduced.

  According to the fourth, eighth, and twelfth aspects of the present invention, the color developing agent is colored black when irradiated with the laser light, by containing the coloring material that changes color by generating heat when the transparent resin layer absorbs the laser light. At the same time, since the resin contained in the transparent resin layer is carbonized to turn black, marking on the transparent resin layer by laser light becomes possible, and if this makes the coloration hues of the transparent resin layer and the thermosensitive recording layer different. It is possible to make it possible to mark a plurality of colors.

  According to the invention of claim 5, regarding the marked marking sheet, the transparent resin layer is fused and laminated on the resin base material provided with the thermosensitive coloring layer, and the thermosensitive coloring layer is an electron. It contains a color developing agent having a donor property, a dye which reacts with the color developing agent to change from colorless to colored, and a binder resin which maintains adhesion with the resin substrate, and the glass transition point of the binder resin is A predetermined color developed in response to a thermal stimulus in a thermosensitive coloring layer for a sheet for marking having a temperature within 30 ° C. on the low temperature side as compared to the melting point of the resin contained in the resin base material and the transparent resin layer By configuring the first information portion to be marked, it is possible to suppress the flow at the time of fusion of the binder resin at the time of fusion of the transparent resin layer, thereby inhibiting the reaction between the dye and the developer To reduce color It is possible to improve the wear resistance of the thermosensitive color developing layer and hence the first information section by fusion bonding of the resin materials, and to improve the peeling resistance of the transparent resin layer, thereby securing the first information section. Can be protected.

  According to the invention of claim 9, regarding the method for producing a sheet for marking, on a resin substrate, a color developing agent having an electron donating property, a dye which reacts with the color developing agent to change color from colorless to colored, and resin A binder resin for maintaining adhesion to a substrate is contained, and the glass transition point of the binder resin is within 30 ° C. on the low temperature side as compared to the melting point of the resin contained in the resin substrate and the transparent resin layer. A thermosensitive coloring layer is coated, and the transparent resin layer is fused on the surface of the resin base provided with the thermosensitive coloring layer at a temperature higher than the melting point of the resin contained in the resin base and the transparent resin layer. By suppressing the flow at the time of fusion of the binder resin at the time of fusion of the transparent resin layer, the reaction between the dye and the color developing agent can be inhibited to suppress the color formation, Abrasion resistance and heat It is capable of improving the peeling resistance of the resin layer.

It is a block diagram of 1st Embodiment of the sheet | seat for marking which concerns on this invention, and a marking sheet. It is process drawing of manufacturing of the sheet | seat for markings of FIG. It is explanatory drawing of the marking with respect to the sheet | seat for markings of FIG. It is explanatory drawing of the marking by the structure of the other thermosensitive coloring layer of the sheet | seat for marking of FIG. It is explanatory drawing of the marking by the structure of the other transparent resin layer of the sheet | seat for markings of FIG. It is a block diagram of 2nd Embodiment of the sheet | seat for marking which concerns on this invention, and a marking sheet.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the cross-sectional views shown in the drawings, dimensions are neglected for easy understanding.
In FIG. 1, the block diagram of 1st Embodiment of the sheet | seat for marking which concerns on this invention, and a marking sheet is shown. The sheet 11 for marking shown in FIG. 1A is provided with the thermosensitive coloring layer 13 at a predetermined position on one surface of the resin base 12 and on the side of the resin base 12 on which the thermosensitive coloring layer 13 is provided. A transparent resin layer 14 is provided.

  The resin base 12 is mainly composed of a resin having a concealing property, and for example, polyvinyl chloride (PVC: melting point 85 to 210 ° C.), polyethylene terephthalate glycol (PET-G), polycarbonate (PC: melting point about 150) C) and the like, and specifically, PG700M manufactured by Taihei Chemicals Co., Ltd. using PET-G is used.

  The transparent resin layer 14 is made of, for example, polyvinyl chloride (PVC), polyethylene terephthalate glycol (PET-G), polycarbonate (PC) or the like, and specifically, CG030M manufactured by Taihei Chemicals Co., Ltd. using PET-G. Is used. The transparent resin layer 14 plays a role of a protective layer, and is provided with a thickness of, for example, 50 μm or more (for example, 50 μm to 100 μm). The resin base 12 and the transparent resin layer 14 are preferably of the same type.

