JP4946209B2 - Hologram transfer foil and molded product with hologram using the same - Google Patents

Description

  The present invention relates to a hologram transfer foil, and more specifically, a hologram that can be transferred into a molding die without being whitened by being inserted into a mold for molding and having good followability to a three-dimensional surface. The present invention relates to a transfer foil and a molded article with a hologram using the transfer foil.

  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”.

  (Main applications) The main applications of the molded article with a hologram using the hologram transfer foil of the present invention include equipment bodies such as daily necessities and daily necessities, containers for food and various articles, housings such as electronic equipment and office supplies. A three-dimensional molded product such as a body, which has a unique design improved by a hologram on the surface of the molded product, and the shape and contents of the molded product are arbitrary. However, there is no particular limitation as long as it is an application in which a hologram is transferred to the surface of a molded product for high design.

  (Background Art) Conventionally, in a molded product by injection molding or the like, a hologram transfer foil is inserted into a mold at the time of molding, and a hologram is transferred simultaneously with injection molding. In order to further increase the design, it is required to transfer a hologram to a three-dimensional part of a molded product. However, the transfer is limited to a flat surface or a curved surface in one direction. In the three-dimensional part, the hologram transfer foil stretches and wrinkles and tears due to the flow of the molten high-temperature injection molding resin, and the glittering property changes due to cracking and expansion and contraction due to stretching and / or shrinkage. In the case of aluminum, the original metallic luster becomes white due to expansion and contraction, and the metallic luster is completely lost, and the hologram is also lost. Conventionally, in order to suppress the influence of expansion and contraction to the minimum, it has been necessary to suppress the influence of expansion and contraction to a minimum by attaching or transferring a hologram to a portion with little expansion and contraction, or making a hologram with a small area. Therefore, a hologram that can transfer a hologram with excellent heat resistance that does not whiten by heat, good followability to expansion and contraction even if the expansion ratio is large, and less deterioration of hologram effects such as cracking and whitening to a three-dimensional surface. There is a need for a hologram transfer foil for obtaining a molded article with a patch.

(Prior Art) Conventionally, an in-mold labeling type injection molding of a label made of a laminated sheet including a base material, a printing layer, a light diffraction structure layer (corresponding to the hologram layer of the present invention) and a thermoadhesive resin layer There is known a cup-shaped container that is integrally molded by the above-described method (for example, see Patent Document 1). However, the peripheral wall on which the hologram layer is formed is a flat surface and not a solid surface.
Further, after the decorative transfer layer (including the hologram layer of the present invention) is transferred to the stretchable material, the surface is transferred to a part of the surface of the molded article body having at least a part of the surface by unevenness or a curved surface by heating and pressing. A decorative molded product is known (for example, refer to Patent Document 2). However, there is a drawback that the decorative transfer layer cannot be directly transferred to a molded product.
Furthermore, a transfer film composed of a base film, a protective layer, a metal thin film (corresponding to the hologram layer and the reflective layer of the present invention), and an adhesive layer is produced, and a pair of molds are clamped with the transfer film interposed therebetween, There is known a method for manufacturing a false nail in which a molten resin is injected into the mold and a metal thin film is applied to the surface of the nail body (see, for example, Patent Document 3). However, the false nail is a large curved surface in one direction, and the transfer film itself is wound around a flat surface, and it is difficult to say that it is three-dimensional. Also, the materials of the protective layer, metal thin film, and adhesive layer constituting the transfer film However, there is no description or suggestion about the stretchability of the material, which is extremely general and is the biggest problem in transfer to a three-dimensional object.

JP 2005-7647 A JP 2004-58599 A Japanese Patent Laid-Open No. 2003-9941

  Accordingly, the present invention has been made to solve such problems. The purpose is to transfer a hologram with excellent heat resistance that does not whiten by heat, good conformity to expansion and contraction even when the expansion ratio is large, and less deterioration of hologram effects such as cracking and whitening to a three-dimensional surface. It is to provide a hologram transfer foil that can be formed, and a molded article with a hologram using the same.

