JP2007086251A - Label with hologram and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a label with a hologram which has superior texture, never has its reverse side seen through, and also has superior durability such as abrasion resistance on a label surface and to provide a method of manufacturing the same. <P>SOLUTION: The method includes the steps of: (1) preparing a primary hologram film 10A provided with a first base material 11A, a hologram layer 15, a reflective layer 17, an anchor layer 21, and a print layer 19; (2) preparing a secondary hologram film 10B by laminating a print layer surface of the primary hologram film 10A and a second base material 11B across an adhesive layer 31 by a dry lamination method; (3) preparing a tertiary hologram film 10C by forming a protective layer 41 on a second base material surface 11B where the secondary hologram film 10B is exposed; and (4) laminating peel paper 53 in a peelable state on a first base material 11A surface of the tertiary hologram film 10C across a black pressure-sensitive adhesive layer 51. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a label with a hologram with a pattern that can be easily attached to an arbitrary article. Is.

  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” and “UV” for “ultraviolet rays”. As defined in JIS-K6900 for a sheet or film, a sheet is a thin and generally flat product whose thickness is small relative to its length and width, and a film is extremely small compared to its length and width. , A thin flat product with an arbitrarily limited maximum thickness, usually supplied in the form of a roll. Therefore, it can be said that a sheet having a particularly small thickness among the sheets is a film, but the boundary between the sheet and the film is not clear and is difficult to distinguish clearly. In this specification, it is defined as a film including the shape of a board, a sheet, and a film.

  (Main applications) Main applications of the article with the hologram label of the present invention include credit cards, certificates, etc., certificates, book covers, brochures, record jackets, packages, clothing, etc. The outermost surface must be scratch resistant. However, the application is not particularly limited as long as the application requires surface scratch resistance.

(Background Art) Holograms can reproduce three-dimensional images using light interference, and since advanced technology is required for production, gold cards such as credit cards and certificates are used as means for preventing counterfeiting. For example, it is attempted to be provided on various articles such as book covers, pamphlets, record jackets, package cages, and clothing with the aim of novelty in appearance. In order to improve the decorativeness and anti-counterfeiting property of such a hologram, it is performed to give a pattern to the hologram. That is, it has been attempted to provide a pattern on the surface of a hologram-attached label attached to an article by printing. The hologram with a pattern formed in this way is provided with a pattern from the top of the formed hologram. There was a problem in durability such as abrasion resistance and scratch resistance of the pattern such as rub-off. In order to eliminate this, a hologram forming layer, a reflective thin film layer, an adhesive layer, and release paper as necessary are provided on the support, and the surface of the label is a resin film (support) such as a PET film. However, durability such as scratch resistance is still insufficient with the resin film alone. Further, the above-mentioned label with hologram has a problem that it is thin and poor in texture, and the back side is seen through because the reflection layer is thin.
Accordingly, there is a demand for a label with a hologram that has excellent texture, the back side is not transparent, and has excellent durability such as scratch resistance on the label surface, and a method for producing a label with hologram that can easily manufacture the label with hologram. ing.

(Prior Art) Conventionally, the present applicant has sequentially laminated a support and a hologram forming layer, a reflective thin film layer, an adhesive layer and, if necessary, a release sheet, on a label with a hologram with a pattern. In addition, it has at least one picture layer between the above-mentioned arbitrary layers, and the picture and the hologram are in harmony with each other, and are beautiful in harmony with the design, color and color tone of the adherend. It is useful as a hologram sticker and exhibits high anti-counterfeiting properties when it is affixed to gold cards such as credit cards and luxury products. In addition, a pattern layer is provided adjacent to the reflective thin film layer, and when it is attempted to rewrite the pattern, the reflective thin film layer is damaged and it can be easily determined whether or not it is a rewritten pattern. A device capable of preventing forgery is disclosed (for example, see Patent Document 1).
However, the support on the outermost surface in the label state (corresponding to the second base material of the present invention) is a resin film such as a PET film, and durability such as scratch resistance is still insufficient with the resin film alone. There is a problem that there is. Accordingly, the present inventors have intensively studied a label with a hologram that improves the durability of the label surface such as scratch resistance, the back side is not transparent, and has an excellent texture, and a method for producing the same.

