JP2007011319A - Volume hologram transfer foil, and volume hologram laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a volume hologram transfer foil having excellent thermo-compression adhesion of a volume hologram layer comprising a light cation monomer and a photoradical monomer to any application member, in particular, a polyester resin card, and effective for prevention of illegal copying, and to provide a volume hologram multilayer structure formed by using the above transfer foil. <P>SOLUTION: The volume hologram transfer foil comprises a substrate (1) and a protective layer (2), a volume hologram layer (3), a primer layer (4) and a heat seal layer (5) comprising a thermoplastic resin, successively layered on the substrate (1), wherein the multilayer structure of the protective layer, the volume hologram layer, the primer layer and the heat seal layer is releasable from the substrate. The volume hologram layer is made of a photosensitive material comprising a cation polymerizable compound and a radical polymerizable compound. The primer layer is formed by using a water-based dispersion liquid of a mixture of a polyurethane adhesive and a curing agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hologram transfer foil that enables a volume hologram to be attached to an arbitrary adherend by hot pressure, and a volume hologram laminate obtained by using the transfer foil.

  The volume hologram is a means capable of recording information in the thickness direction and capable of recording / reproducing a three-dimensional image. Although the volume hologram manufacturing method itself is known, it is difficult to imitate the volume hologram because it requires precise work using an optical device for manufacturing, and it is used to prevent imitation of identification cards, bank cards, etc. ing. Furthermore, since the volume hologram is expressed by the interference color of light, it has an appearance that is difficult to obtain with other image forming means.

  A hologram pressure-sensitive adhesive label in which an adhesive layer is provided on a film-shaped volume hologram using the above characteristics of the volume hologram is known, and is applied to various adherends. For example, Patent Document 1 discloses a transfer hologram having a sequentially laminated structure of a base material, a volume hologram layer, and a heat seal layer. Further, from the viewpoint of preventing imitation, for example, Patent Document 2 discloses a transfer hologram having a structure in which a base material, a relief hologram, and a heat seal layer are sequentially laminated.

  However, in the former, the volume hologram layer is basically composed of a photocured resin layer, whereas the adherend is often different in material from, for example, high-quality paper, and bonded to both. It is difficult to select a heat sealant having excellent properties, and there is a problem that the object as an adherend is limited depending on the type of heat sealant. Therefore, there is a problem that the volume hologram layer is peeled off at any interface between the volume hologram layer and the heat seal layer or between the heat seal layer and the adherend and is easily forged. In the latter case, there is a problem that it is impossible to see through characters, images, and the like on the adherend.

Further, from the viewpoint of preventing counterfeiting, it is necessary to have excellent adhesion between the volume hologram layer and the adherend. From the viewpoint of improving the adhesion between the volume hologram layer and the adherend, for example, Patent Document 3 Discloses that a volume hologram layer and an adherend are bonded via a plurality of heat seal layers, and examples of the adherend include a polyvinyl chloride resin and a polyester resin sheet. However, when a polyvinyl chloride sheet is used, environmental problems such as generation of dioxins during incineration disposal occur, and in recent years, the use of a polyester resin sheet as an adherend is increasing. Is weaker than the polyvinyl chloride resin card, and the volume hologram layer, particularly the volume hologram layer composed of a photocationic monomer and a photoradical monomer, is insufficient, which is a problem from the viewpoint of preventing counterfeiting. It may become. In addition, it is disadvantageous in production with a plurality of heat seal layers, and it is desirable to bond the volume hologram layer and the adherend via a single heat seal layer, particularly when a polyester resin sheet is used as the adherend. Development of a heat seal layer is required.
JP-A 63-284586 Japanese Patent No. 2934281 JP 2002-358018 A

The present invention is excellent in heat-pressure adhesion between a volume hologram layer and an arbitrary adherend, particularly a polyester resin card, and the volume hologram layer is made of a volume hologram photosensitive material comprising a cationic polymerizable compound and a radical polymerizable compound. Even if formed, it is an object to provide a volume hologram transfer foil that is excellent in heat-pressure adhesion with an adherend and is effective in preventing forgery and a volume hologram laminate formed using the transfer foil.

  In the hologram transfer foil of the present invention, a protective layer, a volume hologram layer, a primer layer, and a heat seal layer made of a thermoplastic resin are sequentially laminated on a substrate, and the protective layer, volume hologram layer, primer layer, In a volume hologram transfer foil in which sequential laminates of heat seal layers are peelably laminated, the volume hologram layer is sensitive to light of a cationic polymerizable compound, radical polymerizable compound, and light of a specific wavelength, and polymerizes the radical polymerizable compound. From a photosensitive material comprising a radical polymerization initiator system and a photocationic polymerization initiator system that is low-sensitivity to light of the above specific wavelength and is sensitive to light of another wavelength to polymerize a cationically polymerizable compound. And the primer layer is a mixture of a polyurethane adhesive and a curing agent, and an aqueous dispersion of the mixture is used. Characterized in that it is intended to be formed in.

  The heat seal layer made of a thermoplastic resin is made of a polyester resin having a glass transition temperature of −10 ° C. to −30 ° C.

  The heat seal layer made of a thermoplastic resin is made of a polyester resin having a number average molecular weight of 18,000 to 80,000.

  A heat seal layer made of a thermoplastic resin contains fine particles.

  A release film is further provided on the heat seal layer.

  The volume hologram laminate of the present invention is a volume hologram laminate in which a heat seal layer made of a thermoplastic resin, a primer layer, a volume hologram layer, and a protective layer are sequentially laminated on an adherend, and the volume hologram layer is cationically polymerizable. Compounds, radical polymerizable compounds, photo radical polymerization initiator systems that polymerize radical polymerizable compounds by being exposed to light of a specific wavelength, and light of a different wavelength that is low in sensitivity to light of the specific wavelength A volume hologram recording layer comprising a photosensitive material comprising a photocationic polymerization initiator system that is photosensitized to polymerize a cationically polymerizable compound, and the primer layer is a mixture of a polyurethane-based adhesive and a curing agent, It is formed using an aqueous dispersion of a mixture.

  The adherend is a polyester resin card.

  The present invention is excellent in heat-pressure adhesion between a volume hologram layer, particularly a volume hologram layer comprising a cationic polymerizable compound and a radical polymerizable compound, and an arbitrary adherend, particularly a polyester resin card. After transferring the volume hologram layer onto the adherend using a transfer foil to form a volume hologram laminate, the volume hologram layer and the adherend are destroyed even if the volume hologram layer is peeled off from the adherend. And a volume hologram transfer foil and a volume hologram laminate capable of preventing forgery.

