JP4858133B2 - Hologram label - Google Patents

Description

The present invention relates to a hologram label, and more particularly, color variable by the liquid crystal layer, a bright hologram metallic luster and, in no significant degradation of appearance when affixed to the object to be adhered comprising a metal layer, bright, The present invention relates to a hologram label that is excellent in design and / or security and can prevent counterfeiting such as replacing 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, functional expression, common name, or industry term for “polyethylene terephthalate”, “stamper” for “mold”, and “UV” for “ultraviolet light”.

The Lord applications of the hologram label of (Lord applications) the present invention, used by sticking to the attached body, cash vouchers such as Kurejitsuto card, certificate, certificate, etc., employee ID card, membership card, such as a student ID Media, such as ID cards, gift certificates, admission cards, passports, service points, etc. that prove the rights and qualifications paid (prepaid), book covers, brochures, record jackets, package, clothing , And necessities of design and / or security such as daily necessities. However, if the application of attaching to the design and / or security to be adhered body in need of, but is not particularly limited.

(Background Art) Conventionally, as a hologram label, a metal gloss hologram is known in which a metal thin film is formed on the entire surface by a vacuum film forming method to form a reflective layer. However, although very bright hologram silvery metallic luster with a metal reflective layer is provided, when attached to the object to be adhered comprising a metal layer, a reflective layer of metal thin film is subjected to electric corrosion, reflection It becomes partly, the reflectance decreases, unevenness occurs on the surface, the light is irregularly reflected and the hologram is whitened, the hologram effect is reduced, the appearance is significantly deteriorated, and sometimes the hologram cannot be observed at all There was a problem that. As the reflective layer, an aluminum thin film having a silver color and excellent metallic luster is usually used, but the thickness of the aluminum thin film is very thin, about 100 to 500 nm, and also has a high ionization tendency and is susceptible to electrical corrosion. This is especially true in environments where acidic substances such as sweat, food and medicine are affected. Disappearance, occurrence of unevenness, whitening, the hologram effect is reduced, the appearance is remarkably deteriorated, and sometimes the hologram cannot be observed at all.
Therefore, the hologram label, when affixed to the object to be adhered comprising a metal layer, missing, non-uniformity, and whitening without significant degradation without the appearance, bright, a hologram having excellent design properties and / or security There is a need for hologram labels that can be attached.

(Prior Art) Conventionally, a hologram label is known in which a full-surface reflective layer of a metal thin film is provided by a vacuum film forming method (see, for example, Patent Document 1). However, although bright hologram by silvery metallic luster can be obtained in the metallic reflecting layer and adhering the hologram to be adhered comprising a metal layer with a hologram label, the influence of the metal layer of the sticking material, the label The metal layer is subject to electrical corrosion, resulting in partial reflection, reduced reflectivity, uneven surface, irregular reflection of light, and whitening of the hologram, reducing the hologram effect. As a result, the appearance is significantly deteriorated, and sometimes the hologram cannot be observed at all.
Further, the present applicant discloses one using a high-brightness ink layer as a reflection layer and one using a transparent reflection layer and a high-brightness ink layer in combination (for example, see Patent Document 2). However, in the case of using only a high-brightness ink layer as a reflection layer, although there is little practical problem, the light diffraction effect equivalent to that of a metal reflection layer cannot be obtained, and a combination of a transparent reflection layer and a high-brightness ink layer is used. There is no description of deterioration with respect to electrical corrosion, and the above-mentioned drawbacks are solved by using a transparent reflective layer and a high-brightness ink layer in combination.
Further, the present applicant has disclosed a forgery prevention paper in which a hologram and a thread subjected to cholesteric liquid crystal printing are incorporated (see, for example, Patent Document 3). However, because of the use of a transparent reflective layer black printing and, even when adhered to the sticking member comprising a metal layer, electric corrosion is not received, although color variable state is good by the liquid crystal layer, There is a disadvantage that a hologram with a bright metal layer and gloss cannot be observed.
Conventionally, as a brittle hologram label, a brittle seal in which a base material, a release layer, a hologram layer, a reflective layer, a patterned brittle layer, and an adhesive layer are sequentially laminated is disclosed (for example, see Patent Document 4). ). However, when peeled after stuck to the adherend, destroys vertically frangible seal along the patterned brittle layer, or adhering a hologram to be adhered comprising a metal layer, let alone electrical There is no description of deterioration against corrosion.
Further, a brittle seal in which a base material, a hologram layer, a reflective layer, and an adhesive layer are sequentially laminated, and a surface treatment is performed in a pattern on the base material, and a portion where the surface treatment is performed and a portion where the surface treatment is not performed A brittle seal using the difference in peel strength is disclosed (for example, see Patent Document 5). However, if it is peeled off, it will be destroyed along the pattern of the surface treatment. However, since the peel strength is partially adjusted by the surface treatment, there is a problem that the manufacturing process increases, including the metal layer. or adhered to the hologram to be adhered member, much less is no description of degradation to electrical corrosion.

Japanese Patent No. 2877968 JP 2003-285599 A JP 2005-325482 A JP-A-8-152842 Japanese Patent Laid-Open No. 9-244519

In order to solve the above-described problems, the present inventors have made extensive studies and have completed the present invention. Its purpose is color variable by the liquid crystal layer, a bright hologram metallic luster and, even when adhered to the sticking member comprising a metal layer, electric corrosion is maintained hologram effect does not occur on the label appearance It is intended to provide a hologram label that is bright, excellent in design and / or security, and capable of preventing forgery such as replacing a hologram.

In order to solve the above problems, a hologram label according to the invention of claim 1 includes a base material, and at least a brittle layer, a hologram layer, a transparent reflection layer, a high-brightness ink layer, and one surface of the base material. adhesive layer are laminated in this order, on the other surface of the base material, a hologram label having at least liquid crystal layer, wherein a substrate is a transparent substrate, the high-brightness ink layer is at least an organic fatty acid, methyl silyl isocyanate or it comprises a metal deposited film strip surface treated with a cellulose derivative, and a pattern, wherein a pressure-sensitive adhesive layer is black, even if the hologram label affixed to the object to be adhered comprising a metal layer, the hologram The hologram label is characterized in that the hologram effect is maintained without causing electrical corrosion on the label.
The hologram label according to the invention of claim 2 is such that the transparent reflection layer is made of titanium oxide.
According to a third aspect of the present invention, there is provided a hologram label comprising: the liquid crystal layer, the transparent substrate, the brittle layer, the hologram layer, the transparent reflective layer, the high-brightness ink layer, and the adhesive layer that constitute the hologram label . 3. The hologram label according to claim 1, wherein all layers have a surface resistivity defined by JIS-K6911 of 10 ¹² Ω or more.

