JP2002358018A - Hologram transfer foil - Google Patents

Abstract

(57) [Problem] The present invention relates to a hologram transfer foil that enables a volume hologram to be attached to an arbitrary adherend by applying heat and pressure.
A hologram transfer foil that can be attached to an arbitrary adherend, and that is effective in preventing volumetric hologram layer or adherend material destruction even if the volume hologram is to be peeled off after attachment, Another object of the present invention is to provide a hologram transfer foil that can reliably prevent the influence of a coloring component on a volume hologram layer even when a coloring layer that functions as a back layer is provided. SOLUTION: The hologram transfer foil (1) of the present invention has a base material (7) and a volume hologram in a cured resin layer which are releasably laminated on the base material (7) from an upper layer to a lower layer. A volume hologram layer (2), a first heat seal layer (3), and a second heat seal layer (4),
A hologram transfer foil (1) used by being attached to an adherend from the side of a second heat seal layer (4), wherein the adhesive force between the volume hologram layer (2) and the adherend is a volume hologram layer Alternatively, it is characterized by being larger than the material breaking force of the adherend.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hologram transfer foil capable of attaching a volume hologram to an arbitrary adherend by applying heat and pressure, and relates to a hologram transfer foil useful for preventing forgery after being adhered to an adherend. .

[0002]

2. Description of the Related Art A volume hologram is a means capable of recording information in a thickness direction and recording / reproducing a three-dimensional image. Although a method for manufacturing a volume hologram is known, it is difficult to imitate a volume hologram because manufacturing requires precise work using optical devices, and is used to prevent imitation of identification cards, bank cards, and the like. ing. Furthermore, since volume holograms are represented by interference colors of light,
It has an appearance that is difficult to obtain with other image forming means.
In the sense of utilizing the above properties of the volume hologram, it has been performed to apply a hologram adhesive label in the form of an adhesive label by applying an adhesive to a film-shaped volume hologram to various adherends, for example, JP-A-63-2845
No. 86 discloses a transfer type hologram having a laminated structure of a base material, a volume hologram layer, and a heat seal layer in this order. Further, from the viewpoint of preventing imitation, as a method using a relief hologram, for example, Japanese Patent No. 2934281 discloses a transfer hologram having a sequentially laminated structure of a base material, a relief hologram, and a heat seal layer.

[0003] However, in the former, the volume hologram layer is basically made of a photocured resin layer, whereas the adherend is often made of a high quality paper or the like, and the material is often different. There is a problem that it is difficult to select a heat sealant having excellent adhesiveness to the adhesive, and that the target as an adherend is limited depending on the type of the heat sealant. Therefore, there is a problem in 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, thereby allowing forgery.

[0004] In the latter, the volume hologram is different from the relief hologram, and characters on the adherend,
It has the advantage of making images and the like transparent, and also functions as a back layer when a colored layer is interposed between the volume hologram layer and the adherend, increasing the contrast of the hologram image and increasing visibility. However, since it is difficult to color the volume hologram layer itself, it has been studied to provide another colored layer. For example, the present applicant has filed Japanese Patent Application No. 10-278493.
Japanese Patent Application No. Hei 11-324980 proposes to use a colored pressure-sensitive adhesive layer, but there is a problem that a colored component migrates to the volume hologram layer and affects hologram recording.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a hologram transfer foil capable of adhering a volume hologram to an arbitrary adherend by applying heat and pressure to the hologram transfer foil.
Further, even if an attempt is made to peel off the volume hologram after application, material destruction of the volume hologram layer or the adherend is provided and an effective hologram transfer foil is provided to prevent forgery. An object of the present invention is to provide a hologram transfer foil that can reliably prevent the influence on the volume hologram layer.

[0006]

A hologram transfer foil according to the present invention comprises, from an upper layer to a lower layer, a substrate, a volume hologram layer having a volume hologram in a cured resin layer, the layer being releasably laminated with the substrate. (Hereinafter also referred to as a volume hologram layer), a first heat seal layer, and a second heat seal layer are sequentially laminated.

The hologram transfer foil of the present invention comprises, from the upper layer to the lower layer, a substrate, a surface protective layer (hereinafter referred to as a peelable protective layer) laminated releasably from the substrate, and a volume within the cured resin layer. A volume hologram layer having a hologram, a first heat seal layer, and a second heat seal layer are sequentially laminated.

The above-mentioned hologram transfer foil is used by being adhered to the adherend from the side of the second heat seal layer, and the adhesive force between the volume hologram layer and the adherend shows the material breaking force of the volume hologram layer or the adherend. It is characterized by being larger.

The first heat seal layer is a transparent aqueous first heat seal layer, and the second heat seal layer is a colored second heat seal layer.

The colored second heat seal layer is characterized in that it is a laminated body of a colored layer and a second heat seal layer sequentially from the first heat seal layer side.

[0011] The color layer is an ink layer for forming a color layer.

[0012] The color layer is a layer made of a metal or a metal oxide.

A release sheet is laminated on the surface of the second heat seal layer.

[0014]

FIG. 1 is a diagram showing a cross section of an example of a hologram transfer foil according to the present invention. In FIG.
2 is a volume hologram layer, 3 is a first heat seal layer, 4 is a second heat seal layer or a colored second heat seal layer, 5 is a peelable sheet, 6 is a peelable protective layer, and 7 is a base material. is there.

The volume hologram layer 2 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, in which the three-dimensional structure of the object is recorded as it is. To form this volume hologram layer 2,
Obtained by directly recording the interference light between the object light and the reference light on the layered material for forming the volume hologram on the support film, or by duplicating the original volume hologram by contact exposure. Industrially, the latter method is used.

As a support film for applying the material for forming a volume hologram, a polyethylene terephthalate film (commonly called PET film) having a thickness of 1 μm to 1 mm, preferably 10 μm to 100 μm, polyethylene film, polypropylene film, polyvinyl chloride A film, an acrylic film, a triacetyl cellulose film, a cellulose acetate butyrate film, or the like is used. It is desirable to use a film having high transparency and high smoothness as the support film.

As the material for forming the volume hologram, any of known volume hologram recording materials such as a silver salt material, a gelatin dichromate emulsion, a photopolymerizable resin and a photocrosslinkable resin can be used. Above, the photosensitive material for dry volume phase hologram recording, consisting of a matrix polymer, a photopolymerizable compound, a photopolymerization initiator and a sensitizing dye, and a plasticizer and a surfactant added as needed, It is preferably used as a hologram forming material.

