JP4770342B2 - Method for producing shrink film with hologram - Google Patents

Description

  The present invention relates to a shrink film with a hologram, and more particularly, relates to a hologram transfer foil, a shrink film with a hologram, and a method for manufacturing the same to make the shrink film have good followability to shrink shrinkage and to have as large an area as possible. is there.

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

(Main use) The main use of the shrink film with hologram of the present invention is to shrink packaging three-dimensional molded products such as cans, bottles, bottles, and various products and individual packages. As a result, the contents of molded products and individual packages are arbitrary.
However, the area is not particularly limited as long as it is an area that is as large as possible, or preferably the entire surface, or uses a hologram pattern as a background and other arbitrary printed patterns and requires a more specific design.

(Background technology)
Usually, the brightness of the hologram changes due to the shrinkage, and particularly when the reflective layer is aluminum, the original metallic luster becomes white due to the shrinkage and the metallic luster is lost completely, and the hologram is also lost. Conventionally, in order to suppress the influence of shrinkage to the minimum, it has been necessary to suppress the influence of shrinkage to a minimum by attaching or transferring a hologram to a portion with little shrinkage, or making a hologram with a small area.
The shrink film with hologram is heat resistant to withstand shrinkage due to heat of the shrink film, and has good conformability to shrinkage even if the shrink rate of the shrink film is large, and has excellent design with little decrease in hologram effect. There is a demand for a material having both shrinkage and filtration properties. Further, there is also a demand for a more specific design property with an area as large as possible, or preferably the entire surface, or in combination with other arbitrary printed patterns with a holographic pattern as a background.

(Prior Art) Conventionally, a method is known in which a hologram image is transferred from a hologram transfer sheet to a heat shrinkable film, and the heat shrinkable film is wound around an adherend to be shrunk (for example, see Patent Document 1).
In addition, as a package having a decorative effect and anti-counterfeit function, a package having a hologram on one surface of a heat shrink film and a back-off prevention layer on the other surface is known (for example, Patent Document 2). reference.).
However, Patent Documents 1 and 2 are assigned by the applicant of the present application, and any hologram is transferred or pasted, and the dry lamination method is neither described nor suggested.
The shrinkage rate is also specified in Patent Document 2 so as to be 5% or less, and it is clear that the shrinkage rate is limited to a low shrinkage rate. In order to eliminate the above drawbacks, further diligent research has been carried out, the resin of the hologram layer is limited to a stretchable resin, and the lamination to the shrink film is limited to the dry lamination method using a stretchable polyurethane adhesive. In this way, the shrinkage resistance of the hologram itself is increased, and the shrinkage of the shrink film is made to follow. The shrinkage resistance of the hologram itself is not described or suggested in Patent Documents 1 and 2.

Japanese Patent Laid-Open No. 03-171083 JP 09-77174 A

  Accordingly, the present invention has been made to solve such problems. Its purpose is heat resistance to withstand shrinkage due to heat of the shrink film, good follow-up to shrinkage even if the shrink rate of the shrink film is large, less hologram effect and excellent design, ie heat resistance and shrinkability It is intended to provide a hologram transfer foil, a shrink film with a hologram, and a method for producing the same, which can be balanced, have an area as large as possible, or have the entire surface as large as possible, or have a hologram pattern as a background and a design that is combined with a printed pattern.

In order to solve the above-mentioned problems, a method of manufacturing a shrink film with a hologram according to the invention of claim 1 includes: (1) a substrate, a release layer, a hologram layer, and a reflective layer on one surface of the substrate; preparing a hologram transfer foil having a, (2) a and the reflective layer surface of the hologram transfer foil and shrink film, laminating a dry lamination method using an adhesive layer, (3) the substrate In the method for producing a shrink film with a hologram , wherein the hologram layer comprises (1) an isocyanate having three or more isocyanate groups in the molecule and (2) a hydroxyl group in the molecule. Urethane (meth) acrylate oligo, which is a reaction product of at least one polyfunctional (meth) acrylate having at least two (meth) acryloyloxy groups -Containing a cured product of ionizing radiation curable resin, acrylic oligomer, and reactive silicone containing-, wherein the hologram layer is (1) the coating before ionizing radiation curing is in a finger dry state, and (2) ionizing radiation 180 degreeC atmosphere in the state of the hologram transfer foil provided with the base material, the release layer, the hologram layer, and the reflective layer provided that the breaking elongation at 23 ° C after curing is 5% or more It has heat resistance that does not whiten even if left in it for 1 hour, the pattern of the hologram layer is a pseudo-continuous pattern, and a two-component curable polyurethane adhesive is used as an adhesive in the laminating process, and dry lamination A method for producing a shrink film with hologram, characterized in that it is a step of laminating the entire surface of the reflection layer surface and the shrink film of the hologram transfer foil .