Japanese Utility Model Publication No. 62-154479

  Accordingly, the present invention has been made to solve such problems. The object is to provide a hologram label with excellent texture and durability, such as scratch resistance on the surface of the label, and a method for producing the same.

In order to solve the above problems, a method for producing a hologram-attached label according to the invention of claim 1 includes: (1) a first base material, a hologram layer, a reflective layer, an anchor on one surface of the first base material; And a step of preparing a primary hologram film provided with a layer and a printing layer, and (2) laminating the printing layer surface of the primary hologram film and the second substrate by a dry lamination method through an adhesive layer. A step of forming a secondary hologram film, and (3) a step of forming a protective layer on the exposed second base material surface of the secondary hologram film to form a tertiary hologram film; (4) A step of laminating release paper on the first base material surface of the third hologram film through a black adhesive layer in a peelable manner.
According to a second aspect of the present invention, there is provided a method for producing a label with a hologram, wherein the protective layer is a urethane obtained by reacting an organic isocyanate having a plurality of isocyanate groups in one molecule with a polycaprolactone-modified alkyl (meth) acrylate. It is a cured product of an ionizing radiation curable composition containing (meth) acrylate.
In the method for manufacturing a hologram-attached label according to the invention of claim 3, when the protective layer gives a scratch mark with a vertical load of 2.4 mN using a diamond indenter having a tip diameter of 15 μm, the cured film has a temperature of 25 ° C. The scratches can be recovered by a self-repair function in an atmosphere having a relative humidity of 50%.
The label with hologram according to the invention of claim 4 is manufactured by the method for manufacturing a label with hologram according to any one of claims 1 to 3.

According to the first aspect of the present invention, there is provided a method for producing a label with a hologram, which can easily produce a label with a hologram which is excellent in texture, has a transparent back side, and has excellent durability such as scratch resistance on the label surface. .
According to the second aspect of the present invention, there is provided a method for producing a label with a hologram capable of producing a label with a hologram having excellent durability such as scratch resistance on the label surface.
According to the third aspect of the present invention, there is provided a method for producing a hologram-attached label having a scratch property capable of recovering a scratch mark by a self-repair function.
According to the fourth aspect of the present invention, there is provided a hologram label with excellent texture, the back side is not transparent, and the label surface has excellent durability such as scratch resistance.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view for each process illustrating the manufacturing method of the present invention.

  (First Step) This is a step of preparing a first hologram film 10A in which the hologram layer 15, the reflection layer 17, the anchor layer 21, and the printing layer 19 are provided on one surface of the first base material 11A. The first base material 11A and the second base material 11B are the same material, and the first base material 11A and the second base material 11B are collectively referred to as the base material 11 and described.

  (Substrate) As materials of the first substrate 11A used in the first step and the second substrate 11B used in the second step, various materials can be applied depending on the application. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide resins such as nylon (trade name) 6, polyethylene, polypropylene, polybutene, or polymethylpentene Polyolefin resins, cyclic polyolefin resins such as polynorbonene, vinyl resins, (meth) acrylic resins, styrene resins, polyvinyl alcohol resins, cellophane, cellulose triacetate and other cellulose films, polycarbonate resins ,and so on.

  The first 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 first 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 first substrate 11 is usually about 12 to 250 μm, but can be suitably set within the range of 25 to 100 μm. Usually, polyester films such as polyethylene terephthalate and polyethylene naphthalate are preferably used in view of mechanical strength and cost, and polyethylene terephthalate is most suitable. Prior to application, the first base material 11 is applied to the application surface by corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer (also called an anchor coat, adhesion promoter, or easy adhesive) application treatment, pre-heat treatment, It is preferable to perform easy adhesion treatment such as dust removal treatment, vapor deposition treatment, and alkali treatment. The first substrate 11 is used as a film, sheet, or board formed of at least one layer of these resins.