Examples of the matrix polymer as the binder resin include polymethacrylic acid ester or its partially hydrolyzed product, polyvinyl acetate or its hydrolyzed product, polyvinyl alcohol or its partially acetalized product, triacetyl cellulose, polyisoprene, and polybutadiene. , Polychloroprene, silicone rubber, polystyrene, polyvinyl butyral, polychloroprene, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinylcarbazole or a derivative thereof, poly-N-vinylpyrrolidone or a derivative thereof, styrene and anhydrous Maleic acid copolymer or its half ester, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, acrylonitrile, ethylene, propylene, Vinyl, copolymers and at least one polymerizable component copolymerizable monomers groups such as vinyl acetate or mixtures thereof, are used.

More preferably, the matrix polymer is polyisoprene, polybutadiene, polychloroprene, polyvinyl alcohol, or polyvinyl acetal which is a partially acetalized product of polyvinyl alcohol.
Examples include polyvinyl butyral, polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, and the like, or a mixture thereof.

The step of stabilizing the recorded hologram includes the step of monomer transfer by heating. For this purpose, these matrix polymers preferably have a relatively low glass transition temperature and facilitate monomer transfer. It is necessary to be.

Examples of the photopolymerizable compound include photopolymerizable and photocrosslinkable monomers and oligomers having at least one ethylenically unsaturated bond in one molecule as described below.
Prepolymers, and mixtures thereof, for example, unsaturated carboxylic acids, and salts thereof, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and unsaturated carboxylic acids and aliphatic polyhydric amine compounds. Amide bonds may be mentioned.

Specific examples of unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and their halogen-substituted unsaturated carboxylic acids such as chlorinated unsaturated carboxylic acids. , Brominated unsaturated carboxylic acids, fluorinated unsaturated carboxylic acids, and the like. The salts of unsaturated carboxylic acids include the sodium and potassium salts of the aforementioned acids.

Specific examples of the monomer of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, which are photopolymerizable compounds, include ethylene glycol diacrylate and triglyceride which can be classified into acrylic esters. Ethylene glycol diacrylate, 1,3-
Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether,
Trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol Triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, 2-phenoxyethyl alcohol Relate, 2-phenoxyethyl methacrylate, phenol ethoxylate monoacrylate, 2- (p-chlorophenoxy) ethyl acrylate, p-chlorophenyl acrylate, phenyl acrylate, 2-phenylethyl acrylate, bisphenol A (2-acryloxyethyl) ether Ethoxylated bisphenol A diacrylate, 2-
(1-naphthyloxy) ethyl acrylate, o-biphenyl methacrylate, o-biphenyl acrylate and the like.

Among the specific examples of monomers of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, which are photopolymerizable compounds, those which can be classified as methacrylates include tetramethylene glycol dimethacrylate, Ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol tri Methacrylate, pentaerythritol tetramethacrylate,
Dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate,
Bis- [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p-
(Acryloxyethoxyphenyl) dimethylmethane,
Examples include 2,2-bis (4-methacryloyloxyphenyl) propane and 2-naphthyl methacrylate.

Among the specific examples of monomers of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, which are photopolymerizable compounds, those which can be classified as itaconic esters include ethylene glycol diitaconate and propylene. Glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate,
Pentaerythritol diitaconate, sorbitol tetritaconate and the like.

Among the specific examples of monomers of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, which are photopolymerizable compounds, those which can be classified as crotonic acid esters include ethylene glycol dicrotonate and tetrachloroethylene. Examples include methylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate.

Among the specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, which are photopolymerizable compounds, those which can be classified as isocrotonic acid esters include ethylene glycol diisocrotonate, Pentaerythritol diisocrotonate, sorbitol tetraisocrotonate and the like can be mentioned.

Among the specific examples of monomers of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, which are photopolymerizable compounds, those which can be classified as maleic esters include ethylene glycol dimaleate and triethylene. Glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like can be mentioned.

Examples of the halogenated unsaturated carboxylic acid which is a photopolymerizable compound include 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 2H, 2H-
Heptadecafluorodecyl acrylate, 2,2,3
3-tetrafluoropropyl methacrylate, 1H, 1
H, 2H, 2H-heptadecafluorodecyl methacrylate, 2,4,6-tribromophenyl methacrylate, dibromoneopentyl dimethacrylate (trade name:
NK ester DBN, manufactured by Shin-Nakamura Chemical Co., Ltd., dibromopropyl acrylate (trade name: NK ester A-)
DBP, manufactured by Shin-Nakamura Chemical Co., Ltd.), dibromopropyl methacrylate (trade name: NK ester DBP, manufactured by Shin-Nakamura Chemical Co., Ltd.), methacrylic acid chloride, 2,4,6-trichlorophenyl methacrylate, p-chlorostyrene, methyl-2-chloroacrylate, ethyl-
Examples thereof include 2-chloroacrylate, n-butyl-2-chloroacrylate, tribromophenol acrylate, and tetrabromophenol acrylate.

Specific examples of amide monomers of unsaturated carboxylic acids and aliphatic polyamine compounds, which are photopolymerizable compounds, include methylenebisacrylamide, methylenebismethacrylamide, 1,6-hexamethylenebis Examples include acrylamide, 1,6-hexamethylenebismethacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, N-phenylmethacrylamide, diacetoneacrylamide, and the like.

Other examples of the photopolymerizable compound include a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-B-48-41708, and the following general formula: CH ₂ CC (R ) COOCH ₂ CH (R ′) OH
(Wherein R and R 'represent hydrogen or a methyl group), and a vinyl urethane compound having two or more polymerizable vinyl groups in one molecule to which a hydroxyl-containing vinyl monomer is added. Can be

Further, urethane acrylates described in JP-A-51-37193, JP-A-48-641
No. 83, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 5
Polyester acrylates, epoxy resins and (meth) as described in JP-A-2-30490, respectively.
Examples include polyfunctional acrylates and methacrylates such as acrylic acid.

Further, the Journal of the Adhesion Society of Japan, Vol. 20, N
o7, those introduced as photocurable monomers and oligomers on pages 300 to 308 can also be used.

In another example of the photopolymerizable compound, as a monomer containing phosphorus, mono (2-acryloyloxyethyl) acid phosphate (trade name: Light Ester PA, manufactured by Kyoeisha Yushi Kagaku Kogyo KK) , Thing (2-
(Methacryloiki ethyl) acid phosphate (trade name: Light Ester PM, Kyoeisha Yushi Kagaku Kogyo Co., Ltd.)
And epoxy acrylate-based products such as Lipoxy VR-60 (manufactured by Showa Polymer Co., Ltd.) and trade names: Lipoxy VR-90 (manufactured by Showa Polymer Co., Ltd.).