  FIG. 1 is a diagram showing a cross section of an example of the hologram transfer foil of the present invention, in which 1 is a substrate, 2 is a protective layer, 3 is a volume hologram layer, 4 is a primer layer, and 5 is a heat seal layer. FIG. 2 is a view showing a cross section of another example of the hologram transfer foil of the present invention, in which 6 denotes a release film, and the same reference numerals as those in FIG. 1 denote the same contents. FIG. 3 is a view showing a cross section of an example of a volume hologram laminate obtained by using the hologram transfer foil of the present invention, in which 7 is an adherend, and the same reference numerals as those in FIG. 1 denote the same contents. .

  The volume hologram layer is obtained by recording the interference light between the object light and the reference light on a photosensitive material sufficiently thicker than the interval between the interference fringes, and the three-dimensional structure of the object is recorded as it is. In order to form the volume hologram layer, the interference light between the object beam and the reference beam is directly recorded on the laminate of the volume hologram forming material on the support film, or the volume hologram master is used. It is obtained by duplication by close contact exposure, and industrially uses the latter method. As a support film (not shown) for applying the volume hologram forming material, a polyethylene terephthalate film (common name: PET film) having a thickness of 1 μm to 1 mm, preferably 10 μm to 100 μm, a polyethylene film, a polypropylene film, a poly A vinyl chloride film, an acrylic film, a triacetyl cellulose film, a cellulose acetate butyrate film, or the like is used. As the support film, it is desirable to use a film having high transparency and high smoothness.

The photosensitive material for forming a volume hologram layer in the present invention includes a cationic polymerizable compound, a radical polymerizable compound, a photo radical polymerization initiator system that polymerizes a radical polymerizable compound by exposure to light of a specific wavelength, and the above specific wavelength. It has a low photosensitivity to light, and consists of a photocationic polymerization initiator system that polymerizes a cationically polymerizable compound in response to light of another wavelength.

  This photosensitive material is applied on a support film, and then irradiated with light such as laser light that is photosensitized by a photo radical polymerization initiator system, and then the light such as laser light that is exposed to a photo cationic polymerization initiator system. Hologram recording is performed by irradiating light of another wavelength. After the radical polymerizable compound is polymerized by irradiation with light such as laser light (hereinafter referred to as first exposure), the cationic polymerizable compound is converted into a photocation in the composition by the subsequent overall exposure (hereinafter referred to as post exposure). Cationic polymerization is performed by Bronsted acid or Lewis acid generated by decomposing the polymerization initiator system.

As the cationic polymerizable compound, a liquid compound at room temperature is used so that the polymerization of the radical polymerizable compound is carried out in a composition having a relatively low viscosity throughout. Examples of such cationically polymerizable compounds include diglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether. And resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and phenyl glycidyl ether.

Moreover, the radically polymerizable compound preferably has at least one ethylenically unsaturated double bond in the molecule. Further, the average refractive index of the radical polymerizable compound is larger than that of the cationic polymerizable compound, preferably 0.02 or more, and if it is smaller, the refractive index modulation becomes insufficient, which is not preferable. Examples of the radical polymerizable compound include acrylamide, methacrylamide, styrene, 2-bromostyrene, phenyl acrylate, 2-phenoxyethyl acrylate, 2,3-naphthalenedicarboxylic acid (acryloxyethyl) monoester, methylphenoxyethyl acrylate, and nonyl. Examples thereof include phenoxyethyl acrylate and β-acryloxyethyl hydrogen phthalate.

The radical photopolymerization initiator system may be any initiator system that generates active radicals by the first exposure for producing a hologram, and the active radicals polymerize radical polymerizable compounds, and generally absorbs light. These sensitizers and active radical generating compounds or acid generating compounds may be used in combination. As the sensitizer in the radical photopolymerization initiator system, a colored compound such as a dye is often used to absorb visible laser light, but a cyanine dye is preferable when a colorless transparent hologram is used. Since cyanine dyes are generally easily decomposed by light, the dyes in the hologram are decomposed and absorbed in the visible range by being left exposed for several hours to several days under post-exposure or indoor light or sunlight in the present invention. A colorless and transparent hologram is obtained.

Specific examples of the cyanine dye include anhydro-3,3′-dicarboxymethyl-9-
Ethyl-2,2′thiacarbocyanine betaine, anhydro-3-carboxymethyl-3 ′, 9-diethyl-2,2′thiacarbocyanine betaine, 3,3 ′, 9-triethyl-2,
Examples include 2'-thiacarbocyanine / iodine salt, 3,9-diethyl-3'-carboxymethyl-2,2'-thiacarbocyanine / iodine salt, and the like.

Examples of the active radical generating compound that may be used in combination with a cyanine dye include diaryliodonium salts and 2,4,6-substituted-1,3,5-triazines. The use of diaryliodonium salts is particularly preferred when high photosensitivity is required. Specific examples of the diaryl iodonium salts include diphenyl iodonium, 4,4 ′
-Dichlorodiphenyliodonium, 4,4'-dimethoxydiphenyliodonium, etc. are exemplified, and specific examples of 2,4,6-substituted-1,3,5-triazines include 2-methyl-4,6- Examples thereof include bis (trichloromethyl) -1,3,5-triazine and 2,4,6-tris (trichloromethyl) -1,3,5-triazine.

  The cationic photopolymerization initiator system has low photosensitivity for the first exposure, irradiates light having a wavelength different from that of the first exposure, and then generates Bronsted acid or Lewis acid upon exposure to light. An initiator system for polymerizing the polymerizable compound may be used, and those that do not polymerize the cationic polymerizable compound during the first exposure are particularly preferable. Examples of the cationic photopolymerization initiator system include diaryliodonium salts, triarylsulfonium salts, iron allene complexes, and the like. Preferable diaryl iodonium salts include iodonium tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and the like shown in the photoradical polymerization initiator system. Preferable triarylsulfonium salts include triphenylsulfonium, 4-tertiarybutyltriphenylsulfonium, and the like.

  The photosensitive composition preferably contains inorganic fine particles or organic resin fine particles in order to improve the foil cutting property when the volume hologram layer is formed, and defects may be intentionally formed in the volume hologram layer. The volume hologram layer can be made to have good foil breakability.