In order to solve the above problems, a hologram transfer foil according to the invention of claim 1 is a hologram in which a base material and a release layer, a hologram layer, a reflective layer, and an adhesive layer are provided on one surface of the base material. in the transfer foil, the a release layer melamine resin, a cured product of the hologram layer is ionizing radiation-curable resin and reactive silicones, and polyethylene wax seen including, the ionizing radiation-curable resin (1) molecule Isocyanates having 3 or more isocyanate groups, (2) Polyfunctional (meth) acrylates having at least one hydroxyl group and at least two (meth) acryloyloxy groups in the molecule, or (3) In the molecule Containing a urethane (meth) acrylate oligomer which is a reaction product of a polyhydric alcohol having at least two hydroxyl groups, The content of tyrene wax is based on mass, ionizing radiation curable resin: polyethylene wax = 100: 0.01-10, the hologram layer is (1) the coating film before ionizing radiation curing is in a finger-dried state, (2) Breaking elongation at 23 ° C. after ionizing radiation curing is 5% or more and (3) 1 hour in a 150 ° C. atmosphere in a hologram transfer foil state in which a substrate, a release layer, a hologram layer and a reflective layer are provided The hologram transfer foil is characterized in that it has heat resistance that does not whiten even if left to stand and can transfer a hologram to a three-dimensional surface .
A molded article with a hologram using the hologram transfer foil according to the invention of claim 2 is obtained by transferring a hologram to a three-dimensional surface by an in-mold injection molding method using the hologram transfer foil of claim 1. This is a molded product with a hologram.

According to the first aspect of the present invention, it can be efficiently processed in the form of a winding, has heat resistance that does not whiten by heat, good followability to expansion and contraction, and has excellent design properties with less deterioration of hologram effects such as cracking and whitening. A hologram transfer foil capable of transferring a hologram to a three-dimensional surface is provided.
According to the present invention of claim 2 , a hologram having excellent design properties with little reduction in hologram effect such as cracking and whitening is transferred, and even in extremely harsh environments, long-term use, and / or repeated use many times, A molded article with a hologram using a hologram transfer foil that protects an image and has excellent durability is provided.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a sectional view of a hologram transfer foil showing one embodiment of the present invention.
FIG. 2 is a cross-sectional view of a molded product transferred using the hologram transfer foil of the present invention.

  (In-mold injection molding method) First, the in-mold injection molding method includes (1) a step of preparing a hologram transfer foil, (2) a step of inserting the hologram transfer foil into an injection mold, 3) A step of transferring the hologram layer of the hologram transfer foil onto the surface of the resin by injection molding and adhering the resin to the injection mold, and (4) releasing the mold after cooling and transferring the hologram A molded product in which a hologram is transferred to a three-dimensional surface can be manufactured by an injection molding method comprising a step of peeling a foil base material and taking out a molded product.

  (Hologram Transfer Foil) As shown in FIG. 1, the hologram transfer foil 10 of the present invention has a base material 11 and a release layer 13, a hologram layer 15, a reflective layer 17 and an adhesive layer 19 on one surface of the base material. It is a layer structure. Furthermore, you may provide another layer as needed. For example, the layer configuration may be substrate 11 / release layer 13 / hologram layer 15 / reflection layer 17 / other functional layer 21 (if necessary) / adhesion layer 19. The other functional layer 21 may be arranged at any position other than the base material 11 / release layer 12 / release layer 13 layer. Examples of the other functional layer 21 include a release layer, a printed pattern layer, and an ultraviolet absorption layer.

  (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 / polybutylene terephthalate / polyethylene naphthalate, polyamide resins, vinyl resins such as polyvinyl chloride, acrylic resins, imide resins, engineering resins such as polyarylate, polycarbonate, cellophane, etc. Cellulosic film. 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. Usually, polyester films such as polyethylene terephthalate and polyethylene naphthalate are preferably used because of their good heat resistance and mechanical strength, and polyethylene terephthalate is most suitable.