As other examples of the photopolymerizable compound, trade name: NK ester M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.), trade name: NK ester 23G (manufactured by Shin-Nakamura Chemical Co., Ltd.) ).

Furthermore, triacrylates having the following structural formula (trade name, Aronix M-315, manufactured by Toa Gosei Chemical Industry Co., Ltd.)

[0037]

Embedded image Triacrylates having the following structural formula (manufactured by Toa Gosei Chemical Industry Co., Ltd., trade name, Aronix M-325)

[0038]

Embedded image Also, 2,2'-bis (4-acryloxydiethoxyphenyl) propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, NK
Ester A-BPE-4), tetramethylolmethanetetraacrylate (trade name, NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

Next, as a photopolymerization initiator in the initiator system, 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-
(Butyldioxycarbonyl) benzophenone, N-phenylglycine, 2,4,6-tris (trichloromethyl) -s-triazine, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, and imidazole dimers Etc. are exemplified. The photopolymerization initiator is
From the viewpoint of stabilization of the recorded hologram, it is preferable that the hologram is decomposed after recording the hologram. For example, organic peroxides are preferable because they are easily decomposed by ultraviolet irradiation.

The sensitizing dyes include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, and oxonol dyes having absorption light at 350 to 600 nm. Dyes, cyanine dyes, rhodamine dyes, thiopyrylium salt dyes, pyrylium ion dyes, and diphenyliodonium ion dyes are exemplified. Note that a sensitizing dye having absorption light in a wavelength region of 350 nm or less or 600 nm or more may be used.

The mixing ratio of the material for forming a volume hologram comprising the above matrix polymer (binder resin), a photopolymerizable compound, a photopolymerization initiator and a sensitizing dye is as follows.

The photopolymerizable compound is a binder resin 10
It is used in an amount of 1 to 100 parts by weight, preferably 5 to 10 parts by weight, based on 0 parts by weight.

The photopolymerization initiator is used in a proportion of 1 to 10 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the binder resin.

The sensitizing dye is used in an amount of 0.01 to 1 part by weight, preferably 0.0 to 1 part by weight, based on 100 parts by weight of the binder resin.
It is used in a proportion of 1 part by weight to 0.5 part by weight.

Other components of the material for forming a volume hologram include, for example, a plasticizer, glycerin, diethylene glycol, triethylene glycol and various nonionic surfactants, cationic surfactants, and anionic surfactants. No.

The material for forming the volume hologram is acetone,
Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, 1,4-dioxane, 1,2-dichloroethane, dichloromethane, Using chloroform, methanol, ethanol, isopropanol, etc., or a mixed solvent thereof, and solid content of 15% to
It is a 25% coating liquid.

If the support film is applied in the form of a sheet (each sheet) using these coating solutions, the support film is rolled by bar coating, spin coating, dipping or the like. If it is applied in a long state, it is applied by gravure coating, roll coating, die coating, comma coating, etc., and after applying any, using a drying or curing means according to the application liquid And solidify. The thickness of the volume hologram forming material thus obtained is 0.1 μm to 50 μm.
m, preferably 5 μm to 20 μm.

As such a hologram recording material,
For example, the "Omunidex" series manufactured by Tupon can be used.

Further, as the hologram recording material, a photopolymerizable composition comprising a binder resin, a radical polymerizer, a cationic polymerizer, a sensitizing dye, a radical polymerizable monomer, and a cationic polymerizable monomer can be used.

A cover film may be stuck on the material for forming a volume hologram obtained by applying the film on the support film until the hologram information is exposed. 1μm ~ 1mm thick film for cover
A 10 μm to 100 μm PET film, a polyethylene film, a polypropylene film, a polyvinyl chloride film, an acrylic film, a triacetyl cellulose film, a cellulose acetate butyrate film, etc., having a high transparency and a film having a high smoothness are preferably applied to a rubber roller or the like. It is good to stick. For the cover, instead of attaching a transparent resin film as described above, a coating material in which a film-forming material such as triacetyl cellulose, polyvinyl alcohol, or polymethyl methacrylate is dissolved is applied by spin coating or the like to form a coating. It may be formed.

When a cover film is present on the volume hologram forming material on the support film, or when the cover film is peeled off, two laser beams of laser light, For example, using an argon laser (wavelength: 514.5 nm), a krypton laser (wavelength: 647 nm), or the like, the interference light between the object light and the reference light is recorded, or the protective film is peeled off, and then directly onto the material for forming a volume hologram. The original volume hologram was brought into close contact with the substrate, and an argon laser (wavelength: 514.5) was applied from the support film side of the volume hologram forming material.
nm) is incident, and interference fringes between the reflected light from the original and the incident light are recorded to give volume hologram information. A full-color hologram can be obtained by recording using a laser beam of a bright line having a wavelength of 476.5 nm, 532 nm, or 647 nm as a light source. After recording, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp is used.
1 to 10,000 mJ / cm ² , preferably 10 to 1,
A step of decomposing the photopolymerization initiator by irradiating 000 mJ / cm ² ultraviolet rays and a step of diffusing and moving the photopolymerizable compound by a heat treatment, for example, heating at 120 ° C. for 24 minutes, to obtain a stable volume hologram. I do.

The volume hologram layer 2 of the present invention
Except for the color of the hologram image, the hologram has transparency even if it is colorless and transparent or slightly colored due to various factors, and has sufficient visible light transmittance.

The volume hologram layer 2 obtained by the above process has a structure in which a volume hologram is contained in a cured resin layer and is laminated with a support film. The support film may be peeled off when the volume hologram layer is formed,
Alternatively, for the purpose of preventing the exposed surface of the volume hologram layer 2 from being damaged or contaminated in a subsequent processing step, it is adhered as it is, and is peeled off when processing is necessary, or the hologram is transferred. It is good to peel off just before making it into foil. Alternatively, when a peelable protective layer described later is not required, the support film may be used as it is as the base material in the hologram transfer foil.

A volume hologram in the volume hologram layer is a volume hologram in which interference fringes corresponding to the wavefront of light from an object are recorded in a volume hologram layer cured in the form of transmittance modulation and refractive index modulation. This has the advantage that the volume hologram master can be easily formed by bringing the original into close contact and performing exposure and development.

