JP2009300560A - Manufacturing method of hologram self-adhering label, hologram self-adhesion label, and medium with hologram - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a hologram self-adhering label that has an antifouling protective layer on its outermost surface, is easily stuck and fixed to the adhering object, is removed when desired, and is stuck (fixed) again, and also to provide the hologram self-adhesion label, and a medium with a hologram. <P>SOLUTION: This manufacturing method comprises: (1) a preparing process of a hologram transfer foil 10; (2) a preparing process of the self-adhering label 20; (3) a stacking process of stacking the hologram transfer foil 10 and the self-adhering label 20; (4) an exposing process of exposing a peeling layer 13 surface; and (5) an antifouling protective layer forming process of disposing the antifouling protective layer 14 on the exposed peeling layer 13. The antifouling protective layer 14 includes ionizing radiation curable resin, and fluoride-based and/or silicon-based compound having, at its terminal, one functional group reactable with the ionizing radiation curable resin, and is cured by irradiation of ionizing radiation. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hologram self-adhesive label, and more particularly, to produce a hologram self-adsorption label that can be easily attached and fixed to an adherend, and can be removed and reattached (fixed) when desired. The present invention relates to a method, a hologram self-adhesive label, and a medium with a hologram.

  In the present specification, “ratio”, “part”, “%” and the like indicating the composition are based on mass unless otherwise specified, and the “/” mark indicates that they are integrally laminated. “PET” is an abbreviation, synonym, functional expression, common name, or industry term for “polyethylene terephthalate” and “printing” for “printing”.

  (Main application) As the main application of the hologram-including medium 100 formed by adhering the hologram self-adsorption label 40 of the present invention to the adherend 101, ID cards such as employee cards, membership cards and student cards, A liquid crystal display device or the like, which is suitable for a touch panel. However, if it is an application that can be easily attached and fixed to an adherend, can be removed and reattached (fixed) when desired, and the outermost surface needs protection and antifouling properties There is no particular limitation.

(Background Art) Conventionally, information is displayed as an image on a personal computer, a portable terminal, a cellular phone, and the like, and the image is usually displayed using a display device (image display device). The display device is, for example, a liquid crystal display, an organic electroluminescence display, or the like, and includes a display module and an optical member that covers a light emitting surface. The optical member is in the form of glass or film, and the user views the image through this or touches the touch panel to operate it. That is, since the user directly touches or touches randomly, the surface becomes dirty and scratches easily after repeated many times, resulting in deterioration of the display image quality. In addition to the protective property, the antifouling property of the surface is also necessary. In addition, in cellular phones and the like that have been widely used, it is required to protect the image display unit and at the same time apply a decoration of your choice, and the protection function and / or decoration function is performed using an adhesive label. It can be stuck and fixed, but air bubbles are easily involved, cannot be removed when desired, and cannot be reattached (fixed). Furthermore, for example, with an ID card, images such as letters, numbers, and facial photographs are formed on the surface of the medium. In recent years, these images are often formed by a transfer method by thermal transfer or sublimation transfer using a so-called melt transfer type or sublimation transfer type ink ribbon. The transfer method is a thermal transfer sheet in which a colored transfer layer is formed on a base sheet, and is heated in an image form from the back by a thermal head or the like, and the above-described colored transfer layer is thermally transferred to the surface of the thermal transfer image receiving sheet. An image is formed. This thermal transfer method is roughly classified into two methods, a sublimation transfer type and a thermal melt transfer type, depending on the configuration of the colored transfer layer, and both methods can form a full-color image. In particular, when an image is formed with a sublimation transfer type thermal transfer sheet, a gradation image such as a facial photograph can be accurately formed, but unlike an image with a normal printing ink, weather resistance, friction resistance, There are weaknesses that lack durability such as chemical properties. As a solution, a protective layer thermal transfer film having a thermal transfer resin layer is superimposed on the thermal transfer image, and the thermal transfer resin layer having transparency is transferred using a thermal head, a heating roll, or the like, and the protective layer is formed on the image. Has been made to form. Since the protective layer described above needs to be partially transferred at the time of transfer by a thermal head or a heat roll, it needs to have a foil cutting property. In this case, since the protective layer has to be a resin film having a thickness of about several microns, durability such as tough scratch resistance and chemical resistance cannot be provided. Although the above protective layer can be decorated, it is a fixed pattern and cannot be decorated as desired.
Therefore, it can be easily attached and fixed to a medium (attachment) such as a display device or a card, and can be removed and reattached (fixed) when desired. A method for producing a hologram self-adsorption label that is excellent in surface protection such as scratch resistance, is not easily contaminated with finger grease, and can be easily replaced with another hologram self-adsorption label having a decoration of your choice, There is a need for hologram self-adhesive labels and media with holograms.

(Prior Art) Conventionally, an adhesive layer composed of an ethylene-α-olefin copolymer with limited weight average molecular weight Mw, ratio of weight average molecular weight to number average molecular weight Mn, melting peak temperature in DSC analysis, and heat of fusion, and other A surface protective film is known in which a base material made of a polyolefin-based resin is integrally formed by coextrusion (see, for example, Patent Document 1). However, this is a so-called protective film, and there is no description or suggestion about self-adsorption or removability.
In addition, it has excellent re-peeling performance, and even when it is incorporated and used inside the device, the thermal decomposition product is not generated from the adhesive layer that adheres to the components of the device, or the thermal decomposition product does not easily remain. An optical filter is known (for example, see Patent Document 2). However, it is limited to optical films that use an olefin-based polymer-containing adhesive that has removability to the adherend surface, preventing a decrease in light transmittance due to interface reflection of bubbles, and the film substrate is polycarbonate. Examples include phthalate polymers (polyethylene terephthalate, polyethylene naphthalate, etc.), acrylic polymers, vinyl chloride polymers, crystalline polyurethanes (polycarbonate polyurethane, etc.). Although it has excellent durability, there is a drawback that scratch resistance due to scratching is poor.
Furthermore, an antireflective laminate in which a low refractive index layer containing (A) an oxetane compound, (B) an epoxy compound, and (C) a fluorine-containing curable compound having a specific general formula is formed on a substrate is known (for example, Further, a support, a phosphor layer, an ultraviolet ray or an electron beam curable resin, and a reactive silicone having at least one functional group capable of reacting with the ultraviolet ray or the electron beam curable resin at the terminal. A radiation-emitting panel is known that includes a protective film that is cured by irradiation with ultraviolet rays or electron beams in this order (see, for example, Patent Document 4). However, in Patent Documents 3 and 4, since it is directly processed into an antireflection laminate or a radiation-emitting panel, it cannot be removed or reattached (fixed) when desired, and is a high cost. There is.

Japanese Patent Application Laid-Open No. 8-157791 JP 2004-29673 A JP 2005-316415 A Japanese Patent Laid-Open No. 2002-174697

  Accordingly, the present invention has been made to solve such problems. Its purpose is to adhere to the surface of an adherend such as a liquid crystal display device or employee ID card, and the outermost surface becomes a medium with a protective function (hologram layer) having an antifouling protective layer. Provided are a method for producing a hologram self-adsorbing label, a hologram self-adhesive label, and a hologram-attached medium that can be easily attached and fixed to a body, and can be removed and reattached (fixed) when desired.