According to the present invention of claim 1, and color variable state by the liquid crystal layer, a bright hologram metallic gloss is observed at the same time, and, even when adhered to the sticking member comprising a metal layer, electricity label There is provided a hologram label that does not cause erosion, maintains the hologram effect, has no significant deterioration in appearance, is bright, has excellent design and / or security, and can prevent counterfeiting such as replacing a hologram.
According to the second to third aspects of the present invention, there is provided a hologram label on which a brighter hologram having excellent design and / or security can be attached.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a sectional view of a hologram label showing one embodiment of the present invention.
Figure 2 is a sectional view adhering a hologram label to the object to be adhered comprising a metal layer.

  (Hologram Label) As shown in FIG. 1, the hologram label 1 of the present invention has a base material 11 and a brittle layer 13, a hologram layer 15, a transparent reflection layer 17, a high brightness on one surface of the base material 11. The ink layer 18, the primer layer 21, and the pressure-sensitive adhesive layer 19 are laminated in order, and the liquid crystal layer 41 is provided on the other surface of the substrate 11. The high-brightness ink layer 18 is patterned, and the adhesive layer 19 is black. If necessary, a hard coat layer 45 may be provided on the surface of the liquid crystal layer 41, a primer layer may be provided between the hard coat layer 45 and the liquid crystal layer 41, or a release paper may be provided on the adhesive layer 19 so as to be peelable. In addition, a primer layer may be provided in other layers in order to improve the adhesion between the layers. Hard coat layer 45 (if necessary) / primer layer (if necessary) / liquid crystal layer 41 / substrate 11 / brittle layer 13 / primer layer 12 (if necessary) / hologram layer 15 / transparent reflective layer 17 / high brightness ink layer 18 (pattern shape) / primer layer 21 (if necessary) / adhesive layer 19 (dark black).

In the hologram label 1 of the present invention, the liquid crystal layer 41, the brittle layer 13, the hologram layer 15, the transparent reflection layer 17, the patterned high-brightness ink layer 18, the black adhesive layer 19, and the liquid crystal layer 41 are essential. The high-brightness ink layer 18 contains at least metal vapor-deposited film strips surface-treated with an organic fatty acid, methylsilyl isocyanate, or a cellulose derivative. The brittle layer 13 is a peelable or cohesive breakable layer, or a layer having a partial difference in adhesion. Preferably, the transparent reflective layer 17 is a titanium oxide thin film, and the surface resistivity defined by JIS-K6911 of all layers constituting the hologram label is 10 ⁶ Ω or more, preferably 10 ⁸ Ω or more, more preferably. Is 10 ¹² Ω or more.

When the layer of the hologram label 1 is peeled off in order to counterfeit the hologram, for example, it is a hologram brittle seal that prevents the hologram from being counterfeited by peeling off from the brittle layer 13 so that it cannot be reattached. The brittle layer 13 is a peelable or cohesive fracture layer, or a layer having a partial difference in adhesive force. Therefore, in the case of a peelable layer, the brittle layer 13 is peeled between the substrate 11 and the hologram layer 15. In the case of a cohesive fracture layer, the brittle layer 13 breaks and the hologram layer 15 cannot be replaced. In the case of a layer having a partial difference in adhesion, the hologram layer 15 Forgery can be prevented by being destroyed and becoming non-replaceable. The hologram layer 15, the transparent reflective layer 17, and the patterned high-brightness ink layer 18 produce a bright portion (design) hologram due to the synergistic effect, and the liquid crystal layer 41 is a black adhesive layer in the portion without the patterned high-brightness ink layer 18. With 19 as a background, the color variable state of the adhesive layer 19 can be clearly observed. Then, even when adhering the hologram to be sticking member 100 including a metal layer 103, including the metal layer 103 to be attached body 100 does not include a layer of conductive labels, yet all of the layers Since it is composed of a layer having a high surface resistivity, it is not subject to electrical corrosion with the metal layer 103, and the hologram effect is maintained, so that the reflection becomes partial or the reflectance decreases. Then, unevenness occurs on the surface, the light is irregularly reflected and the hologram is whitened, and the hologram effect is not reduced, and a bright hologram can be observed. By using titanium oxide with high heat resistance for the transparent reflective layer 17, even if some cracks (cracks) enter, it is transparent and not conspicuous, and the reflectivity of the crack part is replaced by the reflection of the high brightness ink layer 18 below it In addition, since the reflectivity is maintained, a bright hologram can be observed.

  Moreover, the hologram can be observed in a pattern by using the hologram layer 15 / transparent reflection layer 17 / patterned high-brightness ink layer 18. Conventionally, in order to create a patterned hologram, after printing in a pattern with a water-soluble resist ink, providing a metal reflective layer on the entire print surface, and then dissolving the resist ink in a solvent such as water, the resist ink This was performed by leaving only the metal reflection layer in a portion without any gap, and there were many steps, waste liquid treatment was also required, and the cost was high. However, according to the present invention, other than the transparent reflective layer made of a titanium oxide thin film formed by the conventional vacuum film forming method, it can be formed by a printing method using existing equipment, and can be produced in a small lot, with a low cost. Can be produced in

(Substrate) The substrate 11 may be a transparent substrate, and various materials can be applied depending on the application. For example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as nylon 6, polyolefin resins such as polypropylene, cyclic polyolefin resins, vinyl resins such as polyvinyl chloride, acrylics such as polymethyl methacrylate Examples thereof include styrene-based resins such as cellulose resins, imide resins, polycarbonates, and ABS resins, and cellulose films such as cellulose triacetate. The 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 substrate 11 may be a stretched film or an unstretched film, but a film stretched in a uniaxial direction or a biaxial direction is preferable for the purpose of improving the strength. The thickness of the substrate 11 is usually about 2.5 to 100 μm, preferably 4 to 50 μm, and most preferably 6 to 25 μm.

  The substrate 11 is used as a film, sheet or board formed of at least one layer of these resins. Usually, polyester-based films such as polyethylene terephthalate and polyethylene naphthalate have good balance in terms of strength, heat resistance and price, and are preferably used. Polyethylene terephthalate is particularly optimal.

  Prior to coating, the substrate 11 is applied to the coated surface by corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer (also called anchor coat, adhesion promoter, or easy adhesive) coating treatment, pre-heat treatment, dust removal. Easy adhesion treatment such as treatment, vapor deposition treatment, and alkali treatment may be performed. Moreover, you may add additives, such as a filler, a plasticizer, a coloring agent, and an antistatic agent, to this resin film as needed.

  (Brittle layer) The brittle layer 13 is a peelable or cohesive breakable layer, or a layer having a partial difference in adhesion. In the case of a peelable layer, it peels between the base material 11 and the hologram layer 15, and in the case of a cohesive fracture layer, the brittle layer 13 breaks, and the hologram layer 15 becomes non-replaceable, Further, in the case of a layer having a partial difference in adhesive strength, forgery can be prevented by destroying the hologram layer 15 and making it impossible to replace it. The interface to be peeled off may be any of the interface between the base material 11 and the brittle layer 13, and the interface between the brittle layer 13 and the hologram layer 15 (primer layer 12 when there is a primer layer). Both interfaces may be mixed.