The first heat seal layer 3 is composed of the volume hologram layer 2 and the second heat seal layer 4 obtained as described above.
The second heat seal layer may be transparent and non-colored together with the second heat seal layer described later. However, when the first heat seal layer is colored, there is a problem of migration of the colorant to the volume hologram layer. Therefore, the first heat seal layer may be made transparent and non-colored, and may be colored in the second heat seal layer described later. Thereby, the contrast of the obtained hologram image can be improved without affecting the transfer of the dye to the volume hologram.

As the first heat seal layer, a solvent-based thermoplastic resin and an aqueous thermoplastic resin are exemplified. As the solvent system, ethylene-vinyl acetate copolymer resin, polyamide resin, polyester resin, polyethylene resin, ethylene-
Isobutyl acrylate copolymer resin, butyral resin,
Thermoplastic elastomers such as polyvinyl acetate resin and its copolymer resin, cellulose derivative, polymethyl methacrylate resin, polyvinyl ether resin, polyurethane resin, polycarbonate resin, polypropylene resin, epoxy resin, phenol resin, SBS, SIS, SEBS, SEPS, Or, a reaction hot melt resin is exemplified. Commercial products include ethylene-vinyl acetate copolymer resin "AD1790-15" manufactured by Toyo Morton Co., Ltd.
"M-720AH" manufactured by IC Corporation, "A-928" manufactured by DIC, a polyester resin, "A-450" manufactured by DIC, an acrylic resin, and DI
"A-100Z-4" manufactured by Company C is exemplified.

The solvent-based thermoplastic resin is dissolved in a solvent such as toluene, methyl ethyl ketone, or the like, and dried by a comma coater, a die coater, a gravure coater, or the like onto a release film having a smooth surface and having a dry film thickness of 2 to 20 μm.
m. It is also possible to apply directly on the volume hologram layer 2. However, since the solvent affects the hologram recording in the volume hologram layer, it is applied and dried on a temporary carrier to form a layer. It is preferable to apply by applying pressure while overlapping the hologram layer.

When a solvent-based thermoplastic resin is used, a solvent-soluble photopolymerizable compound or plasticizer described as a constituent material of the volume hologram layer 2 in the first heat seal layer, If a tackifier (tackifier), a surfactant or the like is added within a range that does not hinder the adhesiveness, the added components migrate to the volume hologram layer to swell or shrink the volume hologram layer 2. A "tuning effect" can be provided, and the color of reproduced image information can be controlled. However, when the second heat-sealing layer contains a solvent-soluble dye, the dye may migrate to the hologram layer via the first heat-sealing layer. It is necessary to use a solvent-insoluble dye or pigment as the colorant.

The first heat seal layer is preferably formed from an aqueous thermoplastic resin. Examples of the aqueous thermoplastic resin include “V-100” and “V-200” manufactured by Mitsui Chemicals, Inc., which are vinyl acetate copolymerized polyolefins, and products manufactured by Chuo Rika Kogyo Co., Ltd., which is an ethylene vinyl acetate copolymerized resin. "E
C-1700 "," MC-3800 "," MC-440 "
Chuo Rika Kogyo Co., Ltd., which is an ethylene methyl methacrylate (EMMA) copolymer resin.
"AC-3100" manufactured by DIC Corporation and "AP-60LM" manufactured by DIC Corporation, which is a polyester-based urethane.

The aqueous thermoplastic resin is dissolved in an alcoholic solvent such as water or propanol, and dried with a comma coater, a die coater, a gravure coater or the like to obtain a dried film having a thickness of 2 to 20 μm.
It is applied and formed to a thickness of μm. In this case, it is also possible to apply directly on the volume hologram layer, but it is also possible to apply it on the temporary carrier and then apply pressure to the volume hologram layer so as to overlap it.

When the first heat-sealing layer is made of water, the dye can be prevented from being transferred to the volume hologram layer even if the second heat-sealing layer described below is colored with a solvent-soluble dye, and the use as a dye is not restricted. There is.

Next, the second heat seal layer 4 is used for bonding the first heat seal layer and the adherend by heat and pressure. It should be selected. Examples of the adherend include a polyvinyl chloride (hereinafter, also simply referred to as a polyvinyl chloride) sheet, a polystyrene sheet, and PET.
Sheets, high-quality papers and the like are exemplified. From the viewpoint of adhesiveness with these adherends, ethylene-vinyl acetate copolymer resin "AD1790-15" manufactured by Toyo Morton Co., Ltd., "M-720AH" manufactured by DIC Corporation, In addition, polyester resin D
"A-928" manufactured by IC Company, DIC which is an acrylic resin
It may be appropriately selected from heat sealants such as "A-450" manufactured by DIC Corporation and "A-100Z-4" manufactured by DIC, which is a vinyl chloride-based resin, in consideration of the adhesiveness to the adherend.

The second heat seal layer 4 may be non-colored and transparent, but can be used as a background of a hologram image by including a coloring agent in the second heat seal layer. An image can be visually recognized, and a hologram image with high contrast can be provided.

As the coloring agent, pigments and dyes may be used alone or as a mixture. As the pigment, a black pigment such as carbon black, copper-iron-manganese, and aniline black, a coloring pigment other than black such as naphthol red F5RK and phthalocyanine blue, and an infrared reflective pigment are used alone or in combination. When a colored infrared reflective pigment is used as the pigment, the back layer of the hologram recording layer can be changed to a state different from that of visible light, and can be used for, for example, forgery prevention and identification.
The pigment has an average particle diameter of 10 μm or less, preferably 1 μm or less.
If the average particle diameter exceeds 10 μm, the surface of the second heat seal layer may have irregularities and the interference fringes recorded on the hologram may be disturbed because the volume hologram layer itself is soft. Further, it is not preferable because the hologram image becomes dark or spots are missing. As a result, the surface smoothness of the surface of the second heat seal layer is ± 0.
The thickness may be 5 μm or less, preferably ± 0.2 μm or less. Such surface smoothness is obtained by forming a second heat seal layer containing a pigment on a release film having a smooth surface, peeling the release film, and laminating the first heat seal layer by thermal transfer from the release surface. This can be easily achieved.

As the dye, acid black,
Examples of the dye include black dyes such as chrome black and reactive black, and dyes such as disperse red, cationic blue, and cationic yellow, which are used alone or in combination.

The pigment or dye is contained in the second heat seal layer in an amount of 1% to 40% by weight, preferably 10% to 30% by weight.
The content is preferably not more than 40% by weight, because the heat sealing property is deteriorated.

The colored second heat seal layer is
O. D. The value is 1.5 or more, preferably 1.9 or more, and it is preferable that the light of the diffraction wavelength of the volume hologram layer is absorbed by 50% or more, preferably 80% or more;
Thereby, a hologram image having excellent contrast can be obtained.