Examples of the organic resin fine particles include low density polyethylene, high density polyethylene, polypropylene, (meth) acrylic resin, polyvinyl chloride, polyamide, polyimide, polycarbonate, epoxy resin, urethane resin and copolymers thereof, and inorganic fine particles. Silica, mica, talc, clay, graphite, calcium carbonate, alumina, aluminum hydroxide, ferrite, china clay, kaolin, titanium dioxide, glass flakes, asbestos, wax stone powder, silica stone powder, barium sulfate, sherben, chamotte, titania Inorganic fine particles such as these are exemplified, and one kind or a mixture of two or more kinds of these fine particles are exemplified. Among these, fluorine-containing resin fine particles and titania fine particles in which part or all of hydrogen in the skeleton or side chain in the resin is substituted with fluorine atoms are preferable. Fluorine-containing resin fine particles are preferable because they have a small friction coefficient and thus have little interaction with other components contained in the volume hologram layer. In addition, as the fluorine-containing resin fine particles, those obtained by treating the surface of the organic resin fine particles exemplified above with a fluorine-based compound can be used, for example, a fluorine-based compound-treated product of (meth) acrylic ester resin fine particles. preferable. Further, fluorine-containing acrylic esters described in JP-A-5-194322, fluorine-containing (meth) acrylic compounds described in JP-A-9-104655, and fluorine-containing polyfunctional (meth) acrylic compounds described in JP-A-2001-72646. Polymers using one or more of the fluorine monomers exemplified in the above, or copolymers of these monomers and other fluorine-containing compounds having at least one ethylenically unsaturated bond in one molecule, JP-A-6-73137 And fluorine-containing (meth) acrylic acid ester copolymers described in JP-A No. 5-194668, and one or more mixed fine particles are exemplified.

  The inorganic fine particles and organic resin fine particles have an average particle size of 100 nm to 600 nm, preferably 150 nm to 500 nm, particularly preferably 200 nm to 500 nm, and have a particle size smaller than the wavelength of the laser beam used for image recording on the volume hologram layer. It is preferable. An excessively large particle size is not preferable because it may adversely affect volume hologram recording. The average particle size of the fine particles is measured by a laser method. The average particle size, particle size distribution, etc. are obtained by thinning and calculating the scattered light obtained by applying a laser beam to a dispersion in which the particles are dispersed in a solvent. This is a value measured using a particle size analyzer “Microtrac UPA Model-9230 manufactured by Leeds & Northrup Co., Ltd.”.

  Inorganic fine particles and organic resin fine particles may be contained in the volume hologram layer in an amount of 1% by mass to 30% by mass, preferably 5% by mass to 20% by mass. If the amount is large, strength and transparency are maintained when the volume hologram layer is formed. It becomes difficult.

  Moreover, you may use together binder resin, a thermal-polymerization inhibitor, a silane coupling agent, a plasticizer, a coloring agent, etc. to the photosensitive composition as needed. The binder resin is used to improve the film formability and film thickness uniformity of the composition before hologram formation, and to stabilize interference fringes formed by polymerization by irradiation with light such as laser light until post-exposure. Used to make it exist. The binder resin only needs to be compatible with the cationic polymerizable compound or the radical polymerizable composition, and specific examples thereof include chlorinated polyethylene, polymethyl methacrylate, methyl methacrylate, and other (meth) acrylic acid alkyl esters. And a copolymer of vinyl chloride and acrylonitrile, polyvinyl acetate, and the like. The binder resin may have reactivity such as a cation polymerizable group in its side chain or main chain.

  In the composition of the photosensitive composition, the cationic polymerizable compound is 2 to 70% by mass, preferably 10 to 50% by mass, and the radical polymerizable compound is 30 to 90% by mass, preferably 40%, based on the total weight of the composition. -70% by mass, photo radical polymerization initiator system is 0.3-8% by mass, preferably 1-5% by mass, and photocationic polymerization initiator system is 0.3-8% by mass, preferably 1-5% by mass. It is good to do.

  The photosensitive composition is composed of essential components and optional components as they are, or as necessary, ketone solvents such as methyl ethyl ketone, ester solvents such as ethyl acetate, aromatic solvents such as toluene and xylene, and cellosolves such as methyl cellosolve. It is prepared by blending with a solvent, an alcohol solvent such as methanol, an ether solvent such as tetrahydrofuran or dioxane, or a halogen solvent such as dichloromethane or chloroform and mixing in a cool and dark place using, for example, a high-speed stirrer.

  If the recording layer made of the photosensitive composition is a coating liquid having a solid content of 15 to 50% by mass, and the support film is in a state of a single wafer (each sheet), a bar coat, The coating is formed by spin coating or dipping. Further, if the support film is applied in a roll-like long state, it may be applied by gravure coating, roll coating, die coating, comma coating, or the like. The volume hologram forming layer is solidified by means of drying or curing according to the coating solution. The volume hologram forming material layer thus obtained has a dry film thickness of 1 μm to 50 μm, preferably 5 μm to 20 μm, and a protective film is attached as necessary.

Volume hologram recording on the volume hologram forming material layer uses light such as laser light (for example, a wavelength of 300 to 1200 nm) by an ordinary holographic exposure apparatus to polymerize a radical polymerizable compound and record interference fringes therein. The At this stage, a diffracted light by the recorded interference fringes is obtained and a hologram is formed. In order to further polymerize the unreacted cationic polymerizable compound, the photocation polymerization initiator system is used as a post-exposure. A hologram may be formed by irradiating the entire surface with photosensitive light (for example, a wavelength of 200 to 700 nm). In addition, the diffraction efficiency, the peak wavelength of the diffracted light, the half width, etc. can be changed by treating the recording layer with heat or infrared rays before post-exposure. The volume hologram transfer foil of the present invention is superior in heat resistance as compared with a photosensitive material (for example, Example of Patent Document 3) using only a radically polymerizable monomer as a polymerizable monomer, and is affected by hot pressure transfer on hologram recording. Can be reduced.
The volume hologram layer in the present invention has a glass transition temperature of 50 ° C. or higher in a state where hologram recording is performed, ultraviolet irradiation and heat treatment are performed, and the upper limit is not particularly limited. Thereby, it is possible to prevent the hologram recording from being affected during the transfer.
Further, the breaking strength in the above state is 0.01 to 5 kgf / mm ² , preferably 0.03 to 3 kgf / mm ² , and the breaking elongation is 0.01 to 30%, preferably 0.1 to Since it is 10% and is brittle, when the volume hologram layer is peeled off, the volume hologram layer itself is broken.
The glass transition temperature of the volume hologram layer depends on the following measurement conditions.
Measuring device: Solid viscoelasticity analyzer RSA-II (manufactured by Rheometrics)
Measurement mode: Film tension measurement frequency: 6.28 rad / s
(1) A sample is set on a film tensile test jig.
(2) The temperature dependence at a frequency of 6.28 rad / s is measured in an arbitrary temperature region, the peak temperature of tan δ is determined, and this is taken as the glass transition temperature.
Further, the breaking strength and breaking elongation of the volume hologram layer are measured under the following conditions by “INSTRON5565” universal material testing machine manufactured by INSTRON in accordance with JIS K7127-1989.
Measurement atmosphere: 25 ° C, RH 50%
Test piece: 25 mm width Tensile speed: 2 mm / min

  Next, the protective layer 2 provided on one surface of the volume hologram layer will be described with reference to FIGS. The protective layer can be peeled off from the base material 1, using a methacrylic resin such as polymethyl methacrylate as a main binder, and various additives for imparting hard coat properties, printability, slip properties and the like. Contains appropriately. Other examples of the binder include polyacrylic ester resin, polyvinyl chloride resin, cellulose resin, silicone resin, chlorinated rubber, and casein. Further, as an additive, one or a mixture of two or more kinds of surfactants, waxes, and metal compounds is added to form an interface having a predetermined refractive index difference that reflects the reproduction wavelength light of the volume hologram. The refractive index is adjusted. The peelable protective layer is preferably formed by inking the above composition with an organic solvent and applied onto a substrate by a method such as coating, and the thickness is preferably 0.1 μm to 3 μm in view of surface protection.