  (Peelable layer) When the brittle layer 13 is a peelable layer, examples of the brittle layer 13 include a release resin, a resin containing a release agent, and a curable resin that crosslinks with ionizing radiation. Applicable. The releasable resin is, for example, a fluorine resin, silicone, melamine resin, epoxy resin, polyester resin, acrylic resin, or fiber resin. The resin containing the release agent is, for example, an acrylic resin, vinyl resin, polyester resin, or fiber resin obtained by adding or copolymerizing a release agent such as fluorine resin, silicone, or various waxes. is there. The curable resin that crosslinks with ionizing radiation is, for example, a resin containing a monomer or oligomer having a functional group that is polymerized (cured) with ionizing radiation such as ultraviolet (UV) or electron beam (EB).

  (Cohesive fracture layer) When the brittle layer 13 is a cohesive fracture layer, the brittle layer 13 may be a synthetic rubber resin such as natural rubber, butyl rubber, polychloroprene or styrene-butadiene copolymer resin. , Silicone resin, acrylic resin, alkylphenol resin, rosin resin such as rosin and hydrogenated rosin, vinyl acetate resin such as polyvinyl acetate and ethylene-vinyl acetate copolymer, urethane resin, acrylonitrile, hydrocarbon resin Etc. are applicable.

  (Adhesive strength difference layer) In the case where the brittle layer 13 is a layer having a partial difference in adhesive strength, the brittle layer 13 is smoothly peeled off from the substrate in the weakly bonded portion, and the strong bonded portion. In the method, there is no particular limitation as long as it is a material that deteriorates or changes its quality due to heat at the time of forming the reflective layer or irradiation of ionizing radiation at the time of forming the hologram layer to increase the adhesive force with the substrate. For example, from acrylic resin, vinyl chloride-vinyl acetate copolymer resin, polyester resin, polymethacrylate resin, polyvinyl chloride resin, cellulose resin, silicone resin, chlorinated rubber, casein, various surfactants, metal oxides, etc. What mixed 1 type (s) or 2 or more types etc. can be used. Among these, an acrylic resin having a molecular weight of about 20,000 to 100,000, or an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin having a molecular weight of 8000 to 20000, and a polyester resin having a molecular weight of 1,000 to 5,000 as an additive. It is preferably composed of a composition containing ˜5% by weight, and is disclosed in detail in JP-A-2005-106857.

The brittle layer 13 is formed by dispersing or dissolving the resin in a solvent, roll coat, reverse roll coat, gravure coat, reverse gravure coat, bar coat, rod coat, kiss coat, knife coat, die coat, comma coat, A coating or coating method such as flow coating or spray coating may be applied to at least one part and dried to form a coating film, or a coating film may be formed by an extrusion coating method.
Further, if necessary, it may be crosslinked by heat drying at a temperature of 30 ° C. to 120 ° C., aging, or irradiation with ionizing radiation.

  The thickness of the brittle layer 13 is usually about 0.5 μm to 15 μm, preferably about 1 μm to 10 μm. If it is less than this range, the peelability is unstable, and if it exceeds this range, the peelability is too good and useless.

  (Primer layer) The primer layer 12 is preferably provided on the surface of the brittle layer 13 in order to stabilize the film formability and adhesiveness of the hologram layer 15. Examples of the primer layer 12 include polyurethane resin, polyester resin, polyamide resin, epoxy resin, phenol resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acid Modified polyolefin resin, copolymer of ethylene and vinyl acetate or acrylic acid, (meth) acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, polybutadiene resin, rubber compound, petroleum resin, alkyl titanate Series compounds, polyethyleneimine compounds, isocyanate compounds, cellulose derivatives and the like can be used.

One or more of the above-mentioned resins or monomers, oligomers, or prepolymers thereof as a main component, and if necessary, for example, various stabilizers, fillers, reaction initiators, curing agents or crosslinking agents, etc. These additives can be used alone or in combination, or a combination of a main agent and a curing agent can be used, such as a one-component curable type or a two-component curable type.
These resins are appropriately dissolved or dispersed in a solvent, and kneaded thoroughly as necessary to prepare a coating agent composition (ink, coating solution), roll coating method, gravure coating method, spray coating method. The primer layer 12 is formed by applying and drying by a known coating method such as the above, or by reacting by aging treatment after drying or drying. The thickness of the primer layer 12 is about 0.05 to 10 μm, preferably 0.1 to 5 μm.

(Hologram layer) The hologram layer 15 is colorless or colored, transparent or translucent, and may be a single layer or a multilayer, and a thermoplastic resin capable of reproducing irregularities by casting or embossing. A curable resin or a photosensitive resin composition capable of forming a cured portion and an uncured portion according to light diffraction pattern information can be used. Specifically, for example, thermoplastic resins such as polyvinyl chloride, acrylic (polymethyl methacrylate), polystyrene, or polycarbonate, unsaturated polyester, melamine, epoxy, polyester (meth) acrylate, urethane (meth) acrylate, epoxy ( It is a thermosetting resin such as (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, or triazine acrylate, each of which is a single, a thermoplastic resin, or a thermosetting resin. It may be a mixture of comrades or a mixture of a thermoplastic resin and a thermosetting resin. An ionizing radiation curable resin composition having a radically polymerizable unsaturated group and having thermoformability or a radically polymerizable unsaturated monomer added can also be used.
As the ionizing radiation curable resin, for example, an epoxy-modified acrylate resin, a urethane-modified acrylate resin, an acrylic-modified polyester, and the like can be applied, and a urethane-modified acrylate resin is preferable.

  Preferably, the material of the hologram layer 15 includes (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. Ionizing radiation curable resin containing urethane (meth) acrylate oligomer which is a reaction product of polyfunctional (meth) acrylates having one or polyhydric alcohols having at least two hydroxyl groups in the molecule (this specification) (Referred to as “ionizing radiation curable resin composition M”), reactive silicone and polyethylene wax. More preferably, a (meth) acrylate oligomer is also included and cured. What is necessary is just to harden with ionizing radiation, after apply | coating this composition and drying and shaping | molding the fine unevenness | corrugation relief which expresses a hologram function. The ionizing radiation curable resin is also called a crosslinkable resin, and the same applies to other layers.

  (Ionizing radiation curable resin composition M) The “ionizing radiation curable resin composition M” is a cured product of an ionizing radiation curable resin containing a urethane (meth) acrylate oligomer. The photocurable resin etc. which are indicated by 329031 gazette can be illustrated, and it mentions also in an example. That is, “ionizing radiation curable resin composition M” (1) isocyanates having 3 or more isocyanate groups in the molecule, (2) at least one hydroxyl group and at least two (meth) acryloyloxy groups in the molecule Reaction product of polyfunctional (meth) acrylates having, or (3) polyhydric alcohols having at least two hydroxyl groups in the molecule.