The colored second heat seal layer 4 is prepared by dissolving or dispersing a pigment and a dye together with an adhesive in a solvent such as ethyl acetate, toluene, methyl ethyl ketone or the like, and then drying the film with a comma coater, a die coater, a gravure coater or the like. 0.5 μm to 100 μm, preferably 1 to 50
It is applied and formed to a thickness of μm.

The colored second heat seal layer 4 may be applied directly on the first heat seal layer 3 or may be formed once on a temporary carrier and then applied. Heat seal layer 4, first heat seal layer 3
May be formed on the volume hologram layer 2 from the first heat seal layer 3 side at a time by superimposing and bonding them together, and then by hot-pressure transfer.

Next, as shown in FIG.
The heat seal layer 4 may have a laminated structure of the colored layer 4 ′ and the second heat seal layer 4 ″ from the first heat seal layer side, and is adhered to the adherend from the second heat seal layer 4 ″ side. You may do so. That is, instead of the colored second heat seal layer 4, a laminated structure of a colored layer 4 'and a second heat seal layer 4 "is provided.

The coloring layer 4 'may be an ink layer comprising a binder and a coloring agent. The binder is not particularly limited as long as it has an adhesive property with the first heat seal layer 3 and the second heat seal layer 4 ″. For example, polyurethane resin, polyester resin, polyacryl resin, vinyl chloride resin, vinyl acetate Resin, polyvinyl chloride-vinyl acetate copolymer resin, polyolefin resin, ethylene-vinyl acetate copolymer resin, styrene-butadiene copolymer resin, polyamide resin and the like are exemplified.

Examples of the coloring agent include the pigments and dyes described in the section of the second heat seal layer 4 which are colored, or a mixture thereof. Pigment or dye is contained in the colored layer 4 '.
% By weight, preferably 10% by weight to 30% by weight, and can be contained in a larger amount than the colored second heat seal layer 4. The coloring layer 4 'is made of O.D. D. A value of 1.5 or more, preferably 1.9
Above, it is preferable that the light of the diffraction wavelength of the volume hologram layer is absorbed by 50% or more, preferably by 80% or more, whereby a hologram image having excellent contrast can be obtained.

The colored layer is formed by dispersing a pigment and a dye in a binder to form an ink, and then drying the dried layer with a comma coater, a die coater, a gravure coater, or the like.
The coating is formed to a thickness of 00 μm, preferably 1 to 50 μm.
The coloring layer may be formed by directly applying on the first heat seal layer 3 or the second heat seal layer 4 ″.

Next, the second heat seal layer 4 ″ is preferably formed using the solvent-based adhesive described in the section of the second heat seal layer 4. After dilution, a comma coater, die coater,
Dry film thickness 0.5μm ~ 100 by gravure coater etc.
μm, preferably 1 to 50 μm.

The second heat seal layer 4 ″ may be formed directly on the colored layer 4 ′. However, after being formed directly on the peelable sheet 5, the second heat seal layer 4 ″ is formed on the colored layer 4 ′ together with the peelable sheet 5. The second heat seal layer 4 ″ and the colored layer 4 ′ may be sequentially formed on the peelable sheet 5, and the first heat seal layer 3 may be formed on the first heat seal layer 3 from the colored layer 4 ′ side. It may be formed by laminating together with the peelable sheet 5. Further, the second heat seal layer 4 ″, the colored layer 4 ′, and the first heat seal layer 3 formed in this order on the release sheet 5 are stacked on the volume hologram layer 2 from the first heat seal layer 3 side at a time. It may be formed by bonding and heat and pressure transfer.

When the colored second heat seal layer has a laminated structure of a colored layer and a second heat seal layer from the side of the first heat seal layer, it is possible to prevent the transfer of the coloring component in the colored layer to the volume hologram layer, Since a hologram image having a higher contrast is provided, and the second heat seal layer does not contain a coloring agent, the second heat seal layer can have excellent adhesion to an adherend, and is particularly useful for preventing forgery such as hologram replacement. .

Although the colored layer 4 'is formed by coating in consideration of the cutting property of the hologram transfer foil, it may be a colored film. In this case, a cut such as a slit is provided in advance. The foil can be cut.

Further, a light reflecting layer may be used as the colored layer 4 '. As the reflective layer, a metal thin film that reflects light is preferably used, and can be formed by a known method such as sublimation, vacuum deposition, sputtering, reactive sputtering, ion plating, or electroplating. Examples of the metal thin film include Cr, Ti, Fe, Co, Ni, Cu, Ag, and A.
u, Ge, A1, Mg, Sb, Pb, Pd, Cd, B
It is a thin film formed of a metal such as i, Sn, Se, In, Ga, and Rb and its oxide, nitride, or the like, alone or in combination of two or more. A1, C among the above metal thin films
Particularly preferred are r, Ni, Ag, Au and the like.
The range is from 10 to 10,000 nm, preferably from 20 to 200 nm. With such a colored layer, the visibility and design of the hologram image can be improved.

Next, in addition to the commonly used release paper, a polyethylene terephthalate resin film or a polypropylene resin film may be used as the release sheet 5 shown in FIGS. A release film obtained by release treatment with a mold agent or the like may be used.

Next, as shown in FIGS. 1 and 2, the peelable protective layer 6 formed on the volume hologram layer 2 is required to have not only the adhesive property with the volume hologram layer 2 but also the peelability with the substrate 7. After the substrate 7 is peeled off, the protective layer of the volume hologram layer 2 is a layer that requires functions such as hard coat properties, printability, and slip properties. From the viewpoint of protection against the volume hologram layer after the substrate 7 has been peeled off, it reacts with ionizing radiation such as ultraviolet rays or electron beams of methacrylic resin such as polymethyl methacrylate, trifunctional or higher, preferably 6 or higher. It is preferable to use ionizing radiation-curable epoxy-modified acrylate resin, urethane-modified acrylate resin, acryl-modified polyester resin, or the like. Also, in order to improve various functions, polyacrylate resin, polyvinyl chloride resin, cellulose resin,
Silicone resin, chlorinated rubber, casein, various surfactants, wax, and at least one of metal compounds are added to form a coating liquid, and the film is formed with a dry film thickness of 0.1 μm to 3 μm, so that peeling force and foil breakage are obtained. Excellent in properties and surface protection.

Considering the effects of additives and solvents, it is not preferable to form the peelable protective layer directly on the volume hologram layer, and it is preferable to use a coating liquid for forming the peelable protective layer on the base material. Is formed, it may be laminated on the volume hologram layer by thermal pressure transfer.

