JP2008139716A - Brittle hologram label - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a brittle hologram label that does not have significant degradation in the appearance, even if hologram label is stuck to a transfer material including a metal layer, that is bright and superior in decorative properties and/or security properties, and that can prevent tamperings, such as replacing of the hologram. <P>SOLUTION: The hologram label has a base material 11, a brittle layer 13, a hologram layer 15, a transparent reflecting layer 17, a high luminance ink layer 18 containing metal vapor-deposited film chips surface-treated with at least an organic fatty acid, methylsilylisocyanate or a cellulose derivative, and a tacky layer 19 are layered successively; the brittle layer 13 is a layer having peeling properties or causing cohesive failure or a layer with locally different adhesive strengths; the transparent reflecting layer 17 is made of titanium oxide; and all the layers, constituting the brittle hologram label, have surface resistivity prescribed by JIS-K6911 as being 10<SP>12</SP>Ω or higher. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a fragile hologram label, and more specifically, even when affixed to a transfer object including a metal layer, the label is not corroded and the hologram effect is maintained, and the appearance is not significantly deteriorated and bright. Further, the present invention relates to a brittle 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”.

  (Main use) The main use of the brittle hologram label of the present invention is such as credit cards, certificates such as certificates, certificates, etc., employee cards, membership cards, student ID cards. Such as ID cards, gift certificates, admission cards, passports, service points, etc., media that proves the rights and qualifications paid (prepaid), book covers, pamphlets, record jackets, package, Such as clothing, daily necessities and the like, which require design and / or security. However, it is not particularly limited as long as it is an application to be applied to a transfer target requiring design and / or security.

(Background Art) Conventionally, as a brittle 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, the metal reflection layer provides a very bright hologram with silver metallic luster. However, when the metal reflection layer is attached to a transfer object including the metal layer, the reflection layer of the metal thin film is subjected to electrical corrosion, and the reflection is partially reflected. , The reflectance decreases, unevenness occurs on the surface, 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. 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, a brittle hologram label is a hologram that has no defects, unevenness, or whitening, has no significant deterioration in appearance, is bright, and has excellent design and / or security when transferred to a transfer material including a metal layer. There is a need for brittle 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, a bright hologram with silver metallic luster can be obtained with a metallic reflective layer. However, when a hologram is attached to a transfer target including a metal layer using a hologram label, the metal layer of the label is affected by the metal layer of the transfer target. Is subject to electrical corrosion, the reflection becomes partial, the reflectance decreases, the surface is uneven, the light is irregularly reflected and the hologram is whitened, the hologram effect is reduced, There is a drawback that the appearance is remarkably deteriorated and sometimes the hologram cannot be observed at all.
Furthermore, the present applicant has disclosed one using a high-brightness ink layer as a reflective layer and one using a transparent reflective 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 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.
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 (see, for example, Patent Document 3). ). However, if it is peeled off after being attached to the adherend, the brittle seal will break up and down along the pattern-like brittle layer, but it will stick a hologram on the transfer object including the metal layer, or even electrical corrosion. There is no description of deterioration at all.
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 4). 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. There is no description of deterioration due to electric corrosion, and a hologram is stuck on the transfer target.

Japanese Patent No. 2877968 JP 2003-285599 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. The purpose is that even when the hologram label is attached to a transfer object including a metal layer, the label is not electrically corroded, the hologram effect is maintained, the appearance is not significantly deteriorated, and it is bright, has a good design and / or An object of the present invention is to provide a brittle hologram label that is excellent in security and can prevent counterfeiting such as replacing a hologram.

In order to solve the above-mentioned problems, a brittle hologram label according to the invention of claim 1 includes a base material, a brittle layer, a hologram layer, a transparent reflection layer, a high-brightness ink layer, and one surface of the base material. A brittle hologram label in which an adhesive layer is laminated in order, wherein the high-brightness ink layer includes at least a metal vapor-deposited thin film surface-treated with an organic fatty acid, methylsilyl isocyanate, or a cellulose derivative, The hologram effect is maintained without causing electrical corrosion on the brittle hologram label even if it is attached to a transfer material including a metal layer.
The brittle hologram label according to the invention of claim 2 is such that the brittle layer is a peelable or cohesive breakable layer, or a layer having a difference in adhesive strength partially.
The brittle hologram label according to the invention of claim 3 is such that the transparent reflection layer is made of titanium oxide.
The brittle hologram label according to the invention of claim 4 is such that the surface resistivity defined by JIS-K6911 of all the layers constituting the label is 10 ¹² Ω or more.

According to the first and second aspects of the present invention, even when the hologram label is attached to a transfer target including a metal layer, the hologram effect is maintained without causing electrical corrosion on the label, and the appearance is not significantly deteriorated. A brittle hologram label is provided that is bright, excellent in design and / or security, and capable of preventing counterfeiting such as replacing a hologram.
According to the third to fourth aspects of the present invention, there is provided a brittle hologram label capable of attaching a brighter hologram having excellent design and / or security.