  ((Meth) acrylate oligomer) The (meth) acrylate oligomer may be a heat-resistant oligomer, and examples thereof include trade names of Nippon Synthetic Chemical Co., Ltd .; Purple light 6630B, 7510B, 7630B and the like.

  (Polyethylene wax) Polyethylene wax includes polyethylene resin particles and beads, and is preferably spherical beads. However, when polyethylene wax is added, the foil breakage is reduced, so the amount added is about 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, with respect to 100 parts by weight of ionizing radiation curable resin. And

  (Reactive silicone) Reactive silicone is a reactive silicone that reacts with and binds with resin when cured with ionizing radiation, and is modified by acrylic, methacrylic, or epoxy modification. The ratio on the basis of mass containing silicone is about 0.1 to 10 parts, preferably 0.3 to 5 parts relative to “ionizing radiation curable resin composition M” 100. If it is less than this range, peeling from the press stamper is insufficient at the time of relief molding, and it is difficult to prevent contamination of the press stamper and the moldability is poor. Further, beyond this range, the adhesiveness of the reflective layer to the hologram layer surface is low, and the commercial value is lost by peeling between the hologram layer and the reflective layer. Addition of conventional silicone oil has poor adhesion to the reflective layer.

  As described above, the hologram layer 15 includes the “ionizing radiation curable resin composition M”, and if necessary, (meth) acrylate oligomer, reactive silicone, and polyethylene wax, thereby providing relief moldability. It has a high light diffraction effect and can also serve as a hard coat function. In particular, by including polyethylene wax, the scratch resistance (scratch resistance) is remarkably improved.

  (Formation of hologram layer) The hologram layer 15 contains the above-mentioned ionizing radiation curable resin, (meth) acrylate oligomer, reactive silicone, and polyethylene wax as required, and further, if necessary, a photopolymerization initiator, A plasticizer, stabilizer, surfactant, etc. are added, dispersed or dissolved in a solvent, applied by a known coating method such as roll coating, gravure coating, comma coating, die coating, and dried to form a coating film. It ’s fine. The thickness of the hologram layer 15 is usually about 0.5 μm to 20 μm, preferably about 1 μm to 10 m, and may be applied multiple times.

  (Hologram) Next, on the surface of the hologram layer 15, a predetermined relief structure such as a hologram that exhibits a light diffraction effect is formed 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.

  As a method for producing these relief shapes, in addition to holograms and diffraction gratings produced using hologram photographing and recording means, holograms produced using an electron beam drawing device based on optical calculations such as interference and diffraction, A diffraction grating can also be mentioned. Also, a relatively large pattern such as a hairline pattern or a line pattern may be a machine cutting method. These holograms and / or diffraction gratings may be recorded single or multiple, or may be recorded in combination. These original plates can be prepared by known materials and methods, and usually, laser beam interference using a glass plate coated with a photosensitive material, using an electron beam drawing apparatus on a glass plate coated with an electron beam resist material. An electron beam drawing method for patterning can be applied.

  (Relief shaping) The relief shape is shaped (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 plate can be duplicated by using it as a mold and superimposing the original plate on the resin layer and then heat-pressing both of them with an appropriate means such as a heating roll.

  (Relief Curing) 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 (hologram layer 15) when cured (reacted) by irradiation with ionizing radiation after the relief is formed. The ionizing radiation may be classified according to the quantum energy of the electromagnetic wave, but in this specification, all ultraviolet rays (UV-A, UV-B, UV-C), visible rays, gamma rays, X-rays, electrons It is defined as including a line. Accordingly, ultraviolet (UV), visible light, gamma rays, X-rays, or electron beams can be applied as ionizing radiation, but ultraviolet (UV) is preferred. An ionizing radiation curable resin that is cured by ionizing radiation may contain a photopolymerization initiator and / or a photopolymerization accelerator in the case of ultraviolet curing, and may not be added in the case of high energy electron beam curing. Can be cured even with thermal energy.

(Relief pattern) The pattern of the hologram layer 15 is not particularly limited, but may be an individual pattern or a pseudo-continuous pattern. When creating a press mold for the pseudo continuous pattern, a plurality of small relief plates may be matched with high accuracy so that the joints are not noticeable, or the joints are filled with resin. In this way, by using a quasi-continuous pattern, the area can be as large as possible, or preferably the entire surface. If the individual pattern previously formed a registration mark tuned to picture and the picture it may be attached to a desired position of the object to be adhered body.

(Transparent reflection layer) / Transparent reflection layer 17 has a substantially colorless and transparent hue, and its optical refractive index is different from that of the hologram layer. Since it can be visually recognized, a transparent 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 may be a mixture of two or more thereof. Titanium oxide (TiO ₂ ) is preferred because of its large heat resistance and refractive index difference.

  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.

  (High-Brightness Ink Layer) By providing the high-brightness ink layer 18 on the surface of the transparent reflection layer 17, the reproduced image of the hologram and / or the diffraction grating can be clearly seen. Conventionally, an aluminum metal thin film formed by a vacuum deposition method has been used as a metallic glossy reflection layer, except for a layer that exhibits a special function. In other aluminum foils, for example, rolled, metal gloss as high as that obtained by vacuum thin film method was not obtained. In addition, other metals have a color tone or are expensive. Thus, vacuum-deposited aluminum thin films have been used over a long period of time for a wide range of practical applications.

  Conventionally, there has been a printing ink that imparts a metallic luster. The ink is a metallic printing ink such as silver or gold using a metal pigment such as aluminum paste or aluminum powder. The aluminum paste has a leafing type and a non-leafing type, but using either of them did not reach the metallic luster of the metal thin film by the vacuum thin film method. Furthermore, although there was an ink using a powder obtained by pulverizing a vapor-deposited aluminum thin film, the surface treatment was different and the dispersibility was poor, and sufficient high luminance could not be obtained.

  However, in the present invention, the transparent reflective layer 15 and a metallic ink layer (high-intensity) printed using a high-brightness ink containing a metal-deposited film strip surface-treated with at least an organic fatty acid, methylsilyl isocyanate, or a cellulose derivative. It has been found that when used in combination with the brightness ink layer 18), it becomes difficult to whiten even when bent at high temperatures and becomes a bright hologram label.

  The metallic ink layer is a printing layer using a printing ink that gives a metallic luster-like appearance (metallic tone), and is a vapor-deposited metal obtained by pulverizing a vapor-deposited metal film that has been surface-treated with at least an organic fatty acid, methylsilyl isocyanate, or a cellulose derivative. It is a printing layer using the high-intensity ink containing the film strip. Since it is a printing method, it may be provided partially, and a high-brightness ink reflecting layer can be manufactured at low cost with existing printing equipment. By printing the metallic print layer 17 using a high-brightness ink composed of a metal thin film piece and a binder on the surface of the transparent reflection layer 15, it is possible to exhibit a higher metallic tone and to provide a reflection layer for a light diffraction image. In addition, it is highly designable, and it is possible to easily determine whether it is true or false by visual inspection, so that security is enhanced, small lot production can be handled, and cost can be reduced. In addition, since the high-brightness ink layer 18 is a printing method, if there is another print layer, it is easy to provide a high-brightness ink layer in synchronization with this print pattern. The design effect is further enhanced by providing the printed pattern so as to be synchronized. The term “partial” refers to all patterns such as letters, numbers, symbols, illustrations, patterns, and photographs.