  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 base material is usually about 2.5 to 50 μm, preferably 2.5 to 12 μm, and most preferably 4 to 6 μm. 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, as needed.

  (Release layer, release layer) In order to improve the releasability at the time of transfer, a release layer 13 may be provided, and if necessary, a release layer 14 may be provided. Both of the release layer 13 and the release layer 14 The transferability can be further improved by providing.

  (Release layer) The release layer 13 usually includes a release resin, a resin containing a release agent, a curable resin that is cross-linked by ionizing radiation, etc. In the present invention, a melamine resin is used, which will be described later. By combining with the hard coat layer 15 to be peeled off, the separation between the release layer 13 and the hard coat layer 15 is stabilized, and the foil breakage during transfer can be remarkably improved.

  The release layer 13 is formed by dispersing or dissolving the resin in a solvent, applying and drying the resin by a known coating method such as roll coating or gravure coating, and baking at a temperature of about 150 ° C to 200 ° C. The thickness of the release layer 13 is usually about 0.01 μm to 5.0 μm, preferably about 0.5 μm to 3.0 μm.

  (Peeling layer) As the peeling layer 14, an acrylic resin, vinyl resin, polyester resin, fiber resin, wax, melamine to which a release agent such as fluorine resin, silicone, various waxes is added or copolymerized is used. In the case where both the release layer 13 and the release layer 14 are provided, they may be used in appropriate combination. In this case, the release layer 14 also has a function as a protective layer after transfer.

  (Hologram Layer) The hologram layer 15 includes at least an ionizing radiation curable resin and a cured product of reactive silicone, and polyethylene wax. 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) The term “ionizing radiation curable resin composition M”) and a cured product of reactive silicone, and polyethylene wax are included. 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.

  (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. 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.

  (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.

The release layer 13 is made of melamine resin, and the hologram layer 15 is made to contain an ionizing radiation curable resin and a cured product of reactive silicone, and polyethylene wax. By doing in this way, the hologram layer 15 (1) the coating film before ionizing radiation curing is not sticky in a finger-dried state and can be wound up without blocking, so that roll-to-roll processing can be performed and workability is improved. Good.
(2) The breaking elongation at 23 ° C. after curing with ionizing radiation can be 5% or more, preferably 7% or more. If it is less than 5%, it cracks or whitens during expansion and contraction. When it is 7% or more, even if the expansion / contraction ratio is high, it does not crack or whiten during expansion / contraction. (3) The substrate 11 / release layer 13 / hologram layer 15 / reflective layer 17 / adhesive layer 19 have heat resistance that does not whiten even when left in a 150 ° C. atmosphere in the hologram transfer foil 10 state. The heat resistance is the same whether or not the adhesive layer 19 is provided. (4) Since the formability is good by including reactive silicone in the hologram layer 15, a fine uneven relief structure that exhibits a hologram function can be easily shaped, and can be cured with ionizing radiation after shaping. . (5) After transfer to a medium such as a card, the hologram layer 15 becomes the outermost layer, but since the hologram layer 15 also has a hard coat function, it can be used in extremely harsh environments and used for a long period of time. , And / or even when used repeatedly many times, the image of the support is protected from solvents, mechanical friction, abrasion and scratches, and is not easily scratched and has excellent durability. (6) Since the hologram layer 15 is in contact with the release layer 13 using a melamine resin, the hologram layer 15 has a stable releasability, has a good foil breakage during transfer, and generates very few burrs. Transfer with good quality.