In order to solve the above-mentioned problems, a method for producing a hologram self-adsorption label according to the invention of claim 1 includes: (1) a transfer substrate, and a release layer, a hologram layer and a reflection layer on one surface of the transfer substrate. A hologram transfer foil preparing step for preparing a hologram transfer foil comprising: (2) a label base material, and a self-adsorbing and releasable adhesive layer provided on one surface of the label base material, the adhesive layer surface A self-adsorbing label preparing step for preparing a self-adsorbing label provided with release paper so that it can be peeled off, and (3) the reflective layer surface of the hologram transfer foil and the label substrate surface of the self-adsorbing label through an adhesive layer (4) an exposure step of peeling and removing the transfer substrate of the hologram transfer foil from the laminate to expose the release layer surface, and (5) the exposed peeling. An antifouling protective layer is provided on the layer surface. And antifouling protective layer forming step, so that a is obtained by.
A hologram self-adhesive label according to the invention of claim 2 is produced by the method for producing a hologram self-adsorption label according to claim 1, and the antifouling protective layer, release layer, hologram layer, reflection layer, adhesive The antifouling protective layer is terminated with an ionizing radiation curable resin and a functional group capable of reacting with the ionizing radiation curable resin. And one or more fluorine-based and / or silicon-based compounds, which are cured by irradiation with ionizing radiation.
According to a third aspect of the present invention, there is provided a hologram-including medium in which the exposed adhesive layer surface of the hologram self-adsorption label according to the second aspect is adhered to an adherend.

According to the first aspect of the present invention, since the hologram transfer foil 10 and the self-adsorption label 20 can be manufactured by the existing technology and the existing equipment, the lamination process, the exposure process, and the antifouling protective layer forming process can be manufactured at low cost. A method of manufacturing a hologram self-adsorption label that can be easily manufactured is provided.
According to the second aspect of the present invention, a high protective function (antifouling protective layer) by attaching to the surface of an adherend such as a liquid crystal display device or an employee ID card, and a design and security function ( It becomes a medium with a hologram layer), which can be easily attached and fixed to the adherend, and can be removed and removed and reattached (fixed) when desired, or it can be reattached to another label when desired. Thus, a hologram self-adhesive label having an outermost surface having both a protective property and an antifouling property is provided.
According to the third aspect of the present invention, the hologram self-adsorption label having an antifouling protective function and a decorative function can be replaced with a decoration of the user's preference, and the outermost surface also has an antifouling property as well as a protective property. As a hologram layer, there is provided a hologram-including medium that is excellent in durability such as heat resistance and weather resistance in addition to scratch resistance and solvent resistance.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view of a hologram transfer foil used in the method for producing a hologram self-adsorption label according to the present invention.
FIG. 2 is a cross-sectional view of a self-adsorbing label transfer foil used in the method for producing a hologram self-adsorbing label of the present invention.
FIG. 3 is a cross-sectional view illustrating a lamination process of the method for producing a hologram self-adsorption label according to the present invention.
FIG. 4 is a cross-sectional view for explaining the exposure process of the method for producing a hologram self-adsorption label according to the present invention.
FIG. 5 is a cross-sectional view of a hologram self-adsorption label showing one embodiment of the present invention.
FIG. 6 is a cross-sectional view of a hologram-including medium in which the hologram self-adsorption label of the present invention is attached to an adherend.

(Method for Producing Hologram Self-Adhesive Label) The method for producing the hologram self-adhesive label 40 of the present invention is as follows: (1) the transfer substrate 11, the release layer 13, the hologram layer 15 and the reflection on one surface of the transfer substrate 11. Hologram transfer foil 10 preparation step for preparing the hologram transfer foil 10 composed of the layer 17; (2) a label base material 21 and a self-adsorbing and releasable adhesive layer on one surface of the label base material 21 29, and a self-adsorbing label 20 preparation step for preparing a self-adsorbing label 20 having a release paper 23 provided on the surface of the adhesive layer 29 so as to be peelable, (3) the reflective layer 17 surface of the hologram transfer foil 10 and the surface A laminating step of laminating the label substrate surface 21 of the self-adsorbing label 20 via the adhesive layer 39 to form a laminate 30, and (4) the transfer substrate 11 of the hologram transfer foil 10 from the laminate 30. Peeling And removed, the exposing step to expose the peeling layer 13 side, (5) said exposure to the release layer surface out, and antifouling protective layer forming step of forming an antifouling protective layer, made of.
(Hologram Self-Adhesive Label) The hologram self-adsorption label 40 of the present invention is a hologram self-adsorption label 40 produced by the method for producing a hologram self-adsorption label 40 according to claim 1, and is an antifouling protective layer 14. , Release layer 13, hologram layer 15, reflection layer 17, adhesive layer 39, label substrate 21, and self-adsorbing and re-peeling adhesive layer 29, and the antifouling protective layer 14 is ionizing radiation. A curable resin and a fluorine-based and / or silicon-based compound having at least one functional group capable of reacting with the ionizing radiation curable resin at the terminal, and cured by irradiation with ionizing radiation (a medium with a hologram) The hologram-including medium 100 of the present invention is formed by adhering the exposed adhesive layer 29 surface of the hologram self-adsorption label 40 according to claim 2 to the adherend 101. The hologram-attached medium 100 has a hologram self-adsorbing label having a protective function and / or a decorative function attached, and the outermost surface is a hologram layer with an antifouling protective layer, so that it has heat resistance, solvent resistance and weather resistance. In addition to the properties of the film, it also has excellent scratch resistance against contact with sharp objects, which is a defect of the film. It can be easily changed. In addition, even when the sticking fails, the same hologram self-adsorption label can be easily peeled off and attached again.

  The hologram self-adsorption label 40 has the following effects. (1) The hologram self-adsorption label 40 can be easily attached and fixed to the adherend 101, and can be removed and reattached (fixed) when desired. In the conventional adhesive layer, depending on the molecular weight and distribution of the constituent components, some of the components remain on the surface of the adherend 101 or migrate (bleed out), resulting in stable removability and re-adsorption. Inferior. (2) When the hologram self-adsorbing label 40 is attached to the adherend 101, it is difficult for air bubbles to be caught between the adherend 101 and the adhesive layer 29. Air bubbles can be released by sticking. When bubbles are involved, the appearance is poor, and the transparency is lowered due to interface reflection at the air interface, which can also be prevented. (3) When the hologram self-adsorption label 40 is attached to the adherend 101, the adhering force (adhesive force) with the adherend 101 surface is less likely to deteriorate with time and is attached with a slight external force. There is no peeling from the surface of the body 101 or partial peeling (so-called floating). In the conventional adhesive layer, due to the molecular weight and distribution of the constituent components, a part of the components migrate to the surface of the adherend 101, the constituent components change, and the self-adsorption property (adhesive force) becomes stronger or weaker. Sometimes. (4) Even after the hologram self-adsorption label 40 is peeled off from the adherend 101, the surface of the adherend 101 is hardly contaminated, and the self-adsorption of the adhesive layer 29 of the hologram self-adsorption label 40 that has been peeled off again. And re-peelability are moderately maintained and can be reused repeatedly. (5) The self-adsorptive and re-peelable adhesive layer 29 of the hologram self-adsorptive label 40 can be easily removed by gas jetting or rinsing even if it is re-peeled, and can be removed just like a new one. It can be used any number of times in the state, and the running cost can be reduced. (6) Since the hologram self-adsorption label 40 is easy to remove (re-peel) from the adherend 101, it is also convenient when recycling the adherend 101 (parts, etc.).