  In addition, an aluminum metal thin film formed by a conventional vacuum deposition method can provide a sufficient metallic luster. However, in order to enhance the design, in order to provide a partial aluminum metal thin film, once the aluminum metal thin film is provided on the entire surface by a vacuum film forming method, a resist is printed and etched in a separate process. The cost is very high, and the number of manufacturing processes increases, making it unsuitable for small lot production. In addition, there is a drawback of whitening when bent at high temperatures.

  (High-brightness ink) By making the transparent reflection layer 15 and the high-brightness ink layer 18 into two layers, the light diffraction image of the bright hologram layer 15 can be visually recognized. The high-brightness ink is a high-brightness ink having a metallic luster comparable to a metal vapor-deposited film. The surface of the metal vapor-deposited film strip is treated with an organic fatty acid, methylsilyl isocyanate, or a cellulose derivative, and dispersed in the ink. The metallic luster of the ink coating film is increased in brightness. The ink is composed of a metal vapor-deposited film strip treated with an organic fatty acid, methylsilyl isocyanate, or a cellulose derivative, a binder, an additive, and a solvent. If necessary, it can be converted into a gravure ink, a screen ink, or a flexo ink. Good.

  As the metal of the metal vapor deposited film strip, aluminum can be applied, but gold, silver, copper, brass, titanium, chromium, nickel, nickel chromium, stainless steel, etc. can also be used as necessary. The thickness of the metal vapor deposition film is preferably 0.01 to 0.1 μm, more preferably 0.03 to 0.08 μm, and the size of the metal vapor deposition film dispersed in the ink is 5 to 25 μm. Is more preferable, and it is 10-15 micrometers more preferably. If the size is less than this range, the brightness of the ink coating will be insufficient, and if it exceeds this range, it will be difficult to enter the gravure plate cell, the screen plate will be clogged easily, and the gloss of the printed coating will decrease. To do.

  The metal vapor deposited film strip is first prepared as a vapor deposited film consisting of polyester film / release layer / deposited film / antioxidation top coat layer on the surface. The release layer and the topcoat layer are not particularly limited, and for example, cellulose derivatives, acrylic resins, chlorinated polypropylene, and the like can be applied. The vapor deposition film is immersed in a solvent, and the metal vapor deposition film is peeled, stirred, filtered and dried to obtain metal vapor deposition film strips. While stirring the metal vapor-deposited film strip at a temperature of 10 to 35 ° C. for about 30 minutes, an organic fatty acid, methylsilyl isocyanate or cellulose derivative solution is added, and the organic fatty acid, methylsilyl isocyanate or cellulose is added to the surface of the metal vapor-deposited film strip. The derivative is adsorbed and the surface treatment of the metal vapor deposited film strip is performed. As the cellulose derivative, nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, ethyl cellulose and the like can be applied. When the metal is aluminum, the addition amount of the cellulose derivative is preferably 1 to 20% by mass with respect to the deposited film strip.

  After the surface treatment, the metal vapor-deposited film strips are separated, or the metal vapor-deposited film strip slurry is blended and dispersed in a binder and a solvent as they are to make an ink. As the binder, known inks may be used, and examples thereof include (meth) acrylic resin, polyester, polyamide, polyurethane, shellac, and alkyd resin. If necessary, additives such as coloring pigments, dyes, waxes, plasticizers, leveling agents, surfactants, dispersants, antifoaming agents, and chelating agents may be added to the ink. As the ink solvent, known ink solvents can be used, for example, aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane, ethyl acetate, acetic acid, and the like. Examples thereof include esters such as propyl, alcohols such as methanol, ethanol and IPA, ketones such as acetone and MEK, alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether.

  Ordinary inks are kneaded by a roll mill, a ball mill, or the like, and the pigment additive is finely dispersed to sub-micron and highly dispersed to give printability. However, the high-intensity ink used in the present invention does not require a kneading step, and can be dispersed only by mixing with a stirrer, and the metallic luster is not impaired. That is, in order to develop a high-brightness metallic luster, the metal vapor-deposited film strip needs to have a size of about 5 to 25 μm, and when the kneading step is performed, the metallic luster is extremely lowered.

(High-brightness ink printing) If the high-brightness ink obtained as described above is printed by known gravure printing, screen printing, or flexographic printing so as to form a pattern, it can be dried and cured as necessary. Good. The shape of the pattern is not particularly limited, but may be any shape (resulting in a pattern) such as letters, numbers, illustrations, circles, rectangles, polygons, and / or stars. And print it. The high-brightness ink layer 18 includes electrically conductive metal vapor-deposited film strips, but is surface-treated and further dispersed in a binder. Therefore, the surface resistivity defined by JIS-K6911 is 10 ¹² Ω or more. is there.

  (Primer layer for pressure-sensitive adhesive layer) Since the high-brightness ink layer 18 has a pattern shape and the transparent reflective layer 17 is exposed in the portion without the pattern, the adhesive strength is improved when the pressure-sensitive adhesive layer 19 is formed. It is preferable to provide a primer layer 21 on the surface. The primer layer 21 is not particularly limited, and examples thereof include polyurethane resins, polyester resins, polyamide resins, epoxy resins, phenol resins, polyvinyl chloride resins, polyvinyl acetate resins, vinyl chloride. -Vinyl acetate copolymer, acid-modified polyolefin resin, copolymer of ethylene and vinyl acetate or acrylic acid, (meth) acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, polybutadiene resin, rubber compound Petroleum resins, alkyl titanate compounds, polyethyleneimine compounds, isocyanate compounds, starch, casein, gum arabic, cellulose derivatives, waxes and the like can be used. The primer layer 21 is prepared by dissolving or dispersing the material resin in a solvent, adding an appropriate additive such as a pigment, and applying and drying by a known method such as roll coating or gravure coating. What is necessary is just to form a layer about 1-10 micrometers.

  Next, the liquid crystal layer 41 is formed on the other surface of the substrate 11. In the case of a hologram label, since the liquid crystal layer 41 is the outermost surface, in order to provide a hard coat layer 45 on the surface of the liquid crystal layer 41 for protection or to improve the adhesion with the hard coat layer 45, It is preferable to provide the hard coat layer 45 after providing the primer layer on the surface of the liquid crystal layer 41.