According to the present invention of claim 1, the followability to a shrink film having a large shrinkage ratio is good, the decrease in the hologram effect is small, and the area or the entire surface is as large as possible, or the hologram pattern is used as a background together with the printed pattern. enhanced design properties, rather is good followability even to large shrink film shrinkage ratio, a manufacturing method of high hologram-shrinkable film designability is provided in conjunction with a printing picture and the background on the entire surface hologram.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view for explaining a method for producing a shrink film with hologram of the present invention.

  (Manufacturing method of shrink film with hologram) As shown in FIG. 1, the manufacturing method of the shrink film with hologram 1 of the present invention includes (1) a substrate 11 and a release layer 13 on one surface of the substrate 11. A step of preparing the hologram transfer foil 10 provided with the hologram layer 15 and the transparent reflection layer 17, and (2) the surface of the transparent transfer layer 17 of the hologram transfer foil 10 and a separately prepared shrink film 21. A description will be given of a process including lamination by a dry lamination method through the layer 31, (3) a process of peeling the substrate 11, and a process including three materials.

  (First Step) In the first step, a hologram transfer foil 10 is prepared as shown in FIG.

  (Hologram Transfer Foil) The hologram transfer foil 10 includes a base material 11, a release layer 13, a hologram layer 15, and a transparent reflection layer 17 on one surface of the base material 11.

(Substrate) As the substrate 11, various materials can be applied depending on the use as long as the substrate 11 has heat resistance, mechanical strength, mechanical strength to withstand manufacturing, solvent resistance, and the like. For example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as nylon 6 and nylon 66, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, vinyl resins such as polyvinyl chloride, polymethacrylate , Acrylic resins such as polymethyl methacrylate, styrene resins such as polycarbonate, polystyrene and high impact polystyrene, cellulose films such as cellophane and cellulose acetate, imide resins such as polyimide, polyarylate, polysulfone, polyaramid and polyether There are engineering resins such as ketones.
Preferably, in terms of heat resistance and mechanical strength, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyethylene terephthalate / polyethylene Polyethylene resin film such as naphthalate coextruded film, and polyethylene terephthalate is most suitable. The thickness of the substrate is usually about 2.5 to 50 μm, but 4 to 25 μm is preferable in terms of transferability.

  The substrate 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 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 substrate is used as a film, sheet or board formed of at least one layer of these resins. Prior to application, the substrate is subjected to 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, dust removal treatment. Alternatively, easy adhesion treatment such as vapor deposition treatment or alkali treatment may be performed. Moreover, you may add additives, such as a filler, a plasticizer, a coloring agent, and an antistatic agent, as needed.

  (Release Layer) As the release layer 13, a release resin, a resin containing a release agent, a curable resin that is cross-linked by ionizing radiation, and the like can be applied. 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).

  The release 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 release layer 13 is usually about 0.01 μm to 5 μm, preferably about 0.5 μm to 3 μm. The thinner the thickness is, the better. However, when the thickness is 0.1 μm or more, better film formation is obtained and the peeling force is stabilized.

  (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, in particular, a resin obtained by curing an ionizing radiation curable resin such as an epoxy-modified acrylate resin, a urethane-modified acrylate resin, or an acrylic-modified polyester can be used.

  (Ionizing radiation curable resin composition M) The ionizing radiation curable resin of the hologram layer 15 is a cured product of an ionizing radiation curable resin containing a urethane (meth) acrylate oligomer, specifically, JP-A-2001-329031. It is preferable to include a photo-curing resin (referred to herein as “ionizing radiation-curable resin composition M”), an acrylic oligomer, and a cured product of a reactive silicone disclosed in Japanese Patent Publication No. JP-A.

  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 or (3) polyhydric alcohols having at least two hydroxyl groups in the molecule, and further including an acrylic oligomer and reactive silicone.

  (Acrylic oligomer) The acrylic oligomer may be (meth) acrylate, (meth) acrylic and heat-resistant oligomer, for example, trade names of Nippon Synthetic Chemical Co., Ltd .; purple light 6630B, 7510B, 7630B, etc. It can be illustrated. The ratio on the basis of mass to be contained is about 10 to 30 parts, preferably 15 to 25 parts with respect to 100 parts of “ionizing radiation curable resin composition M”. If it is less than this range, the heat resistance is insufficient, and if this range is exceeded, the heat resistance is good, but cracking tends to occur.