  The hologram transfer foil 10 of the present invention can be preferably used for transferring a hologram to a three-dimensional molded product by an in-mold injection molding method. FIG. 2 shows a cross section of a molded product to which a hologram is transferred using the hologram transfer foil 10. . In FIG. 2, for the convenience of drawing, the molded product is drawn in a plane but is three-dimensional, heat resistance that does not whiten with the heat of the molten resin, and the hologram layer 15 is stretched in the three-dimensional portion, but the expansion ratio is large. However, it is possible to obtain a molded article with a hologram that can transfer a hologram having excellent design properties with good conformability to expansion and contraction and less deterioration of hologram effects such as cracking and whitening to a three-dimensional surface.

  (Breaking elongation) The stretchability of the hologram layer 15 is expressed in terms of breaking elongation, and the method for measuring the breaking elongation (%) of the layer is that the resin layer after UV curing under conditions of 23 ° C. and 55% RH for 24 hours or more. 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 15, it is difficult to produce only the hologram layer 15 film. Therefore, the 10 μm hologram layer 15 is formed on the 25 μm peeled PET, and then peeled after exposure with a metal halide lamp at an integrated exposure amount of 250 mj. And used as a sample.

  (Heat resistance) The heat resistance of the hologram layer is determined by leaving it in an oven at 150 ° C. to 170 ° C. for 1 hour in a hologram transfer foil state in which a substrate, a release layer, a hologram layer, and an aluminum reflective layer are provided. Those that were not cracked and / or whitened by visual inspection were regarded as acceptable.

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

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

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

  (Relief shaping) The relief shape is shaped (also referred to as replication) on the surface of the hologram layer 15. Hologram shaping can be formed by a known method. For example, when recording diffraction gratings or interference fringes of holograms as reliefs of surface irregularities, a master on which the diffraction gratings or interference fringes are recorded in irregularities is pressed. The concave / convex pattern of the original 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) The hologram layer 15 is irradiated with ionizing radiation during or after embossing with a stamper to cure the ionizing radiation curable resin. The ionizing radiation curable resin becomes an ionizing radiation curable resin (hologram layer 15) when cured (reacted) by irradiation with ionizing radiation after the relief is formed. The ionizing radiation may be classified according to the quantum energy of the electromagnetic wave, but in this specification, all ultraviolet rays (UV-A, UV-B, UV-C), visible rays, gamma rays, X-rays, electrons It is defined as including a line. Accordingly, ultraviolet (UV), visible light, gamma rays, X-rays, or electron beams can be applied as ionizing radiation, but ultraviolet (UV) is preferred. An ionizing radiation curable resin that is cured by ionizing radiation may contain a photopolymerization initiator and / or a photopolymerization accelerator in the case of ultraviolet curing, and may not be added in the case of high energy electron beam curing. Can be cured even with thermal energy.

  (Relief pattern) The pattern of the hologram layer 15 is not particularly limited, but is preferably a pseudo-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.

  (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. As the reflective layer 17, a metal layer or a transparent layer can be usually applied, but when the support 101 has the image 105 such as an ID card, a transparent layer capable of observing the image 105 is preferable. When the image 105 is not provided on the support 101 or when transferring to a part of the support 101, an opaque metal layer may be used.

  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.

  (Adhesive layer) As the adhesive layer 19, a heat-sensitive adhesive that melts or softens when heated and exhibits an adhesive effect can be applied. Specifically, a vinyl chloride resin, a vinyl acetate resin, or vinyl chloride. Examples thereof include vinyl acetate copolymer resins, acrylic resins, and polyester resins. The adhesive layer 19 preferably contains a filler such as microsilica in terms of the ability to break the foil. Further, the resin of the adhesive layer 19 is preferably one having a melting point of 60 to 95 ° C. which melts and adheres at a low temperature of about 95 ° C. and solidifies and adheres at about 60 ° C. When the melting point is less than the above range, the adhesion to the support is insufficient, and the temperature at which the formed image is used is limited. On the other hand, if the melting point exceeds the above range, the transferability becomes insufficient by heating with a thermal head, the foil breakability of the hard coat layer is lowered, and transfer with good resolution becomes difficult. 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 and dried by a known method such as roll coating, gravure coating, or comma coating, and a layer having a thickness of 1 to 30 μm Get.