  The hologram self-adhesive label 40 is manufactured by preparing the hologram transfer foil 10 and the self-adsorption label 20 separately, and forming the laminate 30 and then removing a part of the hologram transfer foil 10 (transfer base material 11). Then, after the surface of the release layer 13 is exposed, the antifouling protective layer 14 is formed on the surface of the release layer 13 through the primer layer 16 as necessary. There are effects like this. (1) Since the hologram transfer foil 10 and the self-adsorption label 20 can be manufactured with existing technology and existing equipment, they can be easily manufactured at low cost. In addition, these general-purpose products can be created together in advance, thereby reducing costs. (2) Moreover, since a lamination | stacking process, peeling exposure process, and antifouling protective layer formation process can also be manufactured with the existing technique and existing equipment, it can manufacture easily at low cost. (3) In the method of manufacturing the hologram self-adsorption label 40 shown in FIG. 5, (a) the self-adsorption label 20 shown in FIG. 2 is once manufactured, and the hologram layer 15 and the reflection layer 17 are formed on the surface of the label base 21. , A method of providing the primer layer 16 and the antifouling protective layer 14, (b) after providing the hologram layer 15, the reflective layer 17, the primer layer 16, and the antifouling protective layer 14 on the surface of the label substrate 21, There is a method in which a self-adsorbing and re-peelable adhesive layer 29 is provided on the surface, and release paper is laminated. However, in the method (a), when a fine uneven relief is formed on the hologram layer 15, the adhesive layer 29 is flexible and cushions, so that the pressure is not sufficiently applied and cannot be formed. Further, when the reflective layer 17 is formed by a vacuum film forming apparatus, it is difficult to form the reflective layer 17 due to degassing from the adhesive layer 29. In the method (b), after the expensive hologram layer 15 and the reflective layer 17 are formed, in order to provide the primer layer 16, the antifouling protective layer 14, the adhesive layer 29 on the other surface, and the release paper, Since there are many processes after 17 and the expensive hologram layer 15 and reflection layer 17 are lost in each process, the yield is low and the cost is high.

  (Method for Producing Hologram Self-Adhesive Label) A method for producing a hologram self-adhesive label includes: (1) a transfer substrate 11 and a release layer 13, a hologram layer 15 and a reflective layer 17 on one surface of the transfer substrate 11. The hologram transfer foil 10 preparation step for preparing the hologram transfer foil 10, and (2) a label base material 21 and a self-adsorbing and re-peelable adhesive layer 29 are provided on one surface of the label base material 21, A self-adsorptive label 20 preparation step for preparing a self-adsorptive label 20 in which a release paper 23 is provided on the surface of the adhesive layer 29 so as to be removable; (3) the reflective layer 17 surface of the hologram transfer foil 10 and the self-adsorptive label 20; (4) peeling off and removing the transfer substrate 11 of the hologram transfer foil 10 from the laminate 30. The An exposure step of exposing the surface of the release layer 13, and (5) an antifouling protective layer forming step of providing an antifouling protective layer 14 via the primer layer 16 on the exposed release layer 13 surface, if necessary. Consists of. The materials will be described in the order of processes.

  (Hologram Transfer Foil Preparation Step) (1) In the hologram transfer foil 10 preparation step, the hologram transfer foil 10 comprises a transfer substrate 11 and a release layer 13 and a hologram layer 15 on one surface of the transfer substrate 11. ing.

  (Transfer Base Material) As the transfer base material 11, various film materials can be applied depending on the application. For example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins, vinyl resins such as polyvinyl chloride, acrylic resins, imide resins, engineering resins such as polyarylate, polycarbonate, cyclic polyolefin resins, cellophane Examples thereof include cellulosic films. The transfer substrate 11 may be a copolymer resin containing these resins as a main component, a mixture (including an alloy), or a laminate composed of a plurality of layers.

  The transfer substrate 11 may be a stretched or unstretched film, but a film stretched in a uniaxial direction or a biaxial direction is preferable for the purpose of improving strength. A thickness of about 2.5 to 50 μm is usually applicable, but 2.5 to 25 μm is preferable. Prior to application, the transfer substrate 11 is subjected to easy adhesion treatment such as corona discharge treatment, plasma treatment, primer (also referred to as anchor coat, adhesion promoter, or easy adhesive) coating treatment, alkali treatment, and the like. May be. Moreover, you may add additives, such as a filler, a plasticizer, a coloring agent, and an antistatic agent, as needed. A biaxially stretched polyethylene terephthalate film is preferably used because of its good heat resistance and mechanical strength.

  (Peeling layer) As the peeling layer, acrylic resins, vinyl resins, polyester resins, fiber resins, waxes, melamine resins to which release agents such as fluorine resins, silicones and various waxes are added or copolymerized Resin etc. can be illustrated. Moreover, in order to improve the peelability at the time of transfer, a release layer and a release layer may be provided as necessary, and when both the release layer and the release layer 13 are provided, the transferability is further improved. Can do. When both the release layer and the release layer 13 are provided, they may be used in combination as appropriate. In this case, the release layer also has a function as a protective layer after transfer. The release layer 13 may be formed by dispersing or dissolving the resin in a solvent, applying and drying the resin by a known coating method such as roll coating or gravure coating, and curing as necessary.

(Release layer) The release layer is not particularly limited. Usually, there are a release resin, a resin containing a release agent, a curable resin which is crosslinked by ionizing radiation, and the like. A melamine resin is preferable.
The release layer is formed by dispersing or dissolving the resin in a solvent, applying and drying by a known coating method such as roll coating or gravure coating, and baking at a temperature of about 150 ° C to 200 ° C. The thickness of the release layer is usually about 0.01 μm to 5.0 μm, preferably about 0.5 μm to 3.0 μm.

  (Hologram layer) The hologram layer 15 contains at least an ionizing radiation curable resin as a main component, and contains a filler as necessary. The ionizing radiation curable resin is preferably (1) an isocyanate having three or more isocyanate groups in the molecule, and (2) at least one hydroxyl group and at least two (meth) acryloyloxy groups in the molecule. Necessary using ionizing radiation curable resin containing urethane (meth) acrylate oligomer which is a reaction product of polyfunctional (meth) acrylates having, or (3) polyhydric alcohols having at least two hydroxyl groups in the molecule Accordingly, polyethylene wax or silica may be included, applied, dried, and cured with ionizing radiation to obtain an ionizing radiation curable resin.