  (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 when the relief is formed, and it is difficult to prevent contamination of the press stamper. 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 is referred to as “ionizing radiation curable resin composition M”), an acrylic oligomer, and a cured product of reactive silicone, thereby having the following three effects. It is.
(1) Since the hologram layer coating film 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) The relief structure can be easily shaped and then cured with ionizing radiation, and the elongation at break at 23 ° C. after ionizing radiation curing can be 5% or more, preferably 7% or more. If it is less than 5%, it cracks or whitens during shrinkage. If it is 7% or more, even if the shrinkage rate is high, it does not crack or whiten during shrinkage.

  (3) In the state of hologram transfer foil provided with a base material, a release layer, a hologram layer, and a reflective layer, it has heat resistance that does not whiten even if left in an atmosphere at 180 ° C. for 1 hour, so the shrink film is usually shrunk Even with heat of 150 to 200 ° C., the hologram does not deteriorate.

  (Breaking elongation) The shrinkage of the hologram layer is expressed by breaking elongation, and the measuring method of breaking elongation (%) of the hologram layer is that the resin layer after UV curing is 24 hours or more under the condition of 23 ° C. and 55% RH. After being allowed to stand, the data processing was performed using the Tensilon multifunctional data processing TYPE MP-100 / 200S Ver. Measurement was performed using No. 44. The sample is 10 mm wide, the distance between chucks is 50 mm, the RANGE is 20%, the load is 100 kg, and the tensile speed is 10 mm / min. The elongation with respect to the length was used. In the measurement of the elongation at break of the hologram layer, it is difficult to produce a single hologram layer. Therefore, a 10 μm hologram layer is formed on a 25 μm peeled PET, exposed to a total exposure amount of 250 mj with a metal halide lamp, and then peeled off. It was.

  (Heat resistance) The heat resistance of the hologram layer is determined by visually observing cracks in an oven at 180 ° C. for 1 hour in a hologram transfer foil state in which a base material, a release layer, a hologram layer, and an aluminum reflective layer are provided. Those that did not crack and / or whiten were considered acceptable.

  The hologram layer is prepared by dispersing or dissolving the above resin and, if necessary, additives in a solvent, applying at least one part by a known coating method such as roll coating, gravure coating, bar coating, etc., and drying. A film may be formed. The thickness of the hologram layer 15 is usually about 0.1 μm to 10 μm, preferably about 0.3 μm to 5 μm.

(Hologram) Next, on the surface of the hologram layer 15, a predetermined relief structure exhibiting a light diffraction effect is formed and cured.
(Relief) 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, Further, 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 plate 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.

  (Relief pattern) The pattern of the hologram layer 15 is preferably a quasi-continuous pattern. When creating a press mold (referred to as a stamper) for the pseudo continuous pattern, it is only necessary to match a plurality of small relief plates with high accuracy to make the joints inconspicuous, or to fill the joints with resin. In this way, by using a quasi-continuous pattern, the area can be as large as possible, or preferably the entire surface. Further unique design can be improved by synchronizing or matching with any other printed pattern against a large area or entire surface of the hologram pattern. The printed pattern may be appropriately provided on the interlayer or the layer surface by a known printing method or the like, and the printed pattern may be provided on either the hologram transfer foil and / or the shrink film.

  (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.

  (Second Step) The second step is a step of laminating the transparent reflection layer 17 surface of the hologram transfer foil 10 and the separately prepared shrink film 21 by the dry lamination method through the adhesive layer 31. The state is shown in FIG.

  (Shrink film) The shrink film may be a known film that shrinks by heat, such as polyethylene, radiation-cured polyethylene, polyvinyl chloride, polypropylene, polyvinylidene chloride, polyester, polystyrene, ethylene-vinyl acetate copolymer, ionomer resin. It is possible to use a film or sheet mainly composed of a resin such as uniaxially or biaxially.

  (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.

  Specific examples of the two-component curable polyurethane resin include, for example, a polymer obtained by reacting a polyfunctional isocyanate and a hydroxyl group-containing compound, specifically, for example, tolylene diisocyanate. , Aromatic polyisocyanates such as diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate. A two-component polyurethane resin obtained by a reaction between a functional isocyanate and a hydroxyl group-containing compound such as a polyether polyol, a polyester polyol or a polyacrylate polyol can be used.