  (In-mold injection molding) Thus, the hologram transfer foil 10 of the present invention can be prepared. Using the hologram transfer foil 10, a molded product in which a hologram is transferred to a three-dimensional surface can be manufactured by an in-mold injection molding method. First, (2) the hologram transfer foil 10 is inserted into an injection mold, and (3) a resin is injection-molded and brought into close contact with the injection mold, and the hologram of the hologram transfer foil 10 is attached to the surface of the resin. (4) After cooling, the mold may be released, and the hologram transfer foil base 11 may be peeled off together with the release layer 13 to take out the molded product. Although a part of the release layer 13 may remain on the hologram layer 15 side, there is no hindrance to peeling, and it is within the scope of the present invention.

  (Injection molded product with hologram) As described above, the release layer 13 and the hologram layer 15 are formed as a hologram transfer foil 10 using a specific material, and the heat is not whitened to the three-dimensional surface by the in-mold injection molding method by the heat of the hologram itself. And a good conformability to expansion and contraction, and a molded article with a hologram to which a hologram excellent in design properties with very little cracking or whitening can be produced. In addition, the hologram transfer foil 10 can be further improved in unique design characteristics in combination with other arbitrary printed patterns with the hologram pattern as a background.

  (Injection molded product) The material of the injection resin is not particularly limited, and may be a known resin such as polystyrene, polyethylene terephthalate, polypropylene, and acrylic resin. The shape of the injection-molded product is not particularly limited, and can be applied as long as at least one part has a three-dimensional part. The three-dimensional portion may be a secondary surface or a tertiary surface, and includes a wave shape, a curved surface shape, a polyhedron shape, a circle or a pyramid shape, a spherical shape, and the like, or a combination of these, or a random shape. The molded product by injection molding can be used for equipment bodies such as daily necessities and daily necessities, containers for food and various articles, electronic equipment such as mobile phones, and housings such as office supplies.

  (Durability) The pencil hardness test of the hologram layer 15 was measured according to JIS-K5400 and had a hardness of H or higher. In addition, the scratch strength of the hologram layer 15 is 150 g or more, preferably 200 g or more, from the viewpoint of sufficient friction resistance on the surface. The scratch strength was measured using a wear resistance tester (HEIDON-18) on a sample conditioned at 23 ° C. and 55% RH for 24 hours, with a 0.8 mmφ sapphire needle at a right angle. As a result, the load applied to the sapphire needle was gradually increased from 0 g to 200 g, and the load when the surface began to be scratched was measured while sliding and moving the sample surface at 60 cm / min. The larger the load, the better.