  The ionizing radiation curable resin containing the urethane (meth) acrylate oligomer (referred to herein as the ionizing radiation curable resin composition M) is a cured ionizing radiation curable resin containing the urethane (meth) acrylate oligomer. Examples thereof include photocurable resins disclosed in Japanese Patent Application Laid-Open No. 2001-329031. Specific examples include MHX405 varnish (made by The Inktec Co., Ltd., ionizing radiation curable resin product name) and Iupimer UV · V3031 (manufactured by Mitsubishi Chemical Co., Ltd., product name of ionizing radiation curable resin).

  (Filler) Examples of the filler include micro silica and polyethylene wax, and examples of the polyethylene wax include polyethylene resin particles and beads, and spherical beads are preferable. The addition amount is about 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. After the transfer, the hologram layer 15 becomes the outermost layer, and the contained filler protects the medium from mechanical friction and abrasion, and also protects unique information such as an image to be described later.

  (1) By including polyethylene wax, the hologram layer 15 becomes the outermost surface layer after transfer, but the solvent can be used even in extremely harsh environments, for a long period of time, and / or for many repeated uses. It protects the image provided on the adherend from mechanical friction and abrasion, and is resistant to scratches and has excellent durability. (2) Since the hologram layer 15 is in contact with the release layer 13 using the melamine-based resin, the hologram layer 15 is peeled between the hologram layer 15 and the release layer 13 and becomes stable peelability.

  (Hologram layer formation) Hologram layer 15 is formed by adding the above-mentioned ionizing radiation curable resin, silicone or filler, photopolymerization initiator, plasticizer, stabilizer, surfactant, etc., if necessary, and dispersing in solvent. Alternatively, it may be dissolved, applied by a known coating method such as roll coating, gravure coating, comma coating, die coating and the like, dried and reacted (cured) with ionizing radiation after shaping the hologram. The thickness of the hologram layer 15 is usually about 1 to 10 μm, preferably 2 to 5 μm.

  (Hologram) The hologram layer 15 is formed on the surface of the hologram layer 15 to form a hologram layer 15, and the reflection layer 17 is provided on the surface of the minute unevenness, thereby providing high design and anti-counterfeiting properties of the hologram. Can be granted.

  (Hologram) Next, predetermined fine unevenness (relief structure) such as a hologram that exhibits a light diffraction effect is formed on the surface of the hologram layer 15 and cured. A hologram is a recording of interference fringes due to the interference of light between object light and reference light in an uneven relief shape, such as a laser reproduction hologram such as a Fresnel hologram, a white light reproduction hologram such as a rainbow hologram, There are color holograms utilizing the above principle, computer generated holograms (CGH), holographic diffraction gratings and the like. The relief shape is a concavo-convex shape, and is not particularly limited, and may have a fine concavo-convex shape such as light diffusion, light scattering, light reflection, light diffraction, etc., such as Fourier transform or lenticular lens. , A light diffraction pattern, and a moth eye. Further, although it does not have a light diffraction function, it may be a hairline pattern, a mat pattern, a line pattern, an interference pattern, or the like that expresses a unique glitter.

  A relief shape is formed (also referred to as replication) on the surface of the hologram layer 15. Hologram shaping can be formed by a known method. For example, when recording diffraction gratings or interference fringes of holograms as reliefs of surface irregularities, a master on which the diffraction gratings or interference fringes are recorded in irregularities is pressed. The concave / convex pattern of the original can be duplicated by using it as a mold (referred to as a stamper) and by superimposing the original on the resin layer and heat-pressing both of them with an appropriate means such as a heating roll.

  Further, the hologram pattern formed on the hologram layer 15 may be single or plural. The hologram layer 15 is irradiated with ionizing radiation during or after embossing with a stamper to cure the ionizing radiation curable resin. The ionizing radiation curable resin becomes an ionizing radiation curable resin (fine irregularities = relief structure = hologram) when it is cured (reacted) by irradiation with ionizing radiation such as ultraviolet rays or electron beams after the relief is formed.

(Reflection layer) Since the reflection layer 17 is provided on the reflection layer 17 on the relief surface of the hologram layer 15 provided with a predetermined relief structure, the reflection reflection and / or diffraction effect is enhanced. If the rate is higher, it is not particularly limited. The reflective layer 17 may be a metallic glossy reflective layer such as a metal thin film by a vacuum thin film method or the like, or a transparent reflective layer, but the metallic glossy reflective layer is partially provided, and the transparent reflective layer is attached to the adherend. Even if it is transferred to the surface of the formed image, it is preferable because the image can be observed. The transparent reflection layer has a substantially colorless and transparent hue, and its optical refractive index is different from that of the hologram layer. A hologram can be produced. For example, there are a thin film having a higher refractive index than the hologram layer 15 and a thin film having a lower refractive index. Examples of the former include ZnS, TiO ₂ , Al ₂ O ₃ , Sb ₂ S ₃ , SiO, SnO _2. ITO, etc., and examples of the latter include LiF, MgF ₂ , and AlF ₃ . Preferably, it is a metal oxide or nitride, specifically, Be, Mg, Ca, Cr, Mn, Cu, Ag, Al, Sn, In, Te, Fe, Co, Zn, Ge, Pb, Cd , Bi, Se, Ga, Rb, Sb, Pb, Ni, Sr, Ba, La, Ce, Au, and other oxides or nitrides, and the like can be exemplified by a mixture of two or more thereof. Also, a general light-reflective metal thin film such as aluminum can be used when it has a thickness of 200 mm or less. The transparent metal compound is formed on the relief surface of the hologram layer 15 by vacuum such as vapor deposition, sputtering, ion plating, and CVD so that the thickness of the relief layer of the hologram layer 15 is about 10 to 2000 nm, preferably 20 to 1000 nm. It may be provided by a thin film method or the like.

  (Preparation process of self-adsorption label) (2) In the self-adsorption label 20 preparation process, the self-adsorption label 20 is self-adsorbing and removable on one side of the label base material 21 and the label base material 21. An adhesive layer 29 is provided, and a release paper 23 is provided on the surface of the adhesive layer 29 so as to be peelable.

  (Label substrate) As the label substrate 21, the same material as that of the transfer substrate 11 can be applied, and the same is applied to the easy-adhesion treatment and the additive. It is about 20-250 micrometers, Preferably it is 25-188 micrometers.

(Adhesive layer) As the adhesive layer 29, a self-adsorptive and re-peelable layer is used.
Here, the self-adhesive property is also called a self-adhesive layer, but has almost no adhesive property, and is a property of adhering while pushing away air when in contact with the adherend. By removability, lifting one end of the sticking surface means that peeling spreads to the periphery and the whole can be removed. In other words, self-adsorbing and removability means that when sticking and fixing to an adherend, if one end is brought into close contact, the sticking spreads to the periphery and self-adsorbs, strongly fixing in the shearing direction, When it is fixed with a weak force in the peeling direction and is peeled from the adherend, on the contrary, when the one end of the sticking surface is lifted and peeled, the peeling spreads to the periphery and the whole can be removed. What has been peeled off can be attached again.