  In the dry lamination method, an adhesive composition containing these as a main component is dissolved or dispersed in an organic solvent, and this is, for example, roll coating, reverse roll coating, gravure coating, or gravure reverse coating. Coating, gravure offset coating, kiss coating, wire bar coating, comma coating, knife coating, dip coating, flow coating, spray coating, etc. The agent layer 31 can be formed. The roll coating method and the reverse roll coating method 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 adhesive application surface may be the transparent reflection layer 17 surface of the hologram transfer foil 10 or the shrink film 21 surface.

  The non-solvent lamination method is basically the same as the dry lamination method, but the adhesive composition is used as it is without dissolving or dispersing the adhesive composition in an organic solvent, but the viscosity is reduced if necessary. In some cases, the adhesive composition is heated and heated.

  (Third Step) The third step is a step of peeling the substrate 11 after laminating by the dry lamination method, and the peeled state is shown in FIG. The peeling method may be a known method, and only the substrate 11 may be mechanically pulled and peeled off. In addition, although one part of the release layer 13 may remain on the shrink film side, there is no hindrance to peeling and is within the scope of the present invention.

(Shrink film with hologram) As described above, the lamination to the shrink film is limited to the dry lamination method using a stretchable polyurethane adhesive, and more preferably, the resin of the hologram layer described above is heat resistant and stretchable ( By limiting to a resin having a breaking elongation), the shrinkage resistance of the hologram itself can be enhanced, and the shrinkage of the shrinkable film can be made to follow.
The shrinkable film with hologram 1 of the present invention thus produced can be used for three-dimensional molded products such as cans, bottles, and bottles, and when shrink-wrapping various products and individual packages. Even if the shrinkage rate is large, the followability to the shrinkage is good and the decrease in the hologram effect is small. Further, the area can be as large as possible, or preferably the entire surface, or in combination with any other printed pattern with the hologram pattern as a background, further unique design can be improved.

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

( Reference Example 1 ) A 25 μm-thick PET film was used as the base material 11 and applied to one surface of the base material 11 by gravure coating so that the melamine resin coating solution was dried to 2 g / m 2. The release layer 13 was formed by drying.
On the surface of the release layer 13, the following ionizing radiation curable resin composition was applied with a gravure reverse coater so that the coating amount after drying was 2 g / m 2 and dried at 100 ° C. to form the hologram layer 15. Formed.
・ <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 blowing air 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.
An ionizing radiation curable resin composition was prepared by adding the reaction product (A), a film-forming resin, a photopolymerization initiator, and a solvent in the following composition.
・ <Ionizing radiation curable resin composition>
Reactive organism (A) 25 parts by mass acrylic oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Murasaki 6630B) 5 parts by mass reactive silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-2445) 0.2 parts by weight of photopolymerization Initiator (product name, Irgacure 184, manufactured by Ciba) 0.9 parts by mass ethyl acetate 70 parts by mass Next, a stamper having a quasi-continuous pattern replicated by a 2P method from a diffraction grating by a two-beam interference method onto the hologram layer surface. It stuck on the embossing roller of the duplication apparatus, and heat-pressed (embossed) between the opposing rollers, and the relief which consists of a fine uneven | corrugated pattern was shaped. Immediately after shaping, it was cured by irradiating with ultraviolet rays using a high-pressure mercury lamp. A titanium oxide thin film having a thickness of 300 nm was formed on the relief surface of the hologram layer 15 by vacuum deposition to obtain the hologram transfer foil 10 of Reference Example 1 as the reflective layer 17.

Reference Example 2 Reference Example 1 except that the following ionizing radiation curable resin composition was used as the ionizing radiation curable resin composition, and an aluminum thin film having a thickness of 500 nm was formed as the reflective layer 17 by vacuum deposition. In the same manner as described above, the hologram transfer foil 10 of Reference Example 2 was obtained.
・ <Ionizing radiation curable resin composition>
Reactive organism (A) 24 parts by mass acrylic oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Muriko 7510B) 6 parts by mass of reactive silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-1602) 0.1 parts by weight of photopolymerization Initiator (Ciba, trade name Irgacure 184) 0.9 parts by mass Ethyl acetate 70 parts by mass

As (Reference Example 3) ionizing radiation curable resin composition, except for using an ionizing radiation-curable resin composition of the following, in the same manner as in Reference Example 1, to obtain a hologram transfer foil 10 of Reference Example 3.
・ <Ionizing radiation curable resin composition>
Reactive organism (A) 24 parts by weight film-forming resin (methacrylic resin: Kuraray Co., Ltd., trade name Parapet GF) 6 parts by weight reactive silicone (Shin-Etsu Chemical Co., trade name X-22-1602) 0.1 mass Part photopolymerization initiator (Ciba, trade name Irgacure 184) 0.9 parts by weight ethyl acetate 70 parts by weight

(Evaluation) The hologram layers before curing in Reference Examples 1 to 3 were all in a finger dry state and could be wound up, and the subsequent steps could be rolled to roll. The heat resistance was 170 ° C. in Reference Example 1 , 170 ° C. in Reference Example 2 , and 150 ° C. in Reference Example 3 . The breaking elongation was 31% in Reference Example 1 , 31% in Reference Example 2 , and 5.5% in Reference Example 3 .