Next, the base material 7 is used as a temporary carrier on the peelable protective layer 6, and after the hologram transfer foil is thermally laminated on the adherend from the second heat seal layer side, the hologram transfer foil is then laminated. 6 from above. As the substrate 7, polyethylene film, polypropylene film, polyfluoroethylene film, polyvinylidene fluoride film, polyvinyl chloride film, polyvinylidene chloride film, ethylene-vinyl alcohol film, polyvinyl alcohol film, polymethyl methacrylate film, Polyethersulfone film, polyetheretherketone film, polyamide film, tetrafluoroethylene-perfluoroalkylvinylether copolymer film, polyester film such as polyethylene terephthalate film, and resin such as polyimide film are exemplified, and the film thickness is 2 μm to 200 μm.
m, preferably 10 μm to 50 μm. The base material 7
The type of the base material, the material of the releasable protective layer, etc. may be appropriately selected and the peeling force may be adjusted so that the releasable protective layer can be separated from the interface, and the peeling force is 1 to 100 gf / in.
ch (90 ° peeling), preferably 1 to 5 gf / inch
Should be within the range.

Further, as shown in FIG.
May be unnecessary. In this case, when the base material 7 used is a release treatment with a fluorine-based release agent, a silicone-based release agent, or the like, or the base material 7 contains a release agent to make itself peelable. When using a material, even if the substrate has no releasability, the volume hologram layer is released from the substrate by curing the volume hologram layer itself after laminating the substrate on the uncured volume hologram layer. This is the case where

As shown in FIG. 4, if the second heat seal layer 4 does not have a blocking property when stacked with another hologram transfer foil or formed into a continuous roll, the release sheet 5 is unnecessary. It may be. However, it is preferable that the releasable sheets 5 are stacked because the second heat seal layer 4 can be surely protected during storage.

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, when the volume hologram is to be peeled off from the adherend for the purpose of forgery after the hologram is transferred to the adherend, the material of the volume hologram layer is destroyed and the hologram image cannot be reproduced. Thus, the relationship between the adhesive force between the volume hologram layer and the adherend and the material breaking force of the volume hologram layer is adjusted. Also, in the case where the adherend is a photograph or a high-quality paper having a low material destructive force, if the volume hologram layer is to be peeled from the adherend for the purpose of forgery,
The thing which can achieve the object of forgery prevention by material destruction of an adherend may be used.

In the present invention, the adhesive force between the volume hologram layer and the adherend needs to be larger than the material breaking force of the volume hologram layer or the adherend.

The material breaking force of the volume hologram layer and the adherend can be shown by the breaking strength measured according to JIS K7127-1989. The breaking strength of the volume hologram layer in the present invention is 0.01 kg / mm ^2. ~ 5kg /
mm ² , usually 0.03 kg / mm ^{2 to 3} kg / mm ²
It is about. In addition, the breaking strength of high quality paper is usually 3.0.
is ^{kg / mm 2 ~5.0kg / mm 2} .

The adhesive strength between the volume hologram layer and the adherend is measured according to a peeling test (JIS K6301), and the adhesive strength of the first heat seal layer and the second heat seal layer is measured. By appropriate selection, 2
It is good to be about 000 gf / inch to about 3000 gf / inch.

Although the material destructive force of the volume hologram layer and the adherend and the adhesive force between the volume hologram layer and the adherend cannot be directly compared numerically, the peeling of the volume hologram layer from the adherend is not possible. It can be easily confirmed whether the material of the volume hologram layer is broken or the material of the adherend is broken. As a guide of the numerical values of the material breaking force of the volume hologram layer or the adherend and the adhesive force between the volume hologram layer and the adherend, when the breaking strength of the volume hologram layer is, for example, 2.30 kg / mm ² , The adhesive force between the hologram layer and the adherend is 1000 gf / inch
This is the case above. Accordingly, when the volume hologram layer is to be peeled off from the adherend for the purpose of forgery, the material of the hologram layer or the adherend can be surely destroyed, and forgery can be prevented.

Next, as a method of manufacturing a hologram transfer foil according to the present invention, as described in Examples below, each laminated structure is provided on a temporary carrier to form a transfer body, and then a layer of the hologram transfer foil is formed. It is preferable to sequentially form the layers by hot-pressure transfer according to the configuration. However, as described in each layer described above, for example, the first heat seal layer and the second heat seal layer are sequentially provided on the temporary carrier. For example, a transfer body may be used by appropriately combining the lamination configurations, such as a transfer body, and used for manufacturing a hologram transfer foil. In the case of the thermal pressure transfer, in order not to affect the recording in the volume hologram layer, the thermal pressure transfer may be performed at 25 ° C to 120 ° C, preferably 60 ° C to 100 ° C.

Further, the hologram transfer foil of the present invention, after the release sheet is peeled off, is placed on an adherend (described later) at 60 ° C. to 20 ° C.
0 ° C., preferably 100 ° C. to 160 ° C., and depending on the type of the adherend, by hot-pressure transfer in the range of 0.5 Mpa to 15 Mpa, and peeling off the base material as necessary, The hologram layer can be transferred onto the adherend.

In the hologram transfer foil of the present invention, the first
The heat seal layer has excellent adhesion to the volume hologram layer,
In addition, the second heat seal layer has excellent adhesiveness to the adherend and can share its function, so that the second heat seal layer can be applied to various objects. When both the first heat seal layer and the second heat seal layer are transparent, the surface of the adherend can be seen through. Furthermore, since the colored hologram transfer foil can be used as the background color of the hologram image, an image with excellent contrast can be obtained. However, if the coloring density of the colored hologram transfer foil is reduced, the lower layer can be transmitted, so that forgery prevention, etc. Useful for

Examples of the object to be applied include glass,
Transparent or opaque materials such as plastics may be used. Examples of the plastic include a vinyl chloride resin, an acrylic resin, a polystyrene resin, a polyester resin such as polyethylene terephthalate, and a polycarbonate resin.

Specific examples of articles made of these materials include, for example, windows, observation windows, and doors of transportation means such as automobiles, railway vehicles, ships, and aircrafts.
Alternatively, there are building windows, doors, mortis windows, light windows, and the like. Further, in the above-mentioned transportation, a hologram transfer foil can be attached to a transparent glass or a transparent plastic plate on instruments or displays provided in a driver's seat, a cockpit, or other places.