  The heat-sensitive color-forming layer 13 comprises a color developing agent which is an electron acceptor (electron donating property) having a melting point equal to or higher than the resin fusion temperature, a dye which reacts with the color developing agent and changes color from colorless to colored. And a binder resin for maintaining adhesion with the resin.

  The developer is higher in melting point than the melting point of the resin contained in the resin base 12 and the transparent resin layer 14 and is used in combination with a dye (a leuco dye described later). For example, it has a component of a phenol derivative such as bisphenol S, and specifically, BPS / FF-1 manufactured by Nichika Chemical Co., Ltd. using bisphenol S having a melting point of 250 ° C. is used. As the dye, for example, a known leuco dye is used. The leuco dye is selected, for example, from phthalide compounds, azaphthalide compounds, fluoran compounds and the like depending on the color to be developed.

  The binder resin has a glass transition point within 30 ° C. on the low temperature side as compared to the melting point of the resin contained in the resin base 12 and the transparent resin layer 14 and is transparent, semitransparent, and not reactive. It has an active property and has sufficient strength after drying, and examples thereof include polyvinyl alcohol (PVA), urethane, styrene, and acrylic. Specifically, the glass transition point Tg is An acrylic resin having a temperature of 130 ° C. or less (preferably 100 ° C.) is used.

  Subsequently, the marking sheet 11A shown in FIGS. 1B and 1C applies stimulation heat to the thermosensitive coloring layer 13 of the marking sheet 11 in FIG. 1A to obtain first information as predetermined information. It is shown as the one in which the part 21 is marked, and the information is characters, figures, and the like.

  Therefore, FIG. 2 shows a process drawing of the sheet for marking of FIG. 1 and FIG. 3 shows an explanatory view of marking on the sheet for marking of FIG. As shown in FIG. 2 (B), the above-mentioned thermosensitive coloring layer 13 is formed by coating at a predetermined position on the above-mentioned resin base 12 shown in FIG. 2 (A) as the production of the marking sheet 11.

  Subsequently, as shown in FIG. 2C, the above-mentioned transparent resin layer 14 is pasted by heat lamination and fused on the entire surface of the resin base 12 on which the thermosensitive coloring layer 13 is formed. It becomes the sheet 11 for marking, and the lamination temperature in heat lamination is performed above melting | fusing point of resin contained in the resin base material 12 and the said transparent resin layer 14 concerned.

  That is, when the glass transition point of the binder resin is within 30 ° C. on the low temperature side as compared with the melting point of the resin contained in the resin base 12 and the transparent resin layer 14, the thermosensitive recording layer 13 is It is possible to suppress the flow during lamination, thereby inhibiting the reaction between the dye and the developer and suppressing the color formation. For example, by laminating at 130 ° C., with the melting point of the developer being 250 ° C. and the melting point Tg of the binder resin being 100 ° C., coloration is suppressed by the dye and the developer as shown in FIG. Peeling resistance is improved by fusion with a binder resin.

  Further, by setting the melting point of the developer to be higher than the melting point of the resin contained in the resin base 12 and the transparent resin layer 14, the developer does not melt at the time of lamination, and color development can be further suppressed. It is a thing.

  Then, as shown in FIG. 3 (A), a thermal heat source 31 such as a thermal head or the like applies thermal stimulus 31A along the information shape to the heat sensitive color developing layer 13 from the transparent resin layer 14 side. As shown in (B), the thermosensitive coloring layer 13 changes color from colorless to colored to develop color, and the first information portion 21 of the information is marked.