  (Hologram layer) As a resin material of the hologram layer 15, a thermoplastic resin, a thermosetting resin, a cured resin of an ionizing radiation curable resin, or the like can be applied. Examples of the thermoplastic resin include acrylic resins such as polyvinyl chloride and polymethyl methacrylate, polystyrene, polycarbonate, and the like. Examples of the thermosetting resin include unsaturated polyester, melamine resin, and epoxy resin. Examples of radiation curable resins include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, and triazine acrylate. What mixed suitably the saturated ethylene monomer and the unsaturated ethylene oligomer is applicable. In particular, ionizing radiation curable resins that are cured with ultraviolet rays or electron beams having excellent durability such as chemical resistance, light resistance, and weather resistance are preferable. As the ionizing radiation curable resin, those obtained by curing an ionizing radiation curable resin such as an epoxy-modified acrylate resin, a urethane-modified acrylate resin, and an acrylic-modified polyester can be applied. Specifically, the following two types are most preferable. .

  (Ionizing radiation curable resin composition S) As a preferable one of the hologram layer 15, an uncured ionizing radiation curable resin composition mainly composed of a urethane-modified acrylic resin represented by the general formula (a) is used. It is a cured product. Specifically, the photo-curable resin composition disclosed in Japanese Patent Application Laid-Open No. 2000-273129 can be applied, and the photo-curable resin composition S described in the above specification is referred to in this specification. This is referred to as “ionizing radiation curable resin composition S”.

（６個のＲ１は夫々互いに独立して水素原子またはメチル基を表わし、Ｒ２は炭素数が１〜２０個の炭化水素基を表わす。ｌ、ｍ、ｎ、ｏ及びｐの合計を１００とした場合に、ｌは２０〜９０、ｍは０〜８０、ｎは０〜５０、ｏ＋ｐは１０〜８０、ｐは０〜４０の整数である。ＸおよびＹは直鎖状または分岐鎖状のアルキレン基を表わし、Ｚはウレタン変性アクリル樹脂を改質するための基を表し、好ましくは嵩高い環状構造の基を表わす。）

(Six R1's each independently represent a hydrogen atom or a methyl group, and R2 represents a hydrocarbon group having 1 to 20 carbon atoms. The total of l, m, n, o and p is 100. In this case, l is 20 to 90, m is 0 to 80, n is 0 to 50, o + p is an integer of 10 to 80, and p is an integer of 0 to 40. X and Y are linear or branched alkylene. Z represents a group for modifying the urethane-modified acrylic resin, and preferably represents a group having a bulky cyclic structure.)

  (Ionizing radiation curable resin composition M) Another preferred hologram layer 15 is a cured product of an ionizing radiation curable resin containing a urethane (meth) acrylate oligomer. Specifically, a photocurable resin disclosed in Japanese Patent Application Laid-Open No. 2001-329031 can be applied, and is referred to as “ionizing radiation curable resin composition M” in this specification.

  (Relief shape) A hologram is a recording of interference fringes due to interference of light between object light and reference light in an uneven relief shape. For example, a laser reproduction hologram such as a Fresnel hologram and a white light reproduction hologram such as a rainbow hologram In addition, there are color holograms utilizing these principles, 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 can be duplicated by using it as a mold (referred to as a stamper) and by superimposing the original on the resin layer and heat-pressing both of them with an appropriate means such as a heating roll.

  (Relief Curing) When an ionizing radiation curable resin is used as the hologram layer 15, the ionizing radiation curable resin is cured by irradiating ionizing radiation during or after embossing with a stamper. 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. When a thermosetting resin is used as the hologram layer 15, it may be cured by aging in a temperature and humidity environment according to the curing conditions of the thermosetting resin to be used.