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 brittle hologram label showing one embodiment of the present invention.
FIG. 2 is a cross-sectional view in which a brittle hologram label is attached to a transfer target including a metal layer.

  (Brittle hologram label) As shown in FIG. 1, the brittle hologram label 1 of the present invention has a base material 11, a brittle layer 13, a hologram layer 15, and a transparent reflecting layer on one surface of the base material 11. 17, a high-brightness ink layer 18, and an adhesive layer 19 are laminated in order as essential layers. Base material 11 / brittle layer 13 / hologram layer 15 / transparent reflection layer 17 / high-brightness ink layer 18 / adhesive layer 19 The layer structure is as follows. If necessary, the primer layer 12 may be provided between the brittle layer 13 and the hologram layer 15. Further, if necessary, the release paper 31 may be provided on the surface of the adhesive layer 19 so as to be peelable.

The brittle hologram label 1 of the present invention essentially comprises a substrate 11, a brittle layer 13, a hologram layer 15, a transparent reflective layer 17, a high-brightness ink layer 18, and an adhesive layer 19, and the brittle layer 13 is peelable or A cohesive fracture layer or a layer having a difference in adhesive strength is used. 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. Preferably, the transparent reflective layer 17 uses a titanium oxide thin film, and the surface resistivity defined by JIS-K6911 of all layers constituting the brittle hologram label 1 is 10 ⁶ Ω or more, preferably 10 ⁸ Ω or more. More preferably, it is 10 ¹² Ω or more.

  When the layer of the brittle 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. Furthermore, a bright hologram is obtained by a synergistic effect of the hologram layer 15, the transparent reflection layer 17, and the high brightness ink layer 18. Even if the hologram is attached to the transfer target 101 including the metal layer 23, the transfer target 101 includes the metal layer 23, but the brittle hologram label 1 does not include a conductive layer, and the transfer layer Since all the layers of 21 are composed of layers having a high surface resistivity, they are not subject to electrical corrosion with the metal layer 23, the reflection becomes partial, the reflectance decreases, the surface As a result, unevenness occurs and light is diffusely reflected to whiten the hologram, so that 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.

  In addition to its transparent reflective layer made of titanium oxide thin film by the conventional vacuum film-forming method, it can be formed by the printing method in existing equipment, can be produced in small lots, and can be produced at low cost. it can.

  (Substrate) As the substrate 11, 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, etc. 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 transfer substrate 21 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. Note that the interface to be peeled off may be either the interface between the base material 11 and the brittle layer 13 or the interface between the brittle layer 13 and the hologram layer 15 (primer layer 12 when there is a primer layer).

  (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 is cross-linked by ionizing radiation is, for example, a resin containing a monomer or oligomer having a functional group that is polymerized (cured) by 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.

(1) Since the coated film of the hologram layer 15 in a coated state before ionizing radiation curing is not sticky in a finger dry state and can be wound up without blocking, roll-to-roll processing can be performed.
(2) When reactive silicone is included in the hologram layer 15, the relief from the unevenness of the stamper gathers on the coating surface and the moldability is improved, and the relief structure can be easily molded, and ionization is performed after molding. When cured with radiation, the reactive silicone also cures.
(3) 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 transfer member from mechanical friction and abrasion, is hardly scratched and has excellent durability.

  (Formation of hologram layer) The hologram layer 15 contains the above-mentioned ionizing radiation curable resin, (meth) acrylate oligomer, reactive silicone, and polyethylene wax, if necessary, and a photopolymerization initiator as necessary. Add a plasticizer, stabilizer, surfactant, etc., disperse or dissolve in a solvent, apply by a known coating method such as roll coating, gravure coating, comma coating, die coating and dry 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 ray, X-ray, electron beam, or the like can be applied as ionizing radiation, but ultraviolet (UV) is preferable. An ionizing radiation curable resin that cures with ionizing radiation may contain a photopolymerization initiator and / or 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. In the case of individual patterns, a registration mark synchronized with the pattern may be formed and transferred to a desired position on the transfer object.

(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 luminance) printed using a high luminance ink containing a metal vapor-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 ink layer 18), it becomes difficult to whiten even when heated or bent, resulting in a bright brittle hologram label.

  The metallic ink layer is a printing layer using a printing ink imparting a metallic luster-like appearance (metallic tone), and is a vapor deposition obtained by pulverizing a vapor-deposited metal film surface-treated with at least an organic fatty acid, methylsilyl isocyanate, or a cellulose derivative. It is a printing layer using the high brightness ink containing the metal 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 a cellulose derivative solution is added to the surface of the metal vapor-deposited film strip. Cellulose derivatives are adsorbed to perform surface treatment of metal vapor deposited film strips. 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 ink obtained as described above is made by known gravure printing, screen printing, or flexographic printing, the required pattern is made, printed, dried, and cured if necessary. Good. The high-brightness ink layer 18 includes electrically conductive metal vapor-deposited film strips, but is surface-treated and further dispersed in the binder, so that the surface resistivity defined by JIS-K6911 is 10 ¹² Ω or more. can do.