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

Example 1 Using a PET film having a thickness of 25 μm as the base material 11, a TCM01 medium (manufactured by Dainippon Ink Co., Ltd., melamine resin product name) coating liquid is applied to one surface of the base material 11 by a gravure coating method. After being dried, it was applied to a thickness of 2 μm, dried, and baked at 080 ° C. for 20 seconds to form a release layer 13.
The surface of the release layer 13 was coated with the following ionizing radiation curable resin composition with a gravure reverse coater so that the thickness after drying was 2 μm and dried at 100 ° C.
・ <Procedure for producing ionizing radiation curable resin composition>
First, “ionizing radiation curable resin composition M” was produced by the following procedure. A reactor equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 206.1 g of ethyl acetate and 133.5 g of isophorone diisocyanate trimer (HULS product, VESTANAT T1890, melting point 110 ° C.), 80 The solution was heated to 0 ° C. and dissolved. After air was blown into the solution, 0.38 g of hydroquinone monomethyl ether, 249.3 g of pentaerythritol triacrylate (product of Osaka Organic Chemical Industry Co., Ltd., Viscoat 300) and 0.38 g of dibutyltin dilaurate were charged. After reacting at 80 ° C. for 5 hours, 688.9 g of ethyl acetate was added and cooled.
The “ionizing radiation curable resin composition M”, a film-forming resin (acrylic oligomer), a reactive silicone, a polyethylene wax, a photopolymerization initiator, and a solvent are blended in the following composition to form an ionizing radiation curable resin. A composition was prepared.
・ <Ionizing radiation curable resin composition of hologram layer>
“Ionizing radiation curable resin composition M” 25 parts by mass Methacrylate oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name Murasaki 6630B) 5 parts by mass of reactive silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-2445) 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 A stamper with a quasi-continuous pattern duplicated from the diffraction grating by the beam interference method by the 2P method is attached to the embossing roller of the duplicating apparatus, and is heated and pressed (embossed) with the opposing roller to form a fine uneven pattern. The relief was shaped. Immediately after shaping, it was cured by irradiating with ultraviolet rays using a high-pressure mercury lamp.
A reflective layer 17 was formed by forming a 100 nm thick aluminum thin film on the relief surface of the hologram layer 15 by vacuum deposition.
The following adhesive layer composition was applied to the surface of the reflective layer 17 with a gravure coater so that the coating amount after drying was 1 μm, and dried at 100 ° C. to form an adhesive layer 19. The hologram transfer foil 10 was obtained.
・ <Adhesive layer composition>
Polyester resin P-170 (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name) 20 parts by mass Microsilica (average particle size 0.5 μm) 10 parts by mass Solvent (MEK: toluene = 1: 1) 70 parts by mass

(Example 2) The following ionizing radiation curable resin composition was used as the ionizing radiation curable resin composition of the hologram layer 15, and a titanium oxide thin film having a thickness of 50 nm was formed as the reflective layer 17 by vacuum deposition. In the same manner as in Example 1, a hologram transfer foil 10 of Example 2 was obtained.
・ <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: Murasakimitsu 7510B) 5 parts by mass 2 parts by mass Polyethylene wax (average particle size 2.0 μm) 2 parts by mass Photopolymerization initiator (Ciba, trade name Irgacure 907) 0.9 parts by mass Ethyl acetate 70 parts by mass

(Example 3) The hologram transfer foil 10 of Example 3 is obtained in the same manner as in Example 1 except that the ionizing radiation curable resin composition described below is used as the ionizing radiation curable resin composition of the hologram layer 15. It was.
・ <Ionizing radiation curable resin composition of hologram layer>
"Ionizing radiation curable resin composition M" 24 parts by weight Methacrylate oligomer (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 Polyethylene wax (average particle size 2.0 μm) 0.3 part by weight Photopolymerization initiator (Ciba, trade name Irgacure 184) 0.9 part by weight Ethyl acetate 70 part by weight

(Comparative Example 1) A hologram transfer foil of Comparative Example 1 was obtained in the same manner as in Example 1 except that the following ionizing radiation curable resin composition was used as the ionizing radiation curable resin composition of the hologram layer 15. .
・ <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 mass of reactive silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-2445) 2 parts by weight Photopolymerization initiator (Ciba, trade name Irgacure 907) 0.9 parts by weight Ethyl acetate 70 parts by weight

(Comparative Example 2) A hologram transfer foil of Comparative Example 2 was obtained in the same manner as in Example 1 except that the following ionizing radiation curable resin composition was used as the ionizing radiation curable resin composition of the hologram layer 15. .
・ <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 mass of reactive silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-2445) 2 parts by mass Polyethylene wax (average particle size 2.0 μm) 5 parts by mass Photopolymerization initiator (Ciba, trade name Irgacure 907) 0.9 parts by mass Ethyl acetate 70 parts by mass

(Examples 4 to 6) <Injection molding> The hologram transfer foils 10 of Examples 1 to 3 and Comparative Example 1 are inserted into an automatic foil feeder of an injection molding apparatus so that the adhesive layer surface is on the molding resin side (insert). Then, Sumipex STH-55 (manufactured by Sumitomo Chemical Co., Ltd., trade name of acrylic resin) was injection molded under normal conditions of a melting temperature of 250 ° C. and a mold temperature of 80 ° C. After cooling, the mold was released, the substrate 11 was peeled off, and the molded article with holograms using the hologram transfer foils of Examples 4 to 6 and Comparative Example 2 was obtained.
The injection molding was continuously performed with a molding cycle of 12 seconds. The obtained molded product was a three-dimensional shape (a member of a CD player having a diameter of 150 mm with a 5 mm border on the periphery and a central portion raised to a spherical shape).