  (Reflection layer) Since the reflection layer 17 is provided on the reflection layer 17 on the relief surface of the hologram layer 15 provided with a predetermined relief structure, the reflection reflection and / or diffraction effect is enhanced. If a rate is higher, it will not specifically limit, For example, a metal thin film can be applied. The metal used for the reflective layer 17 is a metal element thin film that has a metallic luster and reflects light, such as Cr, Ni, Ag, Au, Al, etc., and oxides, sulfides, nitrides thereof, etc. A thin film may be used alone or in combination. The formation of the light-reflective metal thin film can be obtained by a vacuum thin film method such as a vacuum deposition method, a sputtering method, or an ion plating method so as to have a thickness of about 10 to 2000 nm, preferably 20 to 1000 nm. However, it can also be formed by plating. If the thickness of the reflective layer 17 is less than this range, the light is transmitted to some extent and the effect is reduced, and if it is more than that, the reflective effect is not changed, which is wasteful in cost.

Further, the reflective layer 17 has a substantially colorless and transparent hue, and its optical refractive index is different from that of the hologram layer. A simple 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. Also, a general light-reflective metal thin film such as aluminum can be used when it has a thickness of 200 mm or less.

  The transparent metal compound is formed on the relief surface of the hologram layer 15 by vacuum such as vapor deposition, sputtering, ion plating, and CVD so that the thickness of the relief layer of the hologram layer 15 is about 10 to 2000 nm, preferably 20 to 1000 nm. It may be provided by a thin film method or the like. Furthermore, a transparent synthetic resin having a refractive index different from that of the hologram layer 15 may be used. When the refractive index of the adhesive layer 19 material and the hologram layer 15 material is sufficiently different, the adhesive layer 19 is a reflective layer. 19 can also be used.

  (Anchor layer) The anchor layer 21 is an easy-adhesion treatment layer for improving the adhesion between the two, and by providing the anchor layer 21 between the reflective layer 17 and the printed layer 19, the reflective layer 17, for example, Aluminum can prevent erosion, aging, and / or scratching during processing. Examples of the anchor layer 21 include polyurethane resins, polyester resins, polyamide resins, epoxy resins, phenol resins, polyvinyl chloride resins, polyvinyl acetate resins, and vinyl chloride-vinyl acetate copolymers. , Acid-modified polyolefin resins, copolymers of ethylene and vinyl acetate or acrylic acid, (meth) acrylic resins, polyvinyl alcohol resins, polyvinyl acetal resins, polybutadiene resins, rubber compounds, petroleum resins, alkyl titanes -Too compounds, polyethyleneimine compounds, isocyanate compounds, starch, casein, gum arabic, cellulose derivatives, waxes 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 sufficiently kneaded as necessary to prepare a coating agent composition (ink, coating solution), such as a roll coating method or a gravure coating method. It is formed by applying and drying by a known coating method, or by reacting by aging treatment after drying or drying. The anchor layer 13 has a thickness of about 0.05 to 10 μm, preferably 0.1 to 5 μm.

(Print Layer) The print layer 19 may be a known printing method and is not particularly limited. For example, the printing layer 19 may be printed by a known screen printing or gravure printing method using a known ink.
If a fluorescent ink containing a fluorescent pigment or a fluorescent dye is used, the design is more excellent.

  (Second Step) In the second step, the surface of the printed layer 19 of the first hologram film 10A and the second base material 11B are laminated by the dry lamination method through the adhesive layer 31, and the second hologram film 10B. It is a process.

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

  (Adhesive) As an adhesive for the adhesive layer 31 used in the dry lamination method or the non-solvent lamination method, an adhesive that is cured by heat or ionizing radiation such as ultraviolet rays or electron beams can be applied. Specific examples of thermosetting adhesives include two-component curable urethane adhesives, polyester urethane adhesives, polyether urethane adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, A polyvinyl acetate adhesive, an epoxy adhesive, a rubber adhesive, or the like can be applied, but a two-component curable urethane adhesive is preferable.