The peelable protective layer may be formed using an ionizing radiation curable resin. The ionizing radiation curable resin includes an electron beam curable resin or an ultraviolet curable resin, except that the latter ultraviolet curable resin contains a photopolymerization initiator and a sensitizer. The components are the same as those of the resin. An ionizing radiation curable resin is generally a monomer, oligomer or polymer having a radically polymerizable active group in its structure as a film-forming component, and a (meth) acrylic acid ester as a monomer. Examples of the derivatives, etc., and oligomers and polymers include urethane acrylate and polyester acrylate. In order to obtain an ultraviolet curable resin, a photopolymerization initiator such as a monomer having a radical polymerizable active group as described above, acetophenones, benzophenone, Michler benzoylbenzoate, α-aminoxime ester, tetramethylthiuram monosulfide, thioxanthone In addition, a composition to which n-butylamine, triethylamine, tri-n-butylphosphine or the like is added as a photosensitizer may be used. As a curing method, for example, in the case of electron beam irradiation, an electron beam accelerator such as a Cockloft Walton type is used, and an electron beam of 50 to 1000 KeV, preferably 100 to 300 KeV is applied to 0.1 to 100 Mrad. , Preferably 1-10 Mrad. Performed by irradiating, In the case of ultraviolet irradiation, 0.1~10000mJ / cm ² ultraviolet light emitted from a light source such as an ultra-high pressure mercury lamp, and preferably carried out by irradiating 10~1000mJ / cm ² Good.

  Next, the substrate 1 is to be peeled after the volume hologram transfer foil is transferred to the adherend, but the laminated surface is subjected to a release treatment or the releasability in the peelable protective layer. It is good to peel off using. Base materials include polyethylene film, polypropylene film, polyfluorinated ethylene film, polyvinylidene fluoride film, polyvinyl chloride film, polyvinylidene chloride film, ethylene-vinyl alcohol film, polyvinyl alcohol film, polymethyl methacrylate film, poly Examples include ether sulfone film, polyether ether ketone film, polyamide film, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer film, polyethylene terephthalate film, polyimide film, and the like. The film thickness is 2 μm to 200 μm, preferably 10 μm to 50 μm. The base material may be a transparent film or an opaque film in which a concealing pigment such as carbon black is kneaded. This makes it possible to protect the hologram layer until use and to prevent the base material from being forgotten to be peeled off.

  Next, the primer layer 4 laminated on the other surface of the volume hologram layer will be described. The primer layer 4 heat-adheres a volume hologram layer and a heat seal layer made of a thermoplastic resin, which will be described later, and is a mixture of a water-dispersed polyurethane adhesive and a curing agent, and an aqueous dispersion of the mixture The coating formation layer has a low-temperature softening property and a heat sealing property.

  Examples of the water dispersion type polyurethane adhesive include “Takelac W-2501” manufactured by Mitsui Takeda Chemical Co., Ltd. and “Evaphanol HO-30C” manufactured by Nikka Chemical Co., Ltd. Examples of the curing agent include water-dispersed polyisocyanate “Takenate WD-730” manufactured by Mitsui Takeda Chemical Co., Ltd., “NK Assist IS-100N” manufactured by Nikka Chemical. “Takenate WD-730” is a polyisocyanate compound provided with a nonionic hydrophilic group, and is used in combination with a water-dispersed polyurethane adhesive to form a crosslinked structure. Excellent adhesion.

  The blending ratio (mass ratio) of the polyurethane adhesive and the curing agent is preferably such that the OH group in the polyurethane resin and the NCO group ratio of the polyisocyanate compound (NCO / OH) = 1.0 to 2.0, An aqueous dispersion of a mixture of polyurethane resin particles and a polyisocyanate compound may be used, and may be applied and formed on the volume hologram layer with a dry film thickness of 0.1 μm to 10 μm by a bar coater, applicator, gravure coater, or the like.

  When a water-based solvent dispersion containing water as a main component is used as the primer layer, the residual monomer from the volume hologram layer can be prevented from moving to the heat seal layer, and the influence on volume hologram recording can be suppressed. . In addition, by using a highly crystalline resin, it can be melted quickly at the time of hot-pressure transfer, and can be excellent in transferability. Patent Document 3 describes an organic solvent-based polyurethane resin as an adhesive, but as is apparent from Comparative Example 4 to be described later, the adhesion to the volume hologram layer is poor and there is a problem in transferability. .

  Next, the heat seal layer 5 is a thermoplastic resin having heat seal properties, and as a resin capable of forming a heat seal layer using an organic solvent, ethylene-vinyl acetate copolymer resin, polyamide resin, polyester Resin, polyethylene resin, ethylene-isobutyl acrylate copolymer resin, butyral resin, polyvinyl acetate resin, vinyl chloride vinyl acetate copolymer resin, cellulose derivative, acrylic resin such as polymethyl methacrylate resin, polyvinyl ether resin, polyurethane resin, polycarbonate resin Examples thereof include polypropylene elastomers, epoxy resins, phenol resins, thermoplastic elastomers such as SBS, SIS, SEBS, and SEPS, or reactive hot melt resins. Examples of the organic solvent include toluene, methyl ethyl ketone, and the like. The organic solvent may be directly applied and formed on the primer layer laminated on the volume hologram layer with a dry film thickness of 2 to 10 μm by a comma coater, a die coater, a gravure coater or the like.

  In addition, an aqueous dispersion of an aqueous dispersion type thermoplastic resin may be applied and formed. Examples of the aqueous dispersion type thermoplastic resin include vinyl acetate copolymer polyolefin, ethylene vinyl acetate copolymer resin, and ethylene methyl methacrylate (EMMA). A copolymer resin, a polyester resin, etc. are illustrated and it is good to apply and form directly on a primer layer like an organic solvent type.