( Example 1 ) First, a polypropylene film having a thickness of 25 μm, a stretching ratio of 4% in the longitudinal direction and a stretching ratio of 6% in the lateral direction is used as the shrink film 21, and a predetermined pattern is applied to the shrink film 21 by a gravure printing method. Printed.
The surface of the transparent reflective layer 17 of the hologram transfer foil 10 of Reference Example 1 was applied by gravure coating so that the following adhesive layer 31 coating solution was applied so that the coating amount after drying would be 5 g / m 2. Then, the printed surface of the shrink film prepared earlier was immediately laminated with a dry lamination method. Then, it was made to harden | cure at 40 degreeC for 2 days, and the shrink film 1 with a hologram of Example 1 was obtained.
・ <Adhesive layer coating solution>
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 The storage case containing the DVD recording medium was wrapped with the shrink film 1 with hologram, sealed in three directions, and shrink-wrapped through a shrink tunnel at a temperature of 180 ° C. In the package, the transparent hologram was expressed without disappearing, and it was possible to enhance the design of the product with a unique decoration effect in combination with the printed pattern. Furthermore, it was difficult to forge and security was improved.

Example 2 First, a uniaxially stretched polystyrene film having a thickness of 25 μm and a stretching ratio of 6% in the longitudinal direction was used as the shrink film 21, and a predetermined pattern was printed on the shrink film 21 by a gravure printing method.
The surface of the reflection layer 17 of the hologram transfer foil 10 of Reference Example 2 was applied by gravure coating so that the following adhesive layer 31 coating solution was applied at a temperature of 5 g / m 2 after drying at 100 ° C. It dried and immediately laminated | stacked the non-printing surface of the shrink film prepared previously with the dry lamination method. Then, it was made to harden | cure at 40 degreeC for 2 days, and the shrink film 1 with a hologram of Example 2 was obtained.
The printed surface of the shrink film 1 with hologram was sealed on the outside in a cylindrical shape, covered on the barrel of a PET bottle and wound into a cylindrical shape, and then shrink-wrapped through a shrink tunnel at a temperature of 180 ° C. The package exhibited the metallic gloss hologram of aluminum without disappearing, and in combination with the printed pattern, the design of the product could be enhanced with a unique decorative effect.

It is sectional drawing explaining the manufacturing method of the shrink film with a hologram of this invention.

Explanation of symbols

1: Shrink film with hologram 10: Hologram transfer foil 11: Base material 13: Release layer 15: Hologram layer 17: Transparent reflection layer 21: Shrink film 31: Adhesive layer

Claims (1)

(1) a step of preparing a base material and a hologram transfer foil provided with a release layer, a hologram layer, and a reflective layer on one surface of the base material;
(2) the said the reflective layer surface of the hologram transfer foil and shrink film, laminating a dry lamination method using an adhesive layer,
(3) In the method for producing a shrink film with hologram, comprising the step of peeling the base material ,
The hologram layer (1) is an isocyanate having three or more isocyanate groups in the molecule, and (2) a polyfunctional (meth) acrylate having at least one hydroxyl group and at least two (meth) acryloyloxy groups in the molecule. An ionizing radiation curable resin containing a urethane (meth) acrylate oligomer, which is a reaction product with acryl oligomer, and a cured product of reactive silicone,
The hologram layer is (1) the coating film before ionizing radiation curing is finger-dried, (2) the elongation at break at 23 ° C. after ionizing radiation curing is 5% or more,
And (3) heat resistance that does not cause whitening even when left in a 180 ° C. atmosphere in the hologram transfer foil state in which the substrate, the release layer, the hologram layer, and the reflective layer are provided. ,
The pattern of the hologram layer is a pseudo-continuous pattern,
A step of laminating the entire surface of the reflection layer and the shrink film of the hologram transfer foil by a dry lamination method using a two-component curable polyurethane adhesive as an adhesive in the laminating step. A method for producing a shrink film with hologram as a feature.

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