  In the dry lamination method, an adhesive composition mainly composed of these is dissolved or dispersed in an organic solvent, and this is applied by a coating method such as roll coating, gravure coating, or comma coating, and the solvent is dried. Thus, the lamination adhesive layer 31 of the present invention can be formed. Roll coating and reverse roll coating are preferred.

  The thickness of the adhesive layer 31 is about 0.1 to 20 μm (dry state), preferably 1 to 10 μm. Immediately after the formation of the adhesive layer, after laminating the bonded substrates, the adhesive is cured by curing at 30 to 120 ° C. for several hours to several days. When a non-absorbable material such as an organic polymer sheet or film is used as the material for the bonding substrate, an adhesive may be applied to the bonding substrate side, laminated, and bonded. That is, in the present invention, the application surface of the adhesive may be the printed layer surface of the first hologram film or the second substrate surface.

  (Third Step) The third step is a step of forming the third hologram film 10C by forming the protective layer 41 on the surface of the second base material 11B where the second hologram film 10B is exposed.

  (Protective layer) The material of the protective layer 41 contains at least urethane (meth) acrylate, and preferably reacts an organic isocyanate having a plurality of isocyanate groups in one molecule with polycaprolactone-modified alkyl (meth) acrylate. Or urethane (meth) acrylate obtained by reacting an organic isocyanate having a plurality of isocyanate groups in one molecule with polycaprolactone-modified alkyl (meth) acrylate, and 1 Contains an organic isocyanate having a plurality of isocyanate groups in the molecule and a urethane (meth) acrylate obtained by reacting a hydroxyalkyl (meth) acrylate, or an organic isocyanate having a plurality of isocyanate groups in one molecule And Polica Rorakuton a cured product of the modified alkyl (meth) acrylates and hydroxyalkyl (meth) urethane obtained by reacting an acrylate (meth) ionizing radiation curable compositions containing acrylate. Details are disclosed in Japanese Patent Application Laid-Open No. 2003-302501.

  (Method for Forming Protective Layer) The protective layer 41 may be an ionizing radiation curable resin cured by irradiating the composition containing the ionizing radiation curable resin with ionizing radiation. As an ionizing radiation curable resin composition before curing, an oligomer or a prepolymer such as a (meth) acrylate of a polyfunctional compound such as a polyhydric alcohol and a reactive dilution, if necessary, to the ionizing radiation curable resin. An agent, a photopolymerization initiator, a photosensitizer and the like can be applied. An ultraviolet absorber is dissolved or dispersed in the ionizing radiation curable resin composition, if necessary, applied, and cured by irradiation with ionizing radiation to obtain an ionizing radiation curable resin. Examples of photopolymerization initiators include acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime esters, thioxanthones, and photosensitizers include n-butylamine, triethylamine, tri-n-butylphosphine, Use by mixing. The film thickness of the protective layer 41 is usually in the range of 1 to 30 μm, and the formation method thereof is not particularly limited, and a normal coating method can be used.

When curing the composition containing the ionizing radiation curable resin, it is preferable to use a mercury lamp, a metal halide lamp or the like as the ultraviolet ray to be irradiated, and it is preferable to irradiate the ultraviolet ray with an integrated light quantity of 100 to 5000 mJ / cm ² . On the other hand, in the case of curing by irradiation with an electron beam, irradiation with an electron beam of 1 to 20 Mrad at an acceleration voltage of 150 to 250 keV is preferable.

(Scratch Abrasion) The protective layer 41 formed in this way has scratch resistance based on a self-repair function, imparts excellent scratch resistance to the surface of a label with a hologram, and can suppress scratches.
The scratch resistance is a self-repair function when the cured film of the protective layer 41 is scratched using a diamond indenter with a tip diameter of 15 μm and the cured film is at 25 ° C. and 50% relative humidity. In a scratch test in which the critical load (vertical load) [mN] that makes it impossible to recover the scratch mark by a scratch tester manufactured by HEIDON was performed, a self-repair function capable of recovering a scratch mark with a vertical load of 2.4 mN was obtained. It was based on scratch resistance.