Similar displays include appliances, clocks, cameras,
And the like also have various display portions, which are not necessarily colorless and transparent, and some are black when not displayed. However, a hologram transfer foil can also be applied to the surface of such a device. More 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. Devices having a display function. In these,
When the hologram transfer foil has transparency, the hologram images of the volume hologram layer 2 can be overlapped without hindering the display function inherent in the device. In addition to these, luxury watches, jewelry, precious metals, antiques, and the like, or cases thereof, are displayed as genuine products by utilizing the difficulty in manufacturing the volume hologram layer 2 of the hologram transfer foil. It can also be applied for In this case, the object to be pasted may be transparent or opaque.

[0096] The hologram transfer foil can be a sheet such as an identification card, an admission ticket, or a card such as an ID card.
It may be affixed to a booklet such as a passport, and is suitable for use as a certificate showing the safety and hygiene grades of fire protection, disinfection or fire protection, or a certificate showing that measures have been taken. In addition, for applications where a paper certificate has been pasted and sealed, and the target article is transparent and has a substantially flat or quadratic surface, the certificate is basically replaced with a certificate. Can be used. further,
The object to which the hologram transfer foil is to be applied can be broadly used for articles having a portion made of paper, synthetic paper, synthetic resin, metal film or sheet, or glass plate. In addition, utilizing the unique and three-dimensional characteristics of volume holograms, such as books and saddle stitched weekly magazines,
It can also be used as a label to be attached to glass windows of automobiles, premium products, etc.

The hologram image of the volume hologram layer 2 can be designed according to the above-mentioned object, application, and purpose, and can freely include symbols and texts expressing necessary meanings. The hologram image itself can be obtained by calculating a hologram diffraction grating in addition to capturing the actual object, or by using a holographic stereogram technique or the like from two-dimensional or three-dimensional image data obtained from digital images captured by a digital camera or computer graphics. It can be created by appropriate means.

Further, depending on the use, it is preferable to cut in advance according to the shape of the object to be pasted and the portion thereof. Alternatively, when accompanied by the releasable sheet 5, by making a cut in a portion other than the releasable sheet 5, an individual label having a predetermined shape is taken out from a hologram transfer foil having a large size or a wound shape. , Can be applied to the object to be pasted. Such processing can be performed by punching. In order to make a cut only in a portion other than the peelable sheet 5, the punching blade may be moved up and down from the upper surface side of the hologram transfer foil by a stroke leaving the thickness of the peelable sheet 5.

Further, each layer other than the peelable sheet between the adjacent hologram transfer foils may be removed while leaving the individual hologram transfer foils of a predetermined shape. in this case,
A perforation may be provided at the boundary of the peelable sheet so that individual hologram transfer foils can be separated.

[0100]

The present invention will be described below with reference to examples. (Example 1) (Laminate A having hologram-forming layer) PET film / hologram recording material / peelable PET film (HRF)
800x001; manufactured by DuPont).

(Laminate B Having Releasable Protective Layer) The following composition: polymethyl methacrylate resin (weight average molecular weight 95,000) 96.7 parts by weight polyester resin (manufactured by Nippon Polyurethane Co., Ltd., weight average molecular weight)・ 0.3 parts by weight ・ Polyethylene wax (manufactured by Gifu Shellac Co., Ltd., weight average molecular weight: 8000 ″) ・ ・ 3 parts by weight are dissolved and dispersed in methyl ethyl ketone, and then a gravure coater is used on a PET film. And dry film thickness 1μ
m having a peelable protective layer.

(Laminate C Having First Heat Sealing Layer)
Ethylene-vinyl acetate copolymer (Chuo Rika Co., Ltd. “E
After dissolving 60 parts by weight of "C1700" in 40 parts by weight of isopropyl alcohol, on a peelable PET film,
Using a gravure coater, a laminate having a first heat seal layer having a dry film thickness of 2 μm was obtained.

(Laminate D Having Second Heat Sealing Layer)
After dissolving 50 parts by weight of an ethylene-vinyl acetate copolymer (“AD1790-15” manufactured by Toyo Morton Co., Ltd.) in 50 parts by weight of toluene, the dry film thickness is formed on a peelable PET film using a gravure coater. A laminate having a 2 μm second heat seal layer was obtained.

The laminate A having the hologram forming layer was
A Lippmann hologram was recorded using a laser beam having a wavelength of 14 nm, and heated at 100 ° C. for 10 minutes. After peeling off the peelable PET film in the laminate A on which the hologram was recorded, the peelable protective layer surface in the laminate B was thermally laminated at 80 ° C. on the peeled surface. This allows
PET film / peelable protective layer / volume hologram layer / P
A laminate of the ET film was obtained.

Next, after fixing the volume hologram in the laminate using a high-pressure mercury lamp, the PET film in contact with the volume hologram layer was peeled off, and the peeled surface of the laminate C was covered with the first heat seal layer surface by 100 mm. C., and the peelable PET film was peeled off. Next, the second heat seal layer surface of the laminate D was further laminated on the first heat seal layer surface at 100 ° C.

Thus, a transparent hologram transfer foil of PET film / peelable protective layer / volume hologram layer / first heat seal layer / second heat seal layer / peelable PET film was obtained.

(Comparative Example 1) After fixing the volume hologram in the laminate of the PET film / peelable protective layer / volume hologram layer / PET film prepared in Example 1 using a high-pressure mercury lamp. Then, the PET film in contact with the volume hologram layer was peeled off.

The peeled surface was provided with the laminate C described in Example 1.
The first heat seal layer surface of the laminate formed with the first heat seal layer having a thickness of 4 μm
Laminated at ℃.

Thus, the PET film / peelable protective layer / volume hologram layer / first heat seal layer (thickness: 4 μm)
m) / Transparent hologram transfer foil of peelable PET film was obtained.

Comparative Example 2 After fixing the volume hologram in the laminate of PET film / peelable protective layer / volume hologram layer / PET film prepared in Example 1 using a high-pressure mercury lamp. Then, the PET film in contact with the volume hologram layer was peeled off.

On the peeled surface, the second heat seal layer surface of the laminate in which the thickness of the second heat seal layer of the laminate D was 4 μm was laminated at 100 ° C. Thus, a transparent hologram transfer foil of a PET film / peelable protective layer / volume hologram layer / second heat seal layer (thickness: 4 μm) / peelable PET film was obtained.

(Releasability Test) Each of the transparent hologram transfer foils obtained in Example 1 and Comparative Examples 1 and 2 was laminated on a PVC card at 120 to 140 ° C. after the peelable PET film was peeled off. A volume hologram having a peelable protective layer on the surface was thermally transferred. The adhesive strength between the obtained volume hologram layer and the PVC card was measured according to a peeling test (JIS K6301). The results are shown in Table 1 below.