(Adhesive layer) Self-adhesive and re-peelable adhesive layer 29 includes silicon resin-based, polyolefin resin-based, polyurethane-based thermoplastic elastomer-based self-adhesive resins, rubber-based and polyvinyl chloride resin-based materials. It can be illustrated.
A self-adsorbing composite sheet obtained by forming a self-adsorbing and re-peelable adhesive layer 29 on a substrate such as PET or polyolefin resin is commercially available. For example, Sumitomo Chemical Co., Ltd. trade name Sumilon S, Panac Co., Ltd. trade name olefin gel polymer sheet and the like can be preferably used.

  The adhesive layer 29 is preferably a polyolefin-based thermoplastic elastomer system from the following points. (1) The adhesive layer 29 containing polyolefin can be easily attached and fixed to the adherend 101 and can be removed and reattached (reattached) when desired. In the conventional adhesive layer, depending on the molecular weight and distribution of the constituent components, some of the components remain on the surface of the adherend 101 or migrate (bleed out), resulting in stable removability and re-adsorption. Inferior. Moreover, it is more stable because it has high thermal stability and almost no pyrolysis products. (2) When sticking to the adherend 101, it is difficult to entrain air bubbles between the adherend 101 and the adhesive layer 29, and even if the air bubbles are involved, re-peeling and re-adhering, Air bubbles can escape. When bubbles are involved, the appearance is poor, and the transparency is lowered due to interface reflection at the air interface, which can also be prevented. (3) When adhered to the adherend 101, there is little decrease over time in the adsorbing force (adhesive force) with the adherend 101 surface, and the surface is peeled off from the surface of the adherend 101 by a slight external force. Or partial peeling (so-called floating) does not occur. In the conventional adhesive layer, due to the molecular weight and distribution of the constituent components, a part of the components migrate to the surface of the adherend 101, the constituent components change, and the self-adsorption property (adhesive force) becomes stronger or weaker. Sometimes. (4) Even after peeling from the adherend 101, the surface of the adherend 101 is less likely to be contaminated, and the self-adsorbing property and the removability of the peeled adhesive layer 29 are maintained appropriately. Can be reused repeatedly. (5) Even after re-peeling, the dust is simply adhered and can be easily removed by gas jetting or water washing, and can be used as many times as in the new state, and the running cost can be reduced. (6) Since removal (re-peeling) from the adherend 101 is easy, it is convenient also when the adherend 101 (parts, etc.) is recycled.

  Furthermore, when using as an optical member which covers the light-projection surface of the display module of a display apparatus, transparency of 90% or more is preferable in a total light transmittance. The peel strength of the adhesive layer 29 from the PET surface is preferably 0.1 to 10 N / 25 mm width by T-type peeling in that the adherend 101 is not damaged and can be easily peeled off again.

  (Release paper) The release paper 23 (also referred to as separate paper or separate paper) has a release layer on one side of a substrate such as high-quality paper, coated paper, impregnated paper, and plastic film. The release layer is not particularly limited as long as it has a releasability, and examples thereof include silicone resins, organic resin-modified silicone resins, fluororesins, aminoalkyd resins, and polyester resins. These resins can be used in any of emulsion type, solvent type and solventless type. The release paper 23 is preferably provided with a mat treatment or mat treatment layer for facilitating peeling, and an antistatic treatment or antistatic treatment layer for making dust less likely to adhere.

  (Manufacturing) The self-adsorbing label 20 may be manufactured by applying the adhesive layer 29 to the surface of the label base material 21 by melt extrusion and laminating the release paper 23 on the surface of the adhesive layer 29. The thickness of the adhesive layer 29 is usually about 5 to 300 μm, preferably 20 to 150 μm.

  (Lamination process) (3) In the lamination process, the hologram layer 15 surface of the hologram transfer foil 10 and the label base material 21 surface of the self-adsorbing label 20 are laminated via an adhesive layer 39, as shown in FIG. Such a laminated body 30 is used. As a lamination method, a known dry lamination method or the like can be applied.

  (Dry Lamination Method) The dry lamination method is a method in which an adhesive dispersed or dissolved in a solvent (becomes the adhesive layer 39) is applied and dried, and the laminated substrates are stacked and laminated at 30 to 120 ° C. It is a method of laminating two kinds of materials by curing the adhesive by aging for several hours to several days. The non-solvent lamination method is a method in which the adhesive itself is applied and dried without being dispersed or dissolved in a solvent, and the laminated base material is laminated and laminated, and then aged at 30 to 120 ° C. for several hours to several days. This is a method of laminating two kinds of materials by curing the adhesive.

  (Adhesive) As the adhesive for the adhesive layer 39 used in the dry lamination method or the non-solvent lamination method, an adhesive that is cured by heat or ionizing radiation such as ultraviolet rays or electron beams can be applied. Specific examples of thermosetting adhesives include two-component curable urethane adhesives, polyester urethane adhesives, polyether urethane adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, A polyvinyl acetate adhesive, an epoxy adhesive, a rubber adhesive, or the like can be applied, but a two-component curable urethane adhesive is preferable.

  (Exposing Step) (4) In the exposing step, the transfer substrate 11 of the hologram transfer foil 10 is peeled and removed from the laminate 30 to expose the surface of the release layer 13 as shown in FIG. The method of the exposure process is not particularly limited, and the transfer base material 11 is separated in advance from the laminate 30 into two, which may be manual work or a winding machine, and may be peeled off.

  (Anti-fouling protective layer forming step) (5) In the anti-fouling protective layer forming step, an anti-fouling protective layer 14 is provided on the exposed release layer 13 surface via a primer layer 16 as necessary.

  (Primer layer) The primer layer 16 is used when the antifouling protective layer 14 is provided on the surface of the release layer 13 so that the coating solution does not repel and a stable film is obtained. Further, instead of the primer layer 16, easy adhesion treatment such as corona discharge treatment or plasma treatment may be used. As the primer layer 16, for example, a polyurethane resin, a polyester resin, a polyamide resin, an epoxy resin, a vinyl chloride-vinyl acetate copolymer, an isocyanate compound, or the like can be used. Based on the above resin, if necessary, for example, additives such as various stabilizers, fillers, curing agents, etc. are added, and dissolved or dispersed in a solvent as appropriate. Then, a coating agent composition (ink, coating solution) is prepared and applied by a known coating method such as a roll coating method or a gravure coating method and dried, or is reacted by aging treatment after drying or drying. Just do it.

  (Anti-fouling protective layer) The anti-fouling protective layer 14 is a fluorine-based and / or silicon-based resin having at least one ionizing radiation curable resin and one or more functional groups capable of reacting with the ionizing radiation curable resin at the terminal. A composition containing the compound is formed by curing the composition by irradiation with ionizing radiation.

  (Ionizing radiation curable resin) The ionizing radiation curable resin is a resin that is cured by irradiation with ionizing radiation such as ultraviolet rays and electron beams, and includes acrylate monomers, acrylate oligomers, cationic polymerization monomers, cationic polymerization oligomers, etc. There is. Specific examples of the ionizing radiation curable resin include: Nippon Kogyo Chemical Co., Ltd.'s Shimitsu Series, Showa Polymer Co., Ltd.'s Lipoxy SP / VR Series, Shin-Nakamura Chemical Co., Ltd.'s NK Ester, NK Oligo -Series, LUMICURE made by Dainippon Ink & Chemicals, Unidec series, etc. can be exemplified.