When the adherend is a polyester resin card, a heat seal layer is preferably formed of a polyester resin, and the adhesiveness is excellent due to the similarity in structure. The polyester resin has the desired physical properties described above by a conventional method using an esterification catalyst or the like in an inert gas atmosphere and at least one of dicarboxylic acids or their anhydrides or alkyl esterified products and at least one of diols. Is obtained by condensation polymerization so that is obtained. Examples of the organic solvent-type polyester resin and water-dispersed polyester resin include “Byron 550, Tg: −15 ° C., number average molecular weight 48,284”, “Byron BX1001, Tg: −18 ° C., number average molecular weight, manufactured by TOYOBO. 28,678 ”,“ Byron UR8700, Tg: −22 ° C., number average molecular weight 29,208 ”,“ Byronal MD1985, melting point: 110 ° C., Tg: −20 ° C., number average molecular weight 25,248 ”,“ Byronal MD 1930, melting point: 110 ° C., Tg: −10 ° C., number average molecular weight 18,826 ”and the like are exemplified. The above-mentioned “vironal” is composed of water-dispersed high molecular weight copolymerized polyester resin particles having hydrophilic functional groups and water containing a small amount of an organic solvent, and is excellent in water dispersibility of the resin particles, and has a crystalline melting point. And has excellent PET adhesiveness.
The number average molecular weight of the commercially available polyester resin is measured as follows.
(1) “Byron 550” and “Byron BX1001” in sheet form
A sample was dissolved in THF to prepare a solution having a concentration of 0.5 wt%. For the GPC measurement, a liquid chromatogram (HLC-8020 manufactured by Tosoh Corporation) was used. GPC was measured using THF, GPC column (TSKgel G2000H × L + G3000H × L + G5000H × L) as an eluent, a galam temperature of 40 ° C., a flow rate of 1 ml / min, and RI (differential refractive index detector) as a detector.
(2) Solvent type “Byron UR8700”
The sample was vacuum dried at 25 ° C. to obtain a dried product. The obtained dried product was dissolved in NMP to prepare a solution having a concentration of 0.5 wt%. For the GPC measurement, a liquid chromatogram (manufactured by Tosoh Corporation, HLC-8120GPC) was used. An eluent prepared by dissolving LiBr in NMP to a concentration of 1 mM, GPC column (manufactured by Tosoh Corporation, TSKgel α-M × 2), column temperature 40 ° C., flow rate 0.5 ml / min, RI as a detector GPC was measured using a differential refractive index detector.
(3) Water-based ink types “Vaironal MD1985” and “Vaironal MD1930”
The sample was treated for 5 hours at 90,000 rpm in an ultracentrifuge, divided into a supernatant and a precipitate, the precipitate was dissolved in NMP, and a solution having a concentration of 0.5 wt% was prepared. For the GPC measurement, a liquid chromatogram (manufactured by Tosoh Corporation, HLC-8120GPC) was used. A buffer solution prepared by dissolving LiBr and phosphoric acid in NMP so as to have a concentration of 50 mM as an eluent (a buffer solution was used to prevent adsorption of a substance having a large polarity on the column), GPC column ( GPC was measured using Tosoh, TSKgel α-M × 2), column temperature 40 ° C., flow rate 0.5 ml / min, and RI (differential refractive index detector) as a detector.

  The glass transition temperature (Tg) of the polyester resin is −10 ° C. or lower, preferably −10 ° C. to −30 ° C. If the Tg of the polyester resin is too high, a high temperature and a high pressure are required for transferring the pressure to the adherend, and this is not preferable because it may affect the discoloration of the hologram.

  The polyester resin may be an amorphous polyester resin having the above glass transition temperature, and has the above glass transition temperature and a melting point of 80 ° C to 200 ° C, preferably 100 ° C to 150 ° C. A crystalline polyester resin may be used. When a crystalline polyester resin is used, it has a characteristic of being melted quickly, and can be easily melted at a temperature equal to or higher than the melting point and excellent in transferability upon hot-pressure transfer onto an adherend. If the melting point of the crystalline polyester resin is too high, not only the temperature is too high during the hot-pressure transfer to the adherend, but also the hologram recording is affected. On the other hand, if the temperature is too low, tackiness is exhibited depending on the environmental temperature, and there is a problem of blocking during the production of the volume hologram transfer foil.

  The number average molecular weight (Mn) of the polyester resin is 18,000-80,000, preferably 20,000-40,000. When the number average molecular weight is less than 18,000, there are problems such as a decrease in adhesion performance. On the other hand, if it exceeds 80,000, the ink viscosity increases, and there is a problem that troubles occur in actual coating properties.

  The melting point and Tg of the crystalline polyester resin, and the Tg of the amorphous polyester resin can be measured using, for example, “Automatic Differential Scanning Calorimeter DSC-60A” manufactured by Shimadzu Corporation. The molecular weight can be measured by GPC (gel permeation chromatograph) in terms of polystyrene.

  For the purpose of imparting foil breakability and blocking resistance, the above-described inorganic fine particles and resin fine particles may be added to the heat seal layer. As the inorganic fine particles, silica fine particles, alumina fine particles, ZnO fine particles and the like are preferable, and silica fine particles {SiOx (1.5 ≦ x ≦ 2.0, refractive index 1.35 to 1.48)} are preferable. The particle diameter of the fine particles is preferably 0.1 μm to 10 μm. The particle diameter of the fine particles is preferably equal to or less than the film thickness of the heat seal layer. If the particle diameter is larger than the film thickness, the thermal transfer property is lowered, which is not preferable. The blending ratio is polyester resin: fine particles (mass ratio) = 75: 1 to 75:12, preferably 75: 3 to 75: 5. If the addition ratio of the fine particles is higher than the above-mentioned mixing ratio, even if thermal transfer is performed, the adhesion with the adherend is lowered, which is not preferable. The average particle diameter of the fine particles can be measured by a laser diffraction scattering method.

The heat seal layer is formed by dissolving or dispersing the heat seal layer forming material in water or a mixed solvent of water and alcohol, or an organic solvent such as toluene or methyl ethyl ketone, and on the volume hologram layer, a release film, or a temporary film. It is good to apply and form a dry film thickness of 2 to 10 μm on a support film by a comma coater, a die coater, a gravure coater or the like.

  Also, after forming the heat seal layer and the primer layer in this order on the temporary support film, the primer layer and the heat seal layer are simultaneously heat-pressure transferred from the primer layer side onto the volume hologram layer, and then the temporary support film is peeled off. Then, a primer layer and a heat seal layer may be laminated on the volume hologram layer.

  The heat seal layer may be a non-colored transparent layer made of a polyester resin or a mixture of polyester resin and inorganic fine particles, but a colorant layer colored with a heat seal layer / solvent-soluble dye or solvent-dispersed pigment from the volume hologram layer side. Or it is good also as a structure of the sequential laminated body of the metal thin film layer / heat-seal layer which reflects light. If a colorant layer or a metal thin film layer that reflects light is provided, the background color of the hologram image can be obtained, so that an image with excellent contrast can be obtained. In the case of a colorant layer colored with a solvent-soluble dye, a water-dispersed crystalline polyester resin is preferably used as the heat seal layer in contact with the volume hologram layer, and the volume hologram of the colorant component from the colorant layer is used. Transition to the layer can be prevented, and the influence on volume hologram recording can be suppressed. Moreover, there is an advantage that the use of the dye in the colorant layer is not limited.