  Comparative Example 3 A molded article with a hologram using the hologram transfer foil of Comparative Example 2 was obtained in the same manner as in Examples 4 to 6 except that the hologram transfer foil 10 of Comparative Example 1 was used.

  (Evaluation) In any of the molded products of Examples 4 to 6, the hologram transfer foil 10 followed the spherical portion and the edge portion, and the hologram was transferred to the acrylic resin surface. The hologram was not whitened by the heat of injection molding, had good followability to the spherical surface portion, was free of cracks and whitening, and was transferred to a three-dimensional surface with excellent design. However, Comparative Example 3 had poor peelability and was difficult to peel off, and burrs were generated during transfer, and transfer could not be performed normally. In addition, since the hologram transfer foil 10 of Comparative Example 2 had poor hologram moldability and no optical diffraction effect was obtained, injection molding was not performed.

The hologram layers before curing in 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 breaking elongation of the hologram layer 15 was 31% in Example 1, 31% in Example 2, and 505% in Example 3. The heat resistance of the hologram transfer foils 10 of Examples 1 to 3 was 170 ° C. in Example 1, 170 ° C. in Example 2, and 150 ° C. in Example 3.
Furthermore, when the pencil hardness test of the 1st hard-coat layer 15 surface of Examples 1-3 was measured based on JIS-K-5400, all have hardness of 2H or more. The scratch strength of the first hard coat layer 15 surface of No. 3 was 200 g or more of sapphire and had sufficient durability. However, in Comparative Example 1, the scratch strength was poor and the durability was not sufficient.

It is sectional drawing of the hologram transfer foil which shows one Example of this invention. It is the transferred material transferred using the hologram transfer foil of the present invention.

Explanation of symbols

10: Hard coat layer transfer foil 11: Base material 13: Release layer 15: Hologram layer 17: Reflective layer 19: Adhesive layer 21: Ultraviolet absorption layer 100: Medium 101: Support body 103: Image receiving layer 105: Image

Claims (2)

In a hologram transfer foil comprising a substrate and a release layer, a hologram layer, a reflective layer and an adhesive layer provided on one surface of the substrate,
The release layer is a melamine resin;
The hologram layer is a cured product of an ionizing radiation curable resin and a reactive silicone, and a polyethylene wax seen including,
The ionizing radiation curable resin is (1) an isocyanate having three or more isocyanate groups in the molecule, (2) a polyfunctional (meta) having at least one hydroxyl group and at least two (meth) acryloyloxy groups in the molecule. ) Acrylates, or (3) a urethane (meth) acrylate oligomer that is a reaction product of polyhydric alcohols having at least two hydroxyl groups in the molecule,
The content of polyethylene wax in the hologram layer is based on mass, ionizing radiation curable resin: polyethylene wax = 100: 0.01-10,
The hologram layer is (1) the coating film before ionizing radiation curing is finger-dried, (2) the elongation at break at 23 ° C. after curing with ionizing radiation is 5% or more, and (3) the substrate and the mold release In a hologram transfer foil state provided with a layer, a hologram layer, and a reflective layer, it has heat resistance that does not whiten even if left in an atmosphere at 150 ° C. for 1 hour,
A hologram transfer foil characterized in that a hologram can be transferred to a three-dimensional surface . A molded article with a hologram , wherein the hologram is transferred to a three-dimensional surface by an in-mold injection molding method using the hologram transfer foil according to claim 1.

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