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 less susceptible to electrical corrosion even in a high temperature environment. As for the other layers of the label, the hologram layer 15 and the adhesive layer 19 are mainly made of synthetic resin, and the surface resistivity defined by JIS-K6911 is 10 ¹² Ω or more. 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.

  (Adhesive layer) As the adhesive of the adhesive layer 19, a pressure-sensitive adhesive that adheres with a known pressure sensitivity can be applied. 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. A rosin resin such as polyvinyl acetate, ethylene-vinyl acetate copolymer, etc., urethane resin, acrylonitrile, hydrocarbon resin, alkylphenol resin, rosin, rosin triglyceride, hydrogenated rosin can be applied. The material resin is dissolved or dispersed in a solvent, an additive such as a pigment is added as appropriate, and the layer is applied by a known method such as roll coating or gravure coating and dried to obtain a layer having a thickness of 5 to 50 μm.

  (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.

  (Adhesion) As a method for adhering the fragile hologram label 1 to the transfer target, a known adhesion method may be used. For example, a known method such as manual work, a labeler, a jet labeler or the like can be applied. The shape of the label may be any shape such as a circle, an ellipse, a rectangle, a polygon, and a star.

  (Transfer To be Transferred) The transfer target 100 is not particularly limited as long as the metal layer 103 is included, and may be a single layer or a plurality of layers. For example, natural fiber paper, coated paper, tracing paper, plastic film that does not deform by heat during transfer, glass, metal, ceramics, substrates such as wood and cloth, plating, vapor deposition, metal foil and metal A metal layer 103 may be provided by stacking materials including layers, or a metal plate made of only metal may be used. Further, at least a part of the medium of the transfer target 100 may be subjected to image, coloring, printing, or other decoration.

  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., Biscoat 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), printed on the surface of the reflective layer 17 by gravure printing so that the thickness after drying is 2 μm. A high-brightness ink layer 18 was formed.
An adhesive (Nissetsu PE-118 + CK101, manufactured by Nippon Carbide) was applied to the surface of the high-brightness ink layer 18 with a comma coater so that the dry film thickness was 30 μm, and the solvent was stripped by drying at 100 ° C. After the layer 19 is formed, a silicone-treated PET film (SPO5, manufactured by Tokyo Cellophane Paper Co., Ltd.) is bonded as a release paper, and the substrate 11 / brittle layer 13 / primer layer 12 / hologram layer 15 / transparent reflective layer 17 The brittle hologram label 1 of Example 1 having a layer structure of / high brightness ink layer 18 / 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. The brittle hologram label 1 of Comparative Example 1 having a layer structure of base material 11 // brittle layer 13 / primer layer 12 / hologram layer 15 / metal reflective layer / adhesive layer 19 / release paper was obtained.

(Evaluation method) According to an appearance test over time under high temperature and high humidity, the appearance test uses a laminated body in which a synthetic paper having a thickness of 100 μm and a copper foil having a thickness of 50 μm is laminated as a transfer target body. The release paper was removed from the brittle hologram labels 1 of Examples and Comparative Examples, and the pressure-sensitive adhesive layer 19 surface was pressed by hand and pasted. The adhered transfer object with the hologram was left in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH for one week, and then the appearance of the hologram was visually observed.
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.
In the case of using the brittle hologram label 1 of Example 1, there was no significant change in the external appearance, and a bright hologram 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. In addition, the surface resistivity defined 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 where the brittle hologram label 1 of Comparative Example 1 is used, aluminum is electrically corroded, the peripheral portion is missing and the hologram is not observed, and the portion where the aluminum remains is unevenly generated on the surface and whitened. Although it was a non-uniform hologram, a hologram was observed only in the central part, but as a whole, it deteriorated significantly, and both 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.

It is sectional drawing of the brittle hologram label which shows one Example of this invention. It is sectional drawing which stuck the brittle hologram label to the to-be-transferred body containing a metal layer.

Explanation of symbols

1: Brittle hologram label 11: Base material 12: Primer layer 13: Release layer 15: Hologram layer 17: Transparent reflection layer 18: High-brightness ink layer 19: Adhesive layer 31: Release paper 100: Transfer object 101: Transfer object Body substrate 103: Metal layer

Claims (4)

A brittle hologram label in which a brittle layer, a hologram layer, a transparent reflective layer, a high-brightness ink layer, and an adhesive layer are sequentially laminated on one surface of the base material, the high-brightness ink layer Even if it includes a metal vapor-deposited film strip surface-treated with at least an organic fatty acid, methylsilyl isocyanate or a cellulose derivative, the brittle hologram label can be electrically A brittle hologram label characterized in that the hologram effect is maintained without corrosion. 2. The brittle hologram label according to claim 1, wherein the brittle layer is a peelable or cohesive breakable layer, or a layer partially having a difference in adhesive force. The brittle hologram label according to claim 1, wherein the transparent reflective layer is titanium oxide. 3. The brittle hologram label according to claim 1, wherein the surface resistivity defined by JIS-K6911 of all the layers constituting the transfer layer is 10 ¹² Ω or more.

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