  Next, the release film 6 is obtained by releasing a polyethylene terephthalate resin film, a polypropylene resin film, or the like with a fluorine-type release agent, a silicone-type release agent, or the like in addition to the release paper that is usually used. A releasable film may be used.

Next, the anti-counterfeiting property of the hologram transfer foil of the present invention will be described. In the hologram transfer foil of the present invention, a cation polymerizable compound and a radical are used when a volume hologram is to be peeled off from an adherend for the purpose of forgery after the hologram is transferred to the transfer subject (also referred to as an adherend). The adhesive force between the volume hologram layer made of a polymerizable compound, the primer layer, and the heat seal layer is strong, and the material of the volume hologram layer is destroyed so that the hologram image cannot be reproduced. In addition, when a polyester resin card is used as the adherend, a crystalline polyester resin as the heat seal layer is superior in adhesiveness between the volume hologram layer and the adherend, so that the volume hologram layer is surely destroyed upon peeling. be able to. In addition, when the adherend is a photograph or fine paper with a small material destructive force, if the volume hologram layer is peeled from the adherend for the purpose of counterfeiting, the adherend is destroyed and the counterfeiting is prevented. It may be one that can achieve the purpose.

Next, as an example of a method for producing the hologram transfer foil of the present invention,
(1) A step of recording a Lippmann hologram on a volume hologram layer after providing a volume hologram forming layer on a temporary carrier and laminating a protective film on the volume hologram layer;
(2) After recording the volume hologram, the step of heating at 50 to 100 ° C. for 1 to 20 minutes to peel off the protective film,
(3) After a protective layer forming layer is provided on a temporary carrier to form a transfer body, the protective layer forming layer is laminated on the volume hologram layer obtained in (2) from the protective layer forming layer side, and the recording on the volume hologram layer is affected. In order not to exist, the process of hot pressing at 50-100 degreeC using a heat roll,
(4) Step of fixing the volume hologram by irradiating the entire surface of the obtained laminate with ultraviolet rays using a high-pressure mercury lamp (5) After peeling the temporary carrier in the laminate, a primer layer and a heat seal layer are formed on the surface of the volume hologram layer. Apply the coating layer sequentially, or apply the heat seal layer and primer layer on the release film or temporary support film in this order, and then laminate the primer layer and heat seal layer on the volume hologram layer surface from the primer layer side. An example is a production method in which the steps of pressure transfer are sequentially performed.

  The obtained hologram transfer foil is 60 ° C. to 200 ° C., preferably 100 ° C. to 160 ° C. on the adherend described later after the release film is peeled off, and differs depending on the type of adherend. The volume hologram layer can be transferred onto the adherend by performing thermal pressure transfer in the range of 0.5 Mpa to 15 Mpa and peeling the substrate as necessary.

  Examples of the adherend include transparent or opaque materials such as glass and plastic. Examples of the plastic include a vinyl resin, an acrylic resin, a polystyrene resin, a polyester resin such as polyethylene terephthalate, and a polycarbonate resin. The plastic is particularly suitable for a card, sheet, or film made of a polyester resin. Examples of specific articles made of these materials include, for example, windows for transportation such as automobiles, railway vehicles, ships, and aircraft, observation windows, or doors. Or there are building windows, doors, slaughter windows, and light windows. Moreover, in the above transportation systems, the hologram transfer foil can be attached to the instruments provided in the driver's seat, the cockpit and other places, the transparent glass on the surface of the display, or the transparent plastic plate. The same display has various display parts in equipment such as electric appliances, watches, cameras, etc., and it is not necessarily colorless and transparent, and there are also black ones when they are not displayed. Transfer foil can be attached. Specifically, in addition to the above, calculators, portable personal computers, portable terminal devices, mobile phones, IC recorders, CD players, DVD players, MD players, video tape recorders, various audio devices, etc. This is a device having a display function. In these, when the hologram transfer foil has transparency, the hologram image of the volume hologram layer can be overlaid without disturbing the original display function of the device. In addition to these, luxury wristwatches, jewelry, precious metals, antiques, etc., or their cases, etc., display the fact that they are genuine products by taking advantage of the difficulty in manufacturing the volume hologram layer of the hologram transfer foil. Can also be applied. In this case, the object to be pasted may be transparent, but may be opaque.

  The hologram transfer foil may be affixed to a sheet such as an ID card, an examination card, a card such as an ID card, or a booklet such as a passport. It is suitable for use as a certificate indicating the grade or as a certificate of taking measures for it. In addition, in the past, for applications where a paper certificate is pasted and sealed, and the target article is transparent and substantially flat or has a quadratic curved surface, it can be replaced with a certificate in principle. Can be used. Further, the hologram transfer foil can be widely applied to articles having a part made of paper, synthetic paper, synthetic resin, metal film or sheet, glass plate, or the like. In addition, by utilizing the unique and three-dimensional characteristics of volume holograms, it can be used as magazines such as books and saddle-stitched weekly magazines, glass windows of automobiles, premium products, and the like.

  The hologram image of the volume hologram layer can be designed in accordance with the above-mentioned object, application, and purpose, and can freely include a symbol or a sentence expressing a necessary meaning. The hologram image itself can be obtained by calculating a hologram diffraction grating in addition to photographing a real object, or by using a two-dimensional or three-dimensional image data obtained from a digital image captured by a digital camera or computer graphics. It can be created by appropriate means.

Moreover, it is good to cut according to the shape of the object and its part to stick beforehand according to a use. Alternatively, when accompanied by a release film, by taking a cut in a portion other than the release film, take out individual labels of a predetermined shape from a hologram transfer foil of a large size or a wound shape, and paste them. It can be applied to subjects. In order to make a cut only in a portion other than the release film, the punching blade may be moved up and down by a stroke that leaves the thickness of the release film from the upper surface side of the hologram transfer foil. Alternatively, each layer other than the release film between adjacent hologram transfer foils may be removed while leaving each hologram transfer foil having a predetermined shape. In this case, perforations that allow separation of individual hologram transfer foils may be provided at the boundary of the release film.

Hereinafter, the present invention will be described with reference to examples.