(Fluorine compound) As a fluorine compound having at least one functional group capable of reacting with an ionizing radiation curable resin at the terminal, the following general formula (1),
C _d F _{2d + 1} general formula (1)
(D is 1 to 21 integer) perfluoroalkyl group represented _{by, - (CF 2 CF 2)} g perfluoroalkylene group (g is an integer of 1 to 50) represented by, or F - (- CF (CF ₃ ) CF ₂ O—) _e- CF (CF ₃ ) (where e is an integer of 1 to 50), and CF ₂ = CFCF ₂ CF ₂ —, ( It is preferable to have a perfluoroalkenyl group exemplified by CF ₃ ) ₂ C═C (C ₂ F ₅ ) — and ((CF ₃ ) ₂ CF) ₂ C═C (CF ₃ ) —.
The structure of the fluorine compound is not particularly limited as long as it is a compound containing the above functional group. For example, a polymer of a fluorine-containing monomer or a copolymer of a fluorine-containing monomer and a non-fluorine monomer is used. You can also. Among them, in particular, a fluorine-containing polymer segment composed of either a homopolymer of a fluorine-containing monomer or a copolymer of a fluorine-containing monomer and a non-fluorine monomer, and a non-fluorine polymer segment, A block copolymer or graft copolymer consisting of is preferably used. The said fluorine-type compound can be obtained as a commercial product, for example, Nippon Oil & Fats Modiper F series, Dainippon Ink & Chemicals Co., Ltd. defensa MCF series, Nippon Synthetic Chemical Co., Ltd. purple light UT series etc. are used preferably.

  The fluorine-containing polymer segment mainly has a function of improving antifouling properties and water / oil repellency, while the non-fluorine polymer segment has an anchor function because of high compatibility with the binder component. Accordingly, even when the surface is repeatedly rubbed, it is difficult to remove these fluorine-based compounds, and various effects such as antifouling properties can be maintained over a long period of time.

  (Silicon compound) As a silicon compound having one or more functional groups capable of reacting with an ionizing radiation curable resin at the terminal, the following general formula (2),

（式中、Ｒａはメチル基などの炭素数１〜２０のアルキル基を示し、Ｒｂは非置換、もしくはアミノ基、エポキシ基、カルボキシル基、水酸基、パーフルオロアルキル基、パーフルオロアルキレン基、パーフルオロアルキルエーテル基、または( メタ) アクリロイル基で置換された炭素数１〜２０のアルキル基、炭素数１〜３のアルコキシ基、またはポリエーテル変性基を示し、各Ｒａ、Ｒｂは互いに同一でも異なっていても良い。また、ｍは０〜２００、ｎは０〜２００の整数である。）で示される構造を有することが好ましい。

(In the formula, Ra represents an alkyl group having 1 to 20 carbon atoms such as a methyl group, and Rb is unsubstituted, or an amino group, an epoxy group, a carboxyl group, a hydroxyl group, a perfluoroalkyl group, a perfluoroalkylene group, a perfluoro group. An alkyl ether group or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a polyether-modified group substituted with a (meth) acryloyl group. Each Ra and Rb are the same or different from each other. Moreover, m is preferably 0 to 200, and n is an integer of 0 to 200.

Polydimethylsilicone having a basic skeleton such as the above general formula (2) is generally known to have a low surface tension and excellent water repellency and releasability. By introducing a group, further effects can be imparted. For example, reactivity can be imparted by introducing an amino group, epoxy group, carboxyl group, hydroxyl group, (meth) acryloyl group, alkoxy group, etc., and a covalent bond is formed by a chemical reaction with the ionizing radiation curable resin composition. it can. In addition, by introducing perfluoroalkyl groups, perfluoroalkylene groups, and perfluoroalkyl ether groups, oil resistance and lubricity can be imparted, and by introducing polyether-modified groups, leveling properties and lubricity can be provided. Can be improved.
Such a compound can be obtained as a commercially available product. For example, silicone oil FL100 having a fluoroalkyl group (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) or polyether-modified silicone oil TSF4460 (trade name, GE Toshiba). Various modified silicone oils can be obtained according to the purpose.

As a preferred embodiment, the silicon-based compound is represented by the following general formula (3),
R _an SiX _4-n general formula (3),
(In the formula, Ra represents a C3-1000 hydrocarbon group including a perfluoroalkyl group, a perfluoroalkylene group, or a perfluoroalkyl ether group, and X represents a carbon such as a methoxy group, an ethoxy group, or a propoxy group. A hydrolyzable group such as an alkoxy group of formulas 1 to 3, an oxyalkoxy group such as a methoxymethoxy group or a methoxyethoxy group, or a halogen group such as a chloro group, a bromo group or an iodo group, which may be the same or different; And n may be an integer of 1 to 3).

  By including such a hydrolyzable group, it is particularly easy to form a covalent bond or a hydrogen bond with the hydroxyl group of the inorganic component, more preferably, the silica component, and there is an effect that the adhesiveness can be maintained. Specific examples of such a compound include fluoroalkylsilanes such as TSL8257 (trade name, manufactured by GE Toshiba Silicone).

  The fluorine-based and / or silicon-based compound having at least one functional group capable of reacting with the ionizing radiation curable resin at the terminal is 0.01 to 10%, preferably 0.8% with respect to the ionizing radiation curable resin. The content is preferably 1 to 3%. When the content is less than 0.01% by mass, sufficient antifouling property and scratch resistance cannot be imparted, and when it exceeds 10% by mass, the strength of the coating film is extremely lowered. These fluorine compounds and silicon compounds may be used singly or as a mixture of two or more, and by appropriately combining them, antifouling properties, water and oil repellency, slip properties, scratch resistance, durability, leveling properties, etc. These properties can be adjusted to achieve the desired function.

  The fluorine-based and / or silicon-based compound having at least one functional group capable of reacting with the ionizing radiation curable resin preferably has compatibility with the ionizing radiation curable resin, and the coating surface used as the outermost surface Can be imparted with slipperiness that is effective in improving antifouling properties and scratch resistance. “Compatibility” means a decrease in transparency due to white turbidity of the coating film or an increase in haze even when the fluorine-based and / or silicon compound is added to the composition coating film in such an amount that the effect of addition can be confirmed. Means having an affinity that cannot be confirmed.

  At least a part of the fluorine-based and / or silicon-based compound having one or more functional groups capable of reacting with the ionizing radiation curable resin at the end forms a covalent bond with the composition by a chemical reaction to form a coating film. It is preferable to be fixed to the surface, and thereby it is possible to stably maintain slipperiness that is effective in improving antifouling properties and scratch resistance over a long period of time.

  (Formation of antifouling protective layer) The antifouling protective layer 14 is formed by ionizing radiation curable resin and fluorine-based and / or having at least one functional group capable of reacting with the ionizing radiation curable resin. A photopolymerization initiator such as a radical photopolymerization initiator, a cationic photopolymerization initiator, a radical photopolymerization accelerator, and a cationic photopolymerization accelerator, a plasticizer, and a stable Add agent, surfactant, filler, etc., disperse or dissolve in solvent, apply with known coating methods such as roll coating, gravure coating, comma coating, die coating, etc., dry, and by irradiation with ionizing radiation such as ultraviolet rays What is necessary is just to make it react (curing). In addition, when making it harden | cure by irradiation of an electron beam, a photoinitiator is unnecessary.