  As described above, in the marking sheet 11, when the transparent resin layer 14 is fused, it is possible to suppress the flow at the time of fusing of the binder resin of the thermosensitive coloring layer 13 and thereby the reaction between the dye and the developer. It is possible to inhibit color formation and to suppress color development, and to improve the abrasion resistance of the heat-sensitive color forming layer 13 and the peeling resistance of the transparent resin layer 14 by fusion bonding of the resin materials. Thereby, the abrasion resistance of the thermosensitive coloring layer 13 and hence the first information portion 21 can be improved by fusion bonding of the resin materials, and the peeling resistance of the transparent resin layer 14 can be improved, thereby the first information portion 21 is able to be protected surely.

  Next, FIG. 4 is an explanatory view of a marking by the configuration of another thermosensitive coloring layer of the marking sheet of FIG. The marking sheet 11 shown in FIG. 4 is a thermosensitive coloring layer 13A that contains a photothermal conversion material that absorbs laser light and converts it into heat, and the other configuration is the same as that of FIG. 1 (A). The light-to-heat conversion material includes indium tin oxide (ITO), a tungsten oxide compound, and a hexaboride. Specifically, CWO (registered trademark) using cesium tungsten oxide manufactured by Sumitomo Metal Mining Co., Ltd. is used Be done.

  By irradiating (scanning) the heat-sensitive color-developing layer 13A of such a marking sheet 11 with the laser light 32, the light-heat conversion material efficiently converts the laser light 32 into heat, thereby recording at a low laser output. As a result, it is possible to reduce the load on the transparent resin layer 14 and the thermosensitive coloring layer 13A.

  Moreover, in FIG. 5, the explanatory view of the marking by the structure of the other transparent resin layer of the sheet | seat for markings of FIG. 1 is shown. The marking sheet 11 shown in FIG. 5 (A) contains a coloring material that absorbs the laser light 32 and develops black color while generating heat in the transparent resin layer 14A, and the other configuration is shown in FIG. 1 (A). Is the same as For example, ITO and a titanium oxide compound can be mentioned as a color former for PVC, PET-G and PC as a base resin, and specifically, CG033ML-X manufactured by Taihei Chemical Co., Ltd. using PET-G is used.

  That is, as shown in FIG. 5 (B), when the transparent resin layer 14A is irradiated with the laser beam 32, the color former contained turns black, and the contained resin is carbonized to become black. It is possible to form and record the second information portion 22 on the transparent resin layer 14A according to 32. Further, in the case where color is developed by applying stimulating heat 31A to the thermosensitive coloring layer 13 from the coloring heat source 31, the transparent resin layer If the color development hue of the thermosensitive recording layer 13 is made different from that of 14A, plural colors can be colored and marked.

  By forming the thermosensitive coloring layer 13 shown in FIG. 5A as a thermosensitive coloring layer 13A containing the light-to-heat conversion material shown in FIG. 4, the first information portion by the laser light 32 directed to the thermosensitive coloring layer 13A is obtained. The formation of 21 and the formation of the second information portion 22 by the laser light 32 on the transparent resin layer 14A can be performed in the same step. For example, as shown in FIG. 5B, the first information portion 21 such as an authentication mark is marked on the thermosensitive coloring layer 13A, and the second information portion 22 is marked on the transparent resin layer 14A in other regions. It is a thing. Although the second information portion 22 is shown as merely circular marking in the drawing, it is natural that it can be marked as characters and figures.

  Next, FIG. 6 shows a configuration diagram of a marking sheet and a marking sheet according to a second embodiment of the present invention. The sheet 11 for marking shown in FIG. 6A is further provided with the same kind of thermosensitive coloring layer 43 at a predetermined position on the back side of the surface of the resin base 12 shown in FIG. 1A on which the thermosensitive coloring layer 13 is provided. A transparent resin layer 44 is provided on the side of the back surface of the resin base 12 on which the thermosensitive coloring layer 43 is formed.

  For example, as shown in FIG. 6B, the first information portion 21 such as an authentication mark is marked on the thermosensitive coloring layer 13, and as shown in FIG. 6C, the thermosensitive coloring layer 43 on the back side is two-dimensional. It is possible to mark the third information portion 23 such as a code (which may be a bar coat) or the like and to mark both the front and back sides.

  In the second embodiment shown in FIGS. 6A and 6B, the configurations of FIGS. 4 and 5 can be applied.