Example 1
(First laminate having volume hologram forming material layer)
A PET film {Lumirror T60 (thickness: 50 μm): manufactured by Toray Industries, Inc.) is prepared, and a volume hologram forming material having the following composition / binder resin {methyl methacrylate / glycidyl methacrylate copolymer (copolymerization ratio (mass ratio) 90) / 10) Weight average molecular weight 50,000)} ... 30 parts by mass Bis (4-acryloxydiethoxyphenyl) methane 30 parts by mass 1,6-hexanediol diglycidyl ether 30 parts by mass Part ・ Radical radical polymerization initiator (also used as photocationic polymerization initiator) (diphenyliodonium hexafluoroantimonate) ・ ・ ・ 4 parts by mass ・ Sensitizer (3,9-diethyl-3'-carboxymethyl-2,2 ′ -Thiacarbocyanine iodine salt ・ ・ ・ 1 part by mass ・ Fine particles (“Fluon L170J, flat by Asahi Glass Co., Ltd.) The particle size 200nm)
A gravure coat is applied to a volume hologram forming material consisting of 40 parts by mass of a composition consisting of 5 parts by mass and 60 parts by mass of a mixed solvent of methyl ethyl ketone / methanol = 1/1 (mass ratio) so as to have a dry film thickness of 20 μm. And a surface release treatment PET film (“SP-PET” film thickness of 50 μm, manufactured by Tosero Co., Ltd.) was laminated on the coated surface to obtain a first laminate.

(Second laminate having protective layer)
PET film {Lumirror T60 (thickness: 50 μm): manufactured by Toray Industries, Inc.} is prepared, and the protective layer has the following composition: polymethyl methacrylate resin (molecular weight: 35,000), 97 parts by mass, polyethylene wax (molecular weight: 10, 000) 3 mass parts Solvent (methyl ethyl ketone / toluene = 1/1 (mass ratio)) 400 mass parts were obtained using a gravure coater to obtain a laminate having a protective layer with a dry film thickness of 1 μm.

(Volume hologram recording)
A Lippmann hologram was photographed and recorded on the first laminate obtained above using a laser beam having a wavelength of 532 nm. After recording, the laminate was heated in an atmosphere of 100 ° C. for 10 minutes, the surface release-treated PET film was peeled off, and the volume hologram layer was exposed.

  The second laminated body obtained above is overlaid from the protective layer side on the surface of the exposed volume hologram layer and passed between the nipped 80 ° C. heat roller pairs, and the PET film / volume hologram layer / protective layer / PET film After forming the laminate, the volume hologram was fixed by irradiating the entire surface with ultraviolet rays having an irradiation dose of 2500 mJ / cm 2 using a high-pressure mercury lamp.

(Primer layer coating)
After the PET film was peeled off from the laminate of the PET film / volume hologram layer / protective layer / PET film on which the volume hologram was fixed, the volume hologram layer was exposed, and on the surface of the volume hologram layer, the following composition / water dispersion Type polyurethane resin ("Takelac W2501" manufactured by Mitsui Takeda Chemical Co., Ltd.)
・ ・ ・ 100 parts by mass ・ Polyisocyanate curing agent (Takenate WD-730, manufactured by Mitsui Takeda Chemical Co., Ltd.)
A material composed of 5 parts by mass and ion-exchanged water ... 50 parts by mass was gravure coated to form a dry film thickness of 1 µm to form a primer layer.

(Coating of heat seal layer)
In the primer layer surface of the obtained primer layer / volume hologram layer / protective layer / PET film laminate, the following composition / polyester resin (byron 550, Tg: −15 ° C., number average molecular weight 48,284, manufactured by TOYOBO) 20 mass parts Solvent (methyl ethyl ketone / toluene = 1/1 (mass ratio)) 80 mass parts were applied by gravure coating so that the film thickness would be 3 μm after drying, and the volume hologram transfer of the present invention A foil was obtained.

(Example 2)
A volume hologram transfer foil of the present invention was obtained in the same manner as in Example 1 except that a material having the following composition was used for coating the primer layer.
・ Water-dispersed polyurethane resin (“Evaphanol HO-30C” manufactured by Nikka Chemical Co., Ltd.)
・ ・ ・ 100 parts by mass ・ Polyisocyanate curing agent (“NK Assist IS-100N” manufactured by Nikka Chemical Co., Ltd.)
... 7 parts by mass, ion-exchanged water ... 50 parts by mass (Example 3)
A volume hologram transfer foil of the present invention was obtained in the same manner as in Example 1 except that a material having the following composition was used for coating the heat seal layer.
・ Polyester resin (“BYRON UR8700, manufactured by TOYOBO, Tg: −22 ° C., number average molecular weight 29,208”) 30 mass parts Solvent (methyl ethyl ketone / toluene = 1/1 (mass ratio)) 70 mass parts Example 4
A volume hologram transfer foil of the present invention was obtained in the same manner as in Example 1 except that a material having the following composition was used for coating the heat seal layer.
-Polyester resin (TOYOBO "Vironal MD1930, melting point: 110 ° C, Tg: -10 ° C, number average molecular weight 18,826")-50 parts by mass-Solvent (water / isopropyl alcohol = 1/1 (mass ratio) 50 mass parts (Example 5)
A volume hologram transfer foil of the present invention was obtained in the same manner as in Example 1 except that a material having the following composition was used for coating the heat seal layer.
・ Polyester resin (“BYRONAL MD1985, manufactured by TOYOBO, melting point: 110 ° C., Tg: −20 ° C., number average molecular weight 25,248”) ・ 75 mass parts ・ silica fine particles (“Silicia 420” particle size 4 manufactured by Fuji Silysia) .1 μm)
12 parts by mass Solvent (water / isopropyl alcohol = 1/1 (mass ratio)) 250 parts by mass (Example 6)
(Third laminate consisting of primer layer / heat seal layer / release film)
A surface release treated PET film (“SP-PET” manufactured by Tosero Co., Ltd.) having a film thickness of 50 μm is prepared, and a composition comprising the following composition in the order of a heat seal layer on the release treatment surface and a primer layer thereon. The third layered product was obtained by coating so that the film thickness after drying was 4 μm for the heat seal layer and 1 μm for the primer layer.

(Composition of heat seal layer)
-Polyester resin (TOYOBO "Byron 550, Tg: -15 ° C, number average molecular weight 48,284")-20 parts by mass-Solvent (methyl ethyl ketone / toluene = 1/1 (mass ratio))-80 parts by mass (Composition of primer layer)
・ Water-dispersed polyurethane resin (Takelac W2501 manufactured by Mitsui Takeda Chemical Co., Ltd.)
・ ・ ・ 100 parts by mass ・ Polyisocyanate curing agent (Takenate WD-730, manufactured by Mitsui Takeda Chemical Co., Ltd.)
... 5 parts by mass / ion-exchanged water ... 50 parts by mass The PET film was peeled from the laminate of the PET film / volume hologram layer / protective layer / PET film on which the volume hologram prepared in Example 1 was fixed. After the volume hologram layer is exposed, the third laminate is laminated on the volume hologram layer surface from the primer layer side, and is passed between a pair of heated nips at 120 ° C., and the surface release-treated PET A volume hologram transfer foil of the present invention having a laminated structure of film / heat seal layer / primer layer / volume hologram layer / protective layer / PET film was obtained.