  (Fourth Step) The fourth step is a step in which the release paper 53 is detachably laminated via the black adhesive layer 51 on the surface of the first base material 11A of the third hologram film 10C.

  (Adhesive layer) As the adhesive of the black adhesive layer 51, one obtained by adding a dark and dark pigment and / or dye to an 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. 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. The black color is not limited to black and may be a dark and dark color.

  (Release paper) The release paper 53 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.

  (Labeling) As described above, the hologram-attached label produced by the method for producing a hologram-attached label of the present invention may be appropriately half-cut, fully cut, or a label sheet or a roll label. The hologram-attached label of the present invention is formed in the above-described configuration. In use, the release paper 53 is peeled off, the surface of the adhesive layer is overlaid on the adherend, and the adhesive label is heated or heated as necessary. Can be easily attached to the body. The label with hologram attached to the adherend is a beautiful one in which the pattern and the hologram are in harmony with each other, and in harmony with the design, color, and tone of the adherend, and is useful as a hologram sticker. When it is affixed to cards such as credit cards, gold vouchers such as appraisals, and high-end products, it exhibits high anti-counterfeiting properties.

  Moreover, since both sides of the hologram 15 and the printing layer 19 are sandwiched between the first base material 11A and the second base material 11B, there is a certain thickness, and there is a heavy and high-quality texture. In addition, since the reflective layer 17 is thin so that the back side can be seen through, the adhesive layer is a black adhesive layer 53, so that the back side can be used even if a very thin metal reflective layer is used. Even if a transparent reflective layer is used, it is not transparent and a transparent hologram emerges in black, and a high-quality texture is expressed. Therefore, it is possible to obtain a hologram-attached label that has excellent texture, the back side is not transparent, and has excellent durability such as scratch resistance on the label surface.

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

(Example 1) Diafoil T600E50U36 (manufactured by Mitsubishi Chemical Corporation, trade name of PET film) having a thickness of 50 μm was used as the first base material 11A, and the following ionizing radiation curing was applied to the easy adhesion treated surface of the first base material 11A. The photosensitive resin composition was applied with a gravure reverse coater so that the coating amount after drying was 2 μm, and dried at 100 ° C. to form the hologram layer 15.
・ <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. As a result of infrared absorption spectrum analysis, it was confirmed that the obtained reaction product solution had extinguished isocyanate groups. The softening temperature of what distilled ethyl acetate from the reaction product liquid was 43 degreeC.
The reaction product (A), a film-forming resin (acrylic oligomer), reactive silicone, a photopolymerization initiator, and a solvent were blended in the following composition to prepare an ionizing radiation curable resin composition.
・ <Ionizing radiation curable resin composition>
Reactive organism (A) 25 parts by weight Acrylate oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Purple light 6630B) 5 parts by weight Reactive silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-2445) Initiator (product name: Irgacure 184, manufactured by Ciba) 0.9 parts by mass Ethyl acetate 70 parts by mass Next, the embossing of the duplicating apparatus was performed using the unevenness duplicated by the 2P method from the hologram by the two-beam interference method on the hologram layer surface. It was attached to a roller and heated and pressed (embossed) with an opposing roller to form a relief consisting of a fine uneven pattern. Immediately after shaping, the film was cured by irradiating with ultraviolet rays using a high-pressure mercury lamp.
An aluminum thin film having a thickness of 300 nm was formed on the relief surface of the hologram layer 15 by a vacuum deposition method to obtain a reflective layer 17.
Next, the anchor layer 21 was formed by coating the surface of the reflective layer 17 with the following anchor layer composition using a gravure coater so that the coating amount after drying was 1 μm and drying at 100 ° C.
・ <Anchor layer composition>
Polyester resin 10 parts by mass Vinyl chloride-vinyl acetate copolymer 10 parts by mass Solvent (toluene: ethyl acetate = 1: 1) 80 parts by mass Next, a silk screen is applied to the surface of the anchor layer 21 using colored ink and fluorescent ink. Printing was performed by a printing method, and the printed layer 19 was formed in synchronization with the hologram pattern to obtain the first hologram film 10A.
Next, a printing surface of the primary hologram film 10A and an untreated surface of Diafoil T600E50U36 (Mitsubishi Chemical Corporation, PET film product name) having a thickness of 50 μm as a separately prepared second base material 11B, The following adhesive composition was laminated with a known dry laminator so that the thickness after drying was 8 μm, and aged at 40 ° C. for 2 days to obtain a secondary hologram film 10B.
・ <Adhesive composition>
Takelac 310 (Mitsui Takeda Chemical Co., PU adhesive, trade name) 24 parts Takelac A3 (Mitsui Takeda Chemical Co., curing agent, trade name) 2 parts Solvent (ethyl acetate: toluene = 2: 5) 74 parts Next In addition, a self-healing clear UV curable type (manufactured by NATCO, trade name) is used as a solvent (toluene: isobutanol = 2) on the surface of the second base material 11B exposed to the second hologram film 10B. The protective layer composition adjusted to a solid content of 25% by mass in 1) was applied with a known gravure reverse coater so that the thickness after drying was 6 μm, dried, and then irradiated with ultraviolet rays using a high-pressure mercury lamp at 300 mj / cm ^2. Irradiated to cure. A third hologram film 10C was obtained.
Next, a known comma coater is used so that the thickness after drying the known black adhesive layer composition to 30 μm on the unbonded treated surface of the first base material 11A where the third hologram film 10C is exposed. After coating and drying, a commercially available PET separator paper having a thickness of 36 μm was peelably laminated as the release paper 53 to obtain a hologram-attached label of Example 1.