  (Liquid Crystal Layer) As the liquid crystal layer 41, a cholesteric liquid crystal which is a liquid crystal having a selective reflectivity of light and a circular polarization selectivity depending on the viewing angle and causing a color change is preferably used. A cholesteric liquid crystal is a liquid crystal polymer having a helical structure, and has a characteristic that the color tone changes continuously depending on the viewing direction. Since the cholesteric liquid crystal layer has selective reflectivity, when the incident light has an incident angle θ, if the helical period of the liquid crystal is P, the average refractive index of the liquid crystal is n, and the wavelength is λ, P Selectively reflects light having a wavelength satisfying the Bragg reflection condition of cos θ = λ / n. In addition, at this time, according to the structure determined by the absolute configuration of the asymmetric carbon, only the right circularly polarized component or the left circularly polarized component of the light of wavelength λ is selectively reflected. Further, as is apparent from the equation of λ = n · P · cos θ, λ also varies depending on the angle of light incident on the cholesteric surface (film surface).

  Therefore, when the medium having the cholesteric liquid crystal layer is tilted, a color different from the color visually recognized when observed from the original surface is exhibited, and a color changing effect is exhibited. The color called cholesteric color is visible to the human eye as a unique beautiful color that cannot be produced by other means. These wavelength selective reflectivity, circularly polarized light selective reflectivity, color viewing angle dependency, and beautiful colors of cholesteric color are difficult to express with other substances or methods. The determination object is difficult to counterfeit, and it is possible to easily determine the authenticity of the counterfeit product, which is extremely effective in preventing forgery of the authenticity determination object.

  The cholesteric liquid crystal layer can be formed by a method in which a thermotropic cholesteric liquid crystalline polymer is heated to a temperature higher than its liquid crystal transition point to grow a liquid crystal structure and then rapidly cooled to fix the liquid crystal structure. . Various types of cholesteric liquid crystals are commercially available as coating resins, and these can be used. The cholesteric liquid crystal has a red type having a peak at 626.00 nm (7.15%), a green type having a peak at 6.69.00 nm (8.82%), and a blue type having a peak at 502.50 nm (4.43%). There are shapes.

  The cholesteric liquid crystal layer may be a coating layer in which the above cholesteric liquid crystal resin itself is applied to a medium and oriented and cured to form a liquid crystal coating film. And may be printed by a method such as offset, silk screen, gravure, intaglio, or letterpress. Even if these coating resins are directly applied to a substrate by gravure printing or the like and cured and dried, they can be formed by transfer. At the time of coating, the liquid crystal can be aligned by rubbing the surface of the substrate 11, and the adhesiveness can be improved by performing a corona discharge treatment on the surface of the substrate 11.

  In addition, for example, (1) cholesteric liquid crystal having color change effect and polarization is applied in the form of a bar code, (2) cholesteric liquid crystal is uniformly applied or a cholesteric liquid crystal film is applied, and a part is altered by laser. (3) Apply a cholesteric liquid crystal uniformly or affix a cholesteric liquid crystal film and change the polarization state of the light on it to change the alignment state. The method of laminating | stacking a layer etc. is also mentioned.

  The thickness of the liquid crystal layer 41 is desirably about 1 μm to 20 μm in order to take advantage of the characteristics. By combining the cholesteric liquid crystal layer 15 and the dark and dark adhesive layer 19 such as black, a color variable function is provided, so that the transmitted light can be absorbed and a colorful color shift can be confirmed. Easy and more variable color function. In the present invention, the opaque high-brightness ink layer 18 between the liquid crystal layer 41 and the adhesive layer 19 is formed into a pattern, and the portion without the pattern is used as the background of the liquid crystal layer 41, so that the color changing function can be improved. Since the transparent reflection layer 17 and the high-brightness ink layer 18 are the background in the hologram portion, a bright hologram can be observed, and the color variable function of the liquid crystal layer 41 and the bright hologram can be compatible.

  Furthermore, the authenticity of the liquid crystal layer 41 can be determined using a film (discrimination film) having a circularly polarized light selectivity of right circularly polarized light or left circularly polarized light. When the discriminating film is touched or held at a small distance and observed to rotate gradually in parallel, the discriminating film is translucent in appearance, but the direction of circularly polarized light in the cholesteric liquid crystal layer Thus, the reflected light from the liquid crystal layer is blocked or transmitted by the circularly polarizing film. For example, if the print pattern that is a cholesteric liquid crystal layer is discriminated by right-handed circularly polarized light (circularly polarized light), and if it is also right-handed circularly polarized light, the reflected light will be discriminated (circularly polarized) and the color that the printed pattern exhibits Can be observed. Conversely, if the discriminating (circularly polarized) film is left circularly polarized light, the reflected light that is right circularly polarized light is blocked by the discriminating (circularly polarized) film, and the color of the printed pattern disappears at a certain angular position. it can.

(Liquid Crystal Primer Layer) Although the hard coat layer 45 is provided on the surface of the liquid crystal layer 41, it is preferable to provide a primer layer 43 for the liquid crystal layer in order to improve the adhesive strength. The primer layer 43 is not particularly limited, and examples thereof include polyurethane resins, polyester resins, polyamide resins, epoxy resins, phenol resins, polyvinyl chloride resins, polyvinyl acetate resins, and vinyl chloride. -Vinyl acetate copolymer, acid-modified polyolefin resin, copolymer of ethylene and vinyl acetate or acrylic acid, (meth) acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, polybutadiene resin, rubber compound Petroleum resins, alkyl titanate compounds, polyethyleneimine compounds, isocyanate compounds, starch, casein, gum arabic, cellulose derivatives, waxes and the like can be used.
The primer layer 43 is obtained by dissolving or dispersing the material resin in a solvent, adding an additive such as a pigment as appropriate, applying it by a known roll coating method, gravure coating method, etc., and drying it. What is necessary is just to form a layer about 1-10 micrometers.

  (Hard Coat Layer) The hard coat layer 45 is mainly composed of an ionizing radiation curable resin and contains polyethylene wax. 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. Using an ionizing radiation curable resin containing a urethane (meth) acrylate oligomer which is a reaction product of a polyfunctional (meth) acrylate having a polyhydric alcohol having at least two hydroxyl groups in the molecule, or (3) A wax may be included, applied, dried, and cured with ionizing radiation to form 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.

  (Formation of hard coat layer) The hard coat layer 45 is formed by adding polyethylene wax to the above-mentioned ionizing radiation curable resin, and if necessary, adding a photopolymerization initiator, a plasticizer, a stabilizer, a surfactant and the like to the solvent. It may be dispersed or dissolved, applied by a known coating method such as roll coating, gravure coating, comma coating or die coating, dried, and reacted (cured) with ionizing radiation.

  (Thickness of hard coat layer) The thickness of the hard coat layer 45 is usually about 1 to 30 μm, and is not particularly limited. However, the thickness is increased to 10 μm or more, preferably 15 μm or more. It can be protected from external chemical and mechanical forces even when used in extremely harsh environments, with no expiry date, for long periods of use, and / or for many repeated uses.