(Comparative Example 1)
A volume hologram transfer foil for comparison was obtained in the same manner as in Example 1 except that a material having the following composition was used for coating the primer layer.
・ Polyester resin (“TP-219, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Tg: 40 ° C., number average molecular weight 3,000”) ・ ・ 20 parts by mass ・ Solvent (methyl ethyl ketone / toluene = 1/1 (mass ratio)) 80 parts by mass (Comparative Example 2)
A comparative volume hologram transfer foil was obtained in the same manner as in Comparative Example 1 except that a material having the following composition was used for coating the heat seal layer.
・ Acrylic resin (“TS-413A” manufactured by Dainippon Ink & Chemicals, Inc.) ・ ・ 30 parts by mass ・ Solvent (methyl ethyl ketone / toluene = 1/1 (mass ratio)) ・ ・ 70 parts by mass (Comparative Example 3)
A volume hologram transfer foil for comparison was obtained in the same manner as in Example 1 except that a material having the following composition was used for coating the primer layer.
-Polyvinyl butyral resin ("S REC BL-1" manufactured by Sekisui Chemical Co., Ltd.)
20 mass parts Solvent (methyl ethyl ketone / toluene = 1/1 (mass ratio)) 80 mass parts (comparative example 4)
A volume hologram transfer foil for comparison was obtained in the same manner as in Example 1 except that a material having the following composition was used for coating the primer layer.
・ Organic solvent type polyurethane resin ("Takelac E-551T" manufactured by Mitsui Takeda Chemical Co., Ltd.)
・ ・ ・ 100 parts by mass ・ Polyisocyanate curing agent (Takenate D-140N manufactured by Mitsui Takeda Chemical Co., Ltd.)
... 30 parts by mass · Solvent (methyl ethyl ketone / toluene = 1/1 (mass ratio)) · · 100 parts by mass The volume hologram transfer foil obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was obtained at 140 ° C, On the adherend of polyvinyl chloride card, polyester resin card (PET-G card), coated paper ("Swing mat" 64.0 g / m @ 2 manufactured by Mitsubishi Paper Industries) under the conditions of 0.5 sec and 0.7 Mpa. Each was hot-pressed to transfer the volume hologram layer to the adherend by hot-pressure. In addition, the volume hologram transfer foil obtained in Example 6 peeled off the release film and thermally transferred.
(Evaluation of thermal transferability)
Table 1 shows the results of peeling the substrate from the protective layer immediately after lamination (after about 2 seconds) and confirming the transferability of the volume hologram layer. In the evaluation in Table 1, the mark “◯” indicates that the material is clearly transferred to the adherend, and the mark “×” indicates that thermal transfer is not performed.
(Evaluation of adhesion to adherend after transfer)
Also, after the transfer, cello tape (registered trademark, manufactured by Nichiban) was applied from above each protective layer, abruptly peeled off, and the results of a test for evaluating the adhesion between the adherend and the volume hologram layer were also shown in Table 1. Show. In the evaluation in Table 1, the double circle mark was subjected to the tape adhesion test 5 times, and in all cases, when the volume hologram layer remained on the adherend, the circle mark indicates that the volume hologram layer was adhered in 3 times of the tape adhesion test. When it remains in the body, the x mark indicates that the volume hologram layer has moved to the tape side. The (−) mark indicates that the volume hologram layer was not transferred to the adherend and the adhesion with the adherend could not be evaluated.

  When the volume hologram transfer foils of Examples 1 to 6 are used, both the transferability to the adherend and the adhesion to the adherend are excellent, but in the comparative example, the transferability to the adherend and It can be seen that the coherence with the adherend cannot be achieved.

It is a figure for demonstrating an example of the volume hologram transfer foil of this invention with the sectional drawing. It is a figure for demonstrating an example of the volume hologram transfer foil of this invention with the sectional drawing. It is a figure for demonstrating the volume hologram laminated body of this invention with the sectional drawing.

Explanation of symbols

Reference numeral 1 denotes a substrate, 2 denotes a protective layer, 3 denotes a volume hologram layer, 4 denotes a primer layer, 5 denotes a heat seal layer, 6 denotes a release film, and 7 denotes an adherend.

Claims (7)

A protective layer, a volume hologram layer, a primer layer, and a heat seal layer made of a thermoplastic resin are sequentially laminated on the substrate, and a sequential laminate of the protective layer, the volume hologram layer, the primer layer, and the heat seal layer from the substrate. In the volume hologram transfer foil laminated in a peelable manner, the volume hologram layer is a cationic polymerizable compound, a radical polymerizable compound, a photo radical polymerization initiator system that polymerizes a radical polymerizable compound by being exposed to light of a specific wavelength, and the above A volume hologram recording layer made of a photosensitive material having a low photosensitivity with respect to light of a specific wavelength, and a photocationic polymerization initiator system that is sensitive to light of another wavelength and polymerizes a cationically polymerizable compound, The primer layer is a mixture of a polyurethane adhesive and a curing agent, and is formed using an aqueous dispersion of the mixture. The volume hologram transfer foil according to claim. The volume hologram transfer foil according to claim 1, wherein the heat seal layer made of a thermoplastic resin is made of a polyester resin having a glass transition temperature of -10 ° C to -30 ° C. 2. The volume hologram transfer foil according to claim 1, wherein the heat seal layer made of a thermoplastic resin is made of a polyester resin having a number average molecular weight of 18,000 to 80,000. The volume hologram transfer foil according to claim 1, wherein the heat seal layer made of a thermoplastic resin contains fine particles. 2. The volume hologram transfer foil according to claim 1, wherein a release film is further provided on the heat seal layer. In a volume hologram laminate in which a heat seal layer, a primer layer, a volume hologram layer, and a protective layer made of a thermoplastic resin are sequentially laminated on an adherend, the volume hologram layer is a cationic polymerizable compound, a radical polymerizable compound, and a specific wavelength. A photo-radical polymerization initiator system that polymerizes a radically polymerizable compound by being exposed to light of the above, and a low-sensitivity to light of the specific wavelength, and a cationically polymerizable compound that is sensitive to light of another wavelength. A volume hologram recording layer comprising a photosensitive material comprising a photocationic polymerization initiator system to be polymerized, and the primer layer is a mixture of a polyurethane adhesive and a curing agent, and an aqueous dispersion of the mixture is used. A volume hologram laminate, which is formed. The volume hologram laminate according to claim 6, wherein the adherend is a polyester resin card.

Images