  (Evaluation) When scratch marks were given to the surface of the protective layer 41 of the hologram-attached label of Example 1 using a diamond indenter with a tip diameter of 15 μm, the protective layer film was in an atmosphere of 25 ° C. and a relative humidity of 50%. When a critical load (vertical load) [mN] at which the scratch mark cannot be recovered by the self-healing function was measured by a scratch tester manufactured by HEIDON, a self capable of recovering a scratch mark of 2.4 mN vertical load. It had scratch resistance based on the repair function.

It is sectional drawing for every process explaining the manufacturing method of this invention.

Explanation of symbols

10A: primary hologram film 10B: secondary hologram film 10C: tertiary hologram film 11A: first substrate 11B: second substrate 15: hologram layer 17: reflection layer 19: printing layer 21: anchor layer 31 : Adhesive layer 41: Protective layer 51: Black adhesive layer 53: Release paper

Claims (4)

(1) a step of preparing a first substrate and a first hologram film provided with a hologram layer, a reflective layer, an anchor layer, and a print layer on one surface of the first substrate; (2) the first A step of laminating the printed layer surface of the primary hologram film and the second base material by a dry lamination method through an adhesive layer to form a secondary hologram film; and (3) exposure of the secondary hologram film. Forming a third layer hologram film by forming a protective layer on the second substrate surface, and (4) passing the black adhesive layer to the first substrate surface of the third hologram film. And a step of laminating the release paper in a peelable manner, and a method for producing a label with a hologram Curing of an ionizing radiation curable composition containing urethane (meth) acrylate obtained by reacting organic isocyanate having a plurality of isocyanate groups in one molecule and polycaprolactone-modified alkyl (meth) acrylate in the above-mentioned protective layer. The method for manufacturing a label with a hologram according to claim 1, wherein the label is a product. When the protective layer gives a scratch mark at a vertical load of 2.4 mN using a diamond indenter with a tip diameter of 15 μm, the cured film has a self-healing function in the atmosphere of 25 ° C. and a relative humidity of 50%. The method for producing a hologram-attached label according to claim 1, wherein the hologram-containing label has a scratch property capable of recovering. A label with hologram produced by the method for producing a label with hologram according to claim 1.

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