  (Adhesive layer) A pressure-sensitive adhesive layer 19 having a dark and dark color such as black is formed on the surface of the primer layer 21. The adhesive is not particularly limited. For example, natural rubber, butyl rubber, polyisoprene, polyisobutylene, polychloroprene, styrene-butadiene copolymer resin and other synthetic rubber resins, silicone resins, and acrylic resins. Further, vinyl acetate resins such as polyvinyl acetate and ethylene-vinyl acetate copolymer, urethane resins, acrylonitrile, hydrocarbon resins, alkylphenol resins, rosin, rosin triglyceride, hydrogenated rosin and other rosin resins can be applied. Dissolve or disperse the material resin and dark pigment and / or dye such as black in a solvent, add an appropriate additive, and apply and dry by a known roll coating, gravure coating, etc. A layer of 5 μm to 50 μm is obtained.

  (Release paper) The release paper may be a known one, and has a release layer on one surface of a base material such as high-quality paper, coated paper, impregnated paper, or plastic film. The release layer is not particularly limited as long as it has a release property, 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. If necessary, the part excluding the release paper is half-cut to obtain an adhesive label.

The attaching method of the object to be adhered of the (stuck) hologram label 1 may be a known lamination deposition method, for example, can be applied manually, labeler, a known method such as a jet labeler. The shape of the label may be any shape such as a circle, an ellipse, a rectangle, a polygon, and a star.

The (to be adhered member) to be attached body 100 is not particularly limited as including metal layer 103, it may be a plurality of layers in itself. For example, Natural fiber paper, coated paper, tracing paper, plastic film which is not deformed by heat at the time of sticking, glass, metal, ceramics, to a substrate such as a medium, such as wood or cloth, or plating or vapor deposition, metal foil Ya A metal layer 103 may be provided by stacking materials including a metal layer, or a metal plate made of only metal may be used. Further, the medium of the attaching member 100 is at least 1 part, image, colored, printed, or may be other decorative is performed.

A conventional aluminum thin film, which is a reflective layer, has a very thin thickness of about 100 to 500 nm, a high ionization tendency, and is susceptible to electrical corrosion. In addition, it is remarkable in an environment where acidic alkaline substances such as sweat, foods and chemicals are affected. In particular, when an acid is in contact, the influence is remarkable, and the surface resistivity defined by JIS-K6911 is preferably 10 ⁸ Ω or more, more preferably 10 ¹² Ω or more, and is hardly subject to electrical corrosion even in a high temperature environment. In the hologram label of the present invention, the preferred surface resistivity defined by JIS-K6911 is 10 ¹² Ω or more for all layers of the label. The transparent reflective layer 17 is also a metal oxide or nitride, and a preferable titanium oxide has a surface resistivity defined by JIS-K6911 of 10 ¹² Ω or more.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this.

(Example 1) A PET film having a thickness of 50 μm was used as the base material 11, and a release varnish 45-3 (manufactured by Showa Ink Co., Ltd., acrylic resin release ink product name) was solidified on one surface of the base material 11. The solution was diluted with a solvent so as to be 10% by mass, applied by a roll coating method so that the thickness after drying was 1 μm, and dried to form a brittle layer 13.
The primer layer composition ink having the following composition was applied to the surface of the brittle layer 13 by roll coating so that the thickness after drying was 1 μm, dried, and further aged at 50 ° C. for 2 days, A primer layer 12 was formed.
-Composition-RL primer (manufactured by The Inktec Co., Ltd.) 400 parts by mass-XEL curing agent D 20 parts by mass-MEK 65 parts by mass-Toluene 65 parts by mass To the surface of the primer layer 12 the following ionizing radiation curable resin The composition was coated with a gravure reverse coater so that the thickness after drying was 2 μm, and dried at 100 ° C.
・ <Procedure for producing ionizing radiation curable resin composition>
First, “ionizing radiation curable resin composition M” was produced by the following procedure. A reactor equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 206.1 g of ethyl acetate and 133.5 g of isophorone diisocyanate trimer (HULS product, VESTANAT T1890, melting point 110 ° C.), 80 The solution was heated to 0 ° C. and dissolved. After air was blown into the solution, 0.38 g of hydroquinone monomethyl ether, 249.3 g of pentaerythritol triacrylate (product of Osaka Organic Chemical Industry Co., Ltd., Viscoat 300) and 0.38 g of dibutyltin dilaurate were charged. After reacting at 80 ° C. for 5 hours, 688.9 g of ethyl acetate was added and cooled.
The “ionizing radiation curable resin composition M”, a film-forming resin (acrylic oligomer), a reactive silicone, a polyethylene wax, a photopolymerization initiator, and a solvent are blended in the following composition to form an ionizing radiation curable resin. A composition was prepared.
・ <Ionizing radiation curable resin composition of hologram layer>
“Ionizing radiation curable resin composition M” 25 parts by mass Methacrylate oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name Murasaki 6630B) 5 parts by weight of reactive silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-2445) 0. 2 parts by mass Polyethylene wax (average particle size 2.0 m) 0.3 parts by mass Photopolymerization initiator (trade name Irgacure 907, manufactured by Ciba) 0.9 parts by mass Ethyl acetate 70 parts by mass From a fine concavo-convex pattern, a press die with a pseudo-continuous pattern duplicated by the 2P method from a diffraction grating by the beam interference method is attached to an embossing roller of a duplicating apparatus, and heated and pressed (embossed) with an opposing roller. A relief was formed. Immediately after shaping, it was cured by irradiating with ultraviolet rays using a high-pressure mercury lamp.
Titanium oxide with a thickness of 50 nm was formed on the relief surface of the hologram layer 15 by a vacuum deposition method to form a transparent reflective layer 17.
Using a fine wrap super metallic silver ink (manufactured by Dainippon Ink & Chemicals, Inc., trade name of high-brightness ink) on the reflective layer 17 surface, a heart pattern so that the thickness after drying becomes 2 μm by gravure printing. A pattern with a high brightness ink layer 18 was formed by printing a pattern inlaid with.
Primer layer composition (15 parts by mass of polyester resin, 15 parts by mass of vinyl chloride-vinyl acetate copolymer resin, 35 parts by mass of toluene, 35 parts by mass of methyl ethyl ketone) is applied to the surface of the high-brightness ink layer 18 to a dry film thickness of 1 μm. Then, it is coated with a gravure coater and dried at 100 ° C. to volatilize the solvent, thereby forming a primer layer 21, substrate 11 / brittle layer 13 / primer layer 12 / hologram layer 15 / transparent reflective layer 17 / A laminate of the high brightness ink layer 18 / primer layer 21 was obtained.
A cholesteric liquid crystal resin is applied to the surface of the base material 11 of the laminate by a gravure coating method while corona treatment and rubbing treatment, and dried to a thickness of 2 μm. A green liquid crystal layer 41 was formed.
A primer layer composition (15 parts by mass of a polyester resin, 15 parts by mass of vinyl chloride-vinyl acetate copolymer resin, 35 parts by mass of toluene, and 35 parts by mass of methyl ethyl ketone) is applied to the surface of the liquid crystal layer 41 so that the dry film thickness becomes 1 μm. The primer layer 43 was formed by coating with a gravure coater and drying at 100 ° C. to evaporate the solvent.
The surface of the primer layer 43 is coated with the following ionizing radiation curable resin composition with a gravure reverse coater so that the coating thickness after drying is 2.5 μm, dried at 100 ° C., and using a high pressure mercury lamp. The hard coat layer 45 was formed by curing by irradiating ultraviolet rays.
・ <Procedure for producing ionizing radiation curable resin composition>
First, the reactive organism (A) was produced by the following procedure. A reactor equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 206.1 g of ethyl acetate and 133.5 g of isophorone diisocyanate trimer (HULS product, VESTANAT T1890, melting point 110 ° C.), 80 The solution was heated to 0 ° C. and dissolved. After air was blown into the solution, 0.38 g of hydroquinone monomethyl ether, 249.3 g of pentaerythritol triacrylate (product of Osaka Organic Chemical Industry Co., Ltd., Viscoat 300) and 0.38 g of dibutyltin dilaurate were charged. After reacting at 80 ° C. for 5 hours, 688.9 g of ethyl acetate was added and cooled.
The reaction product (A), polyethylene wax, photopolymerization initiator, and solvent were blended in the following composition to prepare an ionizing radiation curable resin composition.
・ <Ionizing radiation curable resin composition>
Reactive organism (A) 30 parts by weight Polyethylene wax (average particle size 5 μm) 0.3 parts by weight Photopolymerization initiator (Ciba, trade name Irgacure 907) 0.9 parts by weight Solvent (ethyl acetate: methyl isobutyl ketone = 1: 1) 70 parts by mass In this way, hard coat layer 45 / liquid crystal layer 41 / base material 11 / brittle layer 13 / primer layer 12 / hologram layer 15 / transparent reflective layer 17 / high brightness ink layer 18 / primer A laminate of layer 21 was obtained.
To the primer layer 21 surface of the laminate, an adhesive (Nissetsu PE-118 + CK101, manufactured by Nippon Carbide) was applied with a comma coater so that the dry film thickness was 30 μm, and dried at 100 ° C. to volatilize the solvent. After forming the adhesive layer 19, a silicone-treated PET film (SPO5, manufactured by Tokyo Cellophane Paper Co., Ltd.) is bonded as a release paper, and the hard coat layer 45 / primer layer 43 / liquid crystal layer 41 / substrate 11 / brittle layer The hologram label 1 of Example 1 having a layer configuration of 13 / primer layer 12 / hologram layer 15 / transparent reflective layer 17 / high brightness ink layer 18 / primer layer 21 / adhesive layer 19 / release paper was obtained.