  (Thickness of the antifouling protective layer) The thickness of the antifouling protective layer 14 is a solvent that can be used even in harsh environments, with no expiry date, for a long period of use, and / or for many repeated uses. In order to protect the image from mechanical friction and abrasion, particularly scratching, and to impart durability against scratching, it is about 1 to 25 μm, preferably 3 to 15 μm.

  (Hologram Self-Adhesive Label) The hologram self-adhesive label 40 is manufactured by the above-described manufacturing method. As shown in FIG. 5, the antifouling protective layer 14, the primer layer 16 (if necessary), the release layer 13, and the hologram The layer 15, the reflective layer 17, the adhesive layer 39, the label substrate 21, and the self-adsorbing and re-peeling adhesive layer 29 are provided, and a release paper 23 is provided as necessary. Alternatively, the sheet including the release paper 23 may be cut into a single-wafer label, or the hologram self-adsorption label 40 may be half-cut with only the release paper 23 left. Half-cut processing methods include inserting a hologram self-adsorption label 40 in a stacked state before cutting between the upper mold with a cutter blade and a pedestal, and moving the upper mold up and down, or a cylinder-type rotary cutter There is no particular limitation as long as it is a method capable of half-cutting, such as a heat treatment method using a laser processing means. It is not necessary to remove the debris portion other than the label portion, but it is preferable to half-cut and leave only the label portion, and to remove and remove the other portions in advance (referred to by those skilled in the art as debris removal). Further, when sticking to the adherend 101, it may be stuck while removing waste. Although it does not specifically limit as a shape of a label, For example, a rectangle, an ellipse, a round shape, a donut shape etc. can be illustrated.

  In the conventional antireflective laminate or radiation-emitting panel according to Patent Documents 3 and 4, since it is directly processed into the antireflective laminate or radiation-emitting panel, it can be removed or reattached (fixed) when desired. If a loss occurs on the way, expensive members and processing costs up to that point are wasted, resulting in high costs. As described above, the method for producing a hologram self-adsorption label according to the present invention includes (1) hologram transfer foil preparation step, (2) self-adsorption label preparation step, (3) lamination step, (4) exposure step, (5) It consists of an antifouling protective layer forming process, and at first glance the process seems complicated, but it is a manufacturing method that makes full use of a stable process combining existing equipment and known technology, and the yield of each process is high, Overall, it can be manufactured at low cost.

  (Hologram-attached medium) As shown in FIG. 6, the hologram-attached medium 100 of the present invention has an adhesive layer 29 surface exposed by removing the release paper 23 from the hologram self-adsorption label 40 of the present invention. 101 is attached. The sticking may be performed manually or by a known automatic machine such as a labeler, and is not particularly limited.

  (Adherent) The adherend 101 is not particularly limited. For example, natural fiber paper, coated paper, tracing paper, plastic film that is not deformed by heat during transfer, glass, metal, ceramics, wood, Outside of cloth, ID cards such as employee cards, membership cards and student cards, and devices such as liquid crystal displays and organic electroluminescence displays (image display devices) such as devices, members, parts, etc. may be used. What is necessary is just to select suitably according to a use. Further, at least one part of the adherend 101 may be provided with an image, coloring, printing, printing, or other decoration, and an information recording body such as a magnetic recording layer, an optical recording layer, or an IC chip. May be provided by means of coating, laminating, transferring, embedding and the like.

  (Durability) Even after repeated use, the surface of the adherend 101 can be protected, it can be protected from mechanical and chemical damage over a long period of time, and can be replaced. For example, ID cards such as employee ID cards, membership cards, and student ID cards, especially ID cards, images such as letters, numbers, and face photographs are formed on the surface of the medium. In recent years, these images are formed by a transfer method using thermal transfer or sublimation transfer using a so-called melt transfer type or sublimation transfer type ink ribbon, but unlike images using ordinary printing inks, weather resistance, friction resistance There are weaknesses that lack durability such as durability and chemical resistance. As a solution to this, the hologram self-adsorbing label 40 is stuck on the thermal transfer image, so that the hologram-including medium 100 is obtained. Can be easily attached and fixed to the adherend 101, can be removed and reattached (fixed) when desired, and has excellent surface protection such as scratch resistance against contact with sharp objects. Further, it can be easily replaced with another hologram self-adhesive label which is hardly contaminated with finger grease or the like and which has a decoration desired by the user. Therefore, you can enter and leave many security-controlled rooms such as gas station cards and construction site cards that are used in extremely harsh environments, as well as long-term entrance / exit cards, point cards, and financial institutions. It can be used suitably also for an entrance / exit card etc. which repeats.

  In addition, it can be easily attached and fixed to the surface of a device such as a liquid crystal display device, and can be removed and reattached (fixed) when desired. Sometimes it can be removed and replaced with another decoration or design you like. Furthermore, for example, if the touch panel is used for a liquid crystal display or an organic electroluminescence display, even if the user touches it directly or randomly, even if the user touches it randomly, the surface of the finger can be soiled. It has excellent antifouling properties that are difficult to resist, has excellent scratch resistance that prevents scratches even when touching sharp objects, and can maintain the image quality of the display.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this. In addition, except a solvent, each composition of each layer is a mass part of solid content conversion.