  The marking sheet, the marked marking sheet, and the method for producing a marking sheet according to the present invention can be used in industries such as production, use, and sales of a sheet for marking information or the like on a medium.

11 sheet for marking 11A marking sheet 12 resin base material 13, 13A, 43 thermosensitive coloring layer 14, 14A, 44 transparent resin layer 21 first information section 22 second information section 23 third information section 31 coloring heat source 31A stimulation heat 32 laser light

Claims (12)

A sheet for marking, wherein a thermosensitive coloring layer is provided on a resin substrate, and a transparent resin layer is fused and laminated on the side of the resin substrate on which the thermosensitive coloring layer is provided,
The thermosensitive coloring layer contains a color developing agent having an electron donating property, a dye which reacts with the color developing agent to change color from colorless to colored, and a binder resin which maintains adhesion with the resin substrate. A sheet for marking, wherein the glass transition point of the binder resin is within 30 ° C. on the low temperature side as compared with the melting point of the resin contained in the resin base material and the transparent resin layer.   The marking sheet according to claim 1, wherein the melting point of the color developing agent is higher than the melting points of the resins contained in the resin base material and the transparent resin layer.   3. The marking sheet according to claim 1, wherein the heat-sensitive color-developing layer contains a light-to-heat conversion material that absorbs laser light and converts it into heat.   The marking sheet according to at least one of claims 1 to 3, wherein the transparent resin layer contains a coloring material which changes color by generating heat by absorbing laser light. . A transparent resin layer is fused and laminated on a resin base provided with a thermosensitive coloring layer, and the thermosensitive coloring layer reacts with a color developing agent having an electron donating property and the color developing agent. A dye that changes color from colorless to colored, and a binder resin that retains adhesion with the resin substrate described above are contained, and the glass transition point of the binder resin is the melting point of the resin contained in the resin substrate and the transparent resin layer A marking sheet that is marked on a marking sheet that is within 30 ° C. on the low temperature side as compared to
A marking sheet, wherein a predetermined first information portion colored in response to a thermal stimulus is marked on the thermosensitive coloring layer.   The marking sheet according to claim 5, wherein the melting point of the color developer contained in the heat-sensitive color forming layer to which the first information part is marked is from the melting point of the resin contained in the resin base material and the transparent resin layer A sheet for marking that is also characterized by being high.   The marking sheet according to claim 5 or 6, wherein the thermosensitive coloring layer contains a photothermal conversion material that absorbs laser light and converts it into heat, and the first information portion is marked by laser light. Marking sheet characterized by   The marking sheet according to at least one of claims 5 to 7, wherein the transparent resin layer contains a coloring material that generates heat by absorbing the laser light and changes color, and the transparent resin layer is changed to the first color by the laser light. 2. A marking sheet characterized in that the information section is marked. What is claimed is: 1. A method of producing a marking sheet comprising a resin base material, a thermosensitive coloring layer, and a transparent resin layer, comprising:
The resin base contains a color developing agent having an electron donating property, a dye which reacts with the color developing agent to change color from colorless to colored, and a binder resin which maintains adhesiveness with the resin base. A step of coating a thermosensitive coloring layer having a glass transition point of the binder resin at 30 ° C. or less on the low temperature side as compared to the melting points of the resin contained in the resin base material and the transparent resin layer;
Fusing the transparent resin layer at a temperature above the melting point of the resin contained in the resin base material and the transparent resin layer on the side of the resin base material on which the thermosensitive coloring layer is provided;
A method of producing a sheet for marking, comprising:   10. The method for producing a marking sheet according to claim 9, wherein the melting point of the color developer is higher than the melting point of the resin contained in the resin base material and the transparent resin layer. Production method.   The method for producing a marking sheet according to claim 9 or 10, wherein the heat-sensitive color-developing layer contains a light-to-heat conversion material that absorbs laser light and converts it into heat. .   The method for producing a marking sheet according to at least one of claims 9 to 11, wherein the transparent resin layer contains a coloring material which generates heat to be discolored by absorbing laser light. Method of manufacturing a sheet for marking.

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