  (Comparative example 1) Instead of the transparent reflective layer 17, aluminum having a thickness of 200 nm was formed by a vacuum deposition method to form a metal reflective layer, and the same as in Example 1 except that the high-brightness ink layer 18 was not provided. From the layer constitution of hard coat layer 45 / primer layer 43 / liquid crystal layer 41 / base material 11 / brittle layer 13 / primer layer 12 / hologram layer 15 / metal reflective layer 17 / primer layer 21 / adhesive layer 19 / release paper A hologram label 1 of Comparative Example 1 was obtained.

Over time according to the appearance test under humidity (Evaluation Method) high-temperature high, the outer appearance test as an object to be adhered body, the laminated body used by laminating a copper foil of a synthetic paper and the thickness 50μm of thickness 100 [mu] m, this indicates a copper foil The release paper was removed from the hologram labels 1 of Examples and Comparative Examples, and the pressure-sensitive adhesive layer 19 surface was pressure-applied by hand to the surface. To be adhered body with adhered hologram, after standing for 1 week in an atmosphere of RH temperature 40 ° C. and 90% humidity was visually observed the appearance of the hologram.
In addition, after the appearance test, the adhered brittle hologram label was peeled by hand, and the peelability from the brittle layer was visually observed.
When the hologram label 1 of Example 1 was used, there was no significant change in appearance, and a bright hologram could be observed. In addition, a heart-shaped silver and bright hologram and a vividly variable liquid crystal layer could be observed. Moreover, when the attached hologram label was peeled by hand after the appearance test, it was easily peeled off and could not be reattached, making it impossible to replace it. The surface resistivity determined by JIS-K6911 of the high brightness ink layer 18 measured when the high brightness ink layer 18 of Example 1 was formed was 6 × 10 13 Ω.
In the case of using the hologram label 1 of Comparative Example 1, the aluminum was subjected to electrical corrosion, the peripheral portion was missing and the hologram was not observed, and the remaining portion of the aluminum was uneven and whitened and uneven. The hologram was observed only in the central portion, but as a whole, the hologram was significantly deteriorated and the design and security were lost.
Moreover, when the attached hologram label was peeled off by hand after the appearance test, it was peeled off entirely between the adhesive layer and the adherend, and the fraud prevention effect was not obtained.

FIG. 1 is a sectional view of a hologram label showing one embodiment of the present invention.
Figure 2 is a cross-sectional view adhering a hologram label to the object to be adhered comprising a metal layer.

Explanation of symbols

1: Hologram label 11: Base material 12: Protective layer 13: Brittle layer 15: Hologram layer 17: Transparent reflection layer 18: High-brightness ink layer 19: Adhesive layer 21, 43: Primer layer 41: Liquid crystal layer 45: Hard coat layer 100: the sticking member 101: the stuck Karadamotozai 103: metal layer

Claims (3)

A substrate, on one surface of the substrate, at least brittle layer, a hologram layer, a transparent reflective layer, a high luminance ink layer and the adhesive layer are laminated in this order on the other surface of the substrate, at least a liquid crystal layer A hologram label comprising:
The substrate is a transparent substrate;
The high-brightness ink layer includes a metal vapor-deposited film strip surface-treated with at least an organic fatty acid, methylsilyl isocyanate, or a cellulose derivative, and has a pattern shape,
The adhesive layer is black;
Wherein even when the hologram label affixed to the object to be adhered comprising a metallic layer, a hologram label, characterized in that electrical corrosion to the hologram label is maintained hologram effects does not occur.   The hologram label according to claim 1, wherein the transparent reflective layer is titanium oxide. Surface resistance defined by JIS-K6911 for all layers of the liquid crystal layer, the transparent substrate, the brittle layer, the hologram layer, the transparent reflective layer, the high-brightness ink layer, and the adhesive layer constituting the hologram label The hologram label according to claim 1, wherein the rate is 10 ¹² Ω or more.

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