(Example 1)
(1) Preparation Step of Hologram Transfer Foil 10 A 25 μm-thick PET film is used as the transfer substrate 11, and the following release layer composition (coating liquid) is applied to one surface of the substrate 11 by a gravure coating method. Was applied to a thickness of 2 μm after drying and dried to form a release layer 13.
・ <Peeling layer composition>
Peeling varnish 45-2 (made by Showa Ink Industries, Peeling varnish product name) 25 parts Solvent (ethyl acetate: toluene = 1: 1) 75 parts Gravure reverse coating of the following hologram layer 15 composition onto the peeling layer 13 surface The embossing of the duplicating machine is a press die with a quasi-continuous pattern that is coated by a 2P method from a diffraction grating by a two-beam interference method after coating and drying at 100 ° C. so that the thickness after drying is 2 μm. It stuck on the roller and heat-pressed (embossed) between the opposing rollers, and the relief which consists of a fine uneven | corrugated pattern was shaped. Immediately after the shaping, the hologram layer 15 was formed by irradiating and curing with ultraviolet rays using a high-pressure mercury lamp. Titanium oxide having a thickness of 50 nm was formed on the relief surface by a vacuum vapor deposition method to form a transparent reflection layer 17, thereby obtaining a hologram transfer foil 10.
・ <Hologram layer composition>
Iupimer UV V3031 (manufactured by Mitsubishi Chemical Co., Ltd., trade name of ultraviolet curable resin) 25 parts methacrylate oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Murasaki 6630B) 5 parts reactive silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22) -1602) 0.5 part Photopolymerization initiator (Ciba, trade name Irgacure 184) 0.9 part Solvent (ethyl acetate: methyl isobutyl ketone = 1: 1) 70 parts (2) Preparation process of self-adsorption label 20 It consists of a PET film (label substrate 21) having a thickness of 100 μm / a self-adsorbing and releasable resin layer (adhesive layer 29) having a thickness of 30 μm / PET separator paper (release paper 23) having a thickness of 38 μm. The product name olefin gel polymer sheet of Panac Co., Ltd. was used as the self-adsorption label 20.
(3) Laminating Step Urethane-based two-component adhesive with the reflective layer 17 surface of the hologram transfer foil 10 and the label base material 21 (pre-adhesively treated) surface of the self-adsorbing label 20 as an adhesive layer 39 Was laminated by a known dry lamination method to obtain a laminate 30.
(4) Exposure process The transfer substrate 11 of the hologram transfer foil 10 was peeled off and removed from the laminate 30 to expose the surface of the release layer 13.
(5) Antifouling protective layer 14 forming step The following primer layer 16 composition is applied to the surface of the release layer 13 exposed as described above by gravure coating so that the thickness after drying becomes 1 μm. The primer layer 16 was formed by drying at 0 ° C.
On the surface of the primer layer 16, the following antifouling protective layer 14 composition was applied by gravure reverse coating so that the thickness after drying was 3 μm, dried at 100 ° C., and then using a high pressure mercury lamp. The hologram self-adhesive label 40 of Example 1 was obtained by forming the antifouling protective layer 14 by irradiating it with ultraviolet rays.
・ <Anti-fouling layer composition>
Purple light UT-4314
(Nippon GOHSEI, fluorine-containing compound UV curable resin trade name) 25 parts Photopolymerization initiator (Ciba, trade name Irgacure 184) 0.3 part Solvent (ethyl acetate: methyl isobutyl ketone = 1: 1 75 parts

(Example 2) A hologram self-adsorption label 40 of Example 3 was obtained in the same manner as in Example 1 except that the following antifouling layer composition was used as the antifouling layer composition.
・ <Anti-fouling layer composition>
Purple light UT-4314
(Nippon GOHSEI, fluorine-containing compound UV curable resin product name) 25 parts Silicon compound (manufactured by Shin-Etsu Chemical Co., Ltd., product name X-22-1602) 0.2 part Photopolymerization initiator (manufactured by Ciba, Product name Irgacure 184) 0.5 part Solvent (ethyl acetate: methyl isobutyl ketone = 1: 1) 75 parts

Example 3 A hologram self-adsorption label 40 of Example 2 was obtained in the same manner as in Example 1 except that the following antifouling layer composition was used as the antifouling layer composition.
・ <Anti-fouling layer composition>
Methacrylate oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Murasaki 6630B) 25 parts Shiko UT-3841 (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name of fluorine compound) 0.7 parts Photopolymerization initiator (manufactured by Ciba, trade name: Irgacure) 184) 0.5 part Solvent (ethyl acetate: methyl isobutyl ketone = 1: 1) 75 parts

  (Examples 4 to 6) A mobile phone is used as the adherend 101, and the release sheet of the hologram self-adsorption label 40 of Examples 1 to 3 is peeled off and removed from the display screen of the liquid crystal display. It stuck on the 29th surface and obtained the medium 100 with a hologram of Examples 4-6.

  (Evaluation) When the pencil hardness test was measured in accordance with JIS-K-5400 on the antifouling protective layer 14 surface of the hologram self-adsorption label 40 of Examples 1 to 3, it had a hardness of 2H or more. It was. Further, on the surface 14 of the antifouling protective layer 14 of the hologram self-adsorption label 40 of Examples 1 to 3, 1 kg of a weak alkaline cleaner [cleaner IC-100S: trade name (manufactured by Lion Corporation)] was immersed in a becot. After reciprocating 30 times with load, the absolute reflectance and haze value were measured, but there was no significant change. The absolute reflectance was measured by using a spectrophotometer (UV-3100PC: trade name) manufactured by Shimadzu Corporation, and the haze value was JIS K 7105: 1981 “Optical characteristics of plastics. The haze value of the outermost surface was measured according to “Test method”. Further, as a scratch resistance evaluation test, the surface of the antifouling protective layer 14 of Examples 1 to 3 was changed to a predetermined friction load (200 g within a range of 200 to 1000 g) using # 0000 steel wool. ), And the subsequent haze value was measured, but there was no significant change.

  Moreover, in the hologram-attached media 100 of Examples 4 to 6, each hologram self-adsorption label 40 portion can be easily removed by peeling with a finger, and when the peeled label is attached again, it can be normally attached and self-adsorption And re-peelability could be confirmed. Furthermore, the hologram-mounted media 100 of Examples 4 to 6 were excellent in design properties and the brightness of the hologram (diffraction grating).

It is sectional drawing of the hologram transfer foil used for the manufacturing method of the hologram self-adsorption label of this invention. It is sectional drawing of the self-adsorption label transfer foil used for the manufacturing method of the hologram self-adsorption label of this invention. It is sectional drawing explaining the lamination process of the manufacturing method of the hologram self-adsorption label of this invention. It is sectional drawing explaining the exposure process of the manufacturing method of the hologram self-adsorption label of this invention. It is sectional drawing of the hologram self-adsorption label which shows one Example of this invention. It is sectional drawing of the medium with a hologram which affixed the hologram self-adsorption label of this invention on the to-be-adhered body.

Explanation of symbols

10: Hologram transfer foil 11: Transfer base material 14: Antifouling protective layer 15: Hologram layer 16: Primer layer 17: Reflective layer 20: Self-adsorption label 21: Label base material 23: Release paper 29: Adhesive layer 30: Lamination Body 39: adhesive layer 40: hologram self-adhesive label 100: medium with hologram 101: adherend

Claims (3)

(1) a transfer substrate, a hologram transfer foil preparation step for preparing a hologram transfer foil comprising a release layer, a hologram layer, and a reflective layer on one surface of the transfer substrate; (2) a label substrate and the label A self-adsorbing label preparing step of providing a self-adsorbing label having a self-adsorbing and re-peelable adhesive layer on one surface of the substrate, and a release paper provided on the adhesive layer surface so as to be peelable; (3 And (4) transferring the hologram transfer foil from the laminate by laminating the reflective layer surface of the hologram transfer foil and the label base material surface of the self-adsorbing label via an adhesive layer. It is characterized by comprising: an exposure step of peeling and removing the substrate to expose the release layer surface; and (5) an antifouling protective layer forming step of providing an antifouling protective layer on the exposed release layer surface. A method for manufacturing a hologram self-adsorption label. A hologram self-adhesive label manufacturing method according to claim 1, wherein the antifouling protective layer, release layer, hologram layer, reflective layer, adhesive layer, label substrate, and self-adsorbing and re-peeling are manufactured. A fluorine-based and / or silicon-based compound having an adhesive layer, wherein the antifouling protective layer has an ionizing radiation curable resin and at least one functional group capable of reacting with the ionizing radiation curable resin at the terminal. A hologram self-adhesive label characterized by being cured by irradiation with ionizing radiation. A medium with a hologram, wherein the exposed adhesive layer surface of the hologram self-adsorption label according to claim 2 is adhered to an adherend.

Images