[0113]

[Table 1] (Example 2) "M-720AH" manufactured by DIC was used as the second heat seal layer in the laminate D in Example 1.
Was used in the same manner as in Example 1 to obtain a transparent hologram transfer foil of PET film / peelable protective layer / volume hologram layer / first heat seal layer / second heat seal layer / peelable PET film.

(Example 3) As the second heat seal layer in the laminate D in Example 1, "A-
928 "in the same manner as in Example 1 except that PE
A transparent hologram transfer foil of T film / peelable protective layer / volume hologram layer / first heat seal layer / second heat seal layer / peelable PET film was obtained.

(Example 4) As the second heat seal layer of the laminate D in Example 1, "A-4" manufactured by DIC Corporation was used.
PET ”in the same manner as in Example 1 except that“ 50 ”was used.
A transparent hologram transfer foil of a film / peelable protective layer / volume hologram layer / first heat seal layer / second heat seal layer / peelable PET film was obtained.

(Example 5) As the second heat seal layer in the laminate D in Example 1, "A-1" manufactured by DIC Corporation was used.
00Z-4 ", except for using" 00Z-4 ".
PET film / peelable protective layer / volume hologram layer / first heat seal layer / second heat seal layer / peelable PET
A transparent hologram transfer foil of the film was obtained.

The hologram transfer foils obtained in Examples 1 to 5 were respectively transferred onto vinyl chloride, polystyrene, polyethylene terephthalate, and high-quality paper as card substrates in the same manner as in Example 1, and the adhesive strength was measured in the same manner. . The results are shown in Table 2 below.

In Table 1 and Table 2 below, for example, in the case of the combination of PVC card and Example 1,
The adhesive strength is described as “> 3.0 kgf / inch”, which is 3.0 kgf / inch in the adhesive strength test.
Since the material destruction of the volume hologram layer occurred at the inch, the adhesive strength was determined to be 3.0 kgf / inch or more.

[0119]

[Table 2] ^{* 1} : Destruction of material of volume hologram layer ^{* 2} : Destruction of material of adherend As can be seen from Table 2, in Examples 1 and 2, the adherend was made of polyvinyl chloride, polystyrene, polyethylene terephthalate,
In any case of high-quality paper, the prevention of forgery can be ensured. In the case of the third embodiment, when the adherend is PVC or high-quality paper, the forgery prevention is surely prevented. Further, in the case of Examples 4 and 5, when the adherend is high-quality paper, the forgery thereof can be surely prevented.

The combination of the PVC card and the examples 4 and 5 and the combination of the polystyrene and PET and the examples 3, 4 and 5 have low adhesive strength and the second heat Peeling occurred between the seal layer and the adherend or between the volume hologram layer and the second heat seal layer.

(Example 6) (Laminate A having hologram-forming layer) PET film / hologram recording material / peelable PET film (HRF
800x001; manufactured by DuPont).

(Laminate B Having Releasable Protective Layer) The following composition: polymethyl methacrylate resin (weight average molecular weight 95,000) 96.7 parts by weight polyester resin (manufactured by Nippon Polyurethane Co., Ltd., weight average molecular weight)・ 0.3 parts by weight ・ Polyethylene wax (manufactured by Gifu Shellac Co., Ltd., weight average molecular weight: 8000 ″) ・ ・ 3 parts by weight are dissolved and dispersed in methyl ethyl ketone, and then a gravure coater is used on a PET film. And dry film thickness 1μ
m having a peelable protective layer.

(Laminate C having Uncolored First Heat Sealing Layer) As a water-based thermoplastic resin, ethylene-vinyl acetate copolymer (60 parts by weight of “EC1700” manufactured by Chuo Rika Co., Ltd., was added to 40 parts by weight of water) After dissolution, a dry film thickness of 2 μm was formed on the peelable PET film using a gravure coater.
Having a non-colored first heat seal layer was obtained.

(Laminated product D having colored second heat seal layer) Ethylene-vinyl acetate copolymer (45 parts by weight of "AD1790-15" manufactured by Toyo Morton Co., Ltd.) and a black dye (Nippon Kayaku Co., Ltd. 5) by weight of “Kayaset Black KR”) dissolved in 50 parts by weight of toluene, and dried on a peelable PET film using a gravure coater to form a colored second heat seal layer having a dry film thickness of 2 μm. Was obtained.

A Lippman hologram was recorded on the laminate A using a laser beam having a wavelength of 514 nm, and
Heated at 0 ° C. for 10 minutes. After peeling off the peelable PET film in the laminate A on which the hologram was recorded, the peelable protective layer surface in the laminate B was thermally laminated at 80 ° C. on the peeled surface. Thus, a laminate of PET film / peelable protective layer / volume hologram layer / PET film was obtained.

Next, after fixing the volume hologram in this laminate using a high-pressure mercury lamp, the PET film in contact with the volume hologram layer was peeled off, and the peeled surface was the surface of the uncolored first heat seal layer in the laminate C. At 100 ° C
And the peelable PET film was peeled off. Next, the colored second heat seal layer surface of the laminate D was further laminated at 100 ° C. on the uncolored first heat seal layer surface.

Thus, a colored hologram transfer foil of PET film / peelable protective layer / volume hologram layer / uncolored first heat seal layer / colored second heat seal layer / peelable PET film was obtained.

(Comparative Example 3) After fixing the volume hologram in the laminate of PET film / peelable protective layer / volume hologram layer / PET film prepared in Example 6 using a high-pressure mercury lamp, The PET film in contact with the volume hologram layer was peeled off, and the surface of the colored second heat seal layer of the laminate D was laminated on the peeled surface at 100 ° C. Thereby, a colored hologram transfer foil of PET film / peelable protective layer / volume hologram layer / colored second heat seal layer / peelable PET film was obtained.

(Dye Transfer Test) The peelable PET film was peeled off from the colored hologram transfer foil obtained in Example 6 and Comparative Example 3, and then hot-pressed on a PVC card at 120 to 140 ° C. and peeled. A volume hologram having a hydrophilic protective layer on the surface was thermally transferred.

The transferred volume hologram layer had a strong adhesive force to the adherend and tried to peel off from the adherend, but the volume hologram layer was broken. In contrast, when the volume hologram layer obtained in Comparative Example 3 was peeled off from the adherend,
Peeling was performed between the volume hologram layer and the colored second heat seal layer.

Further, in the volume hologram layer obtained in Example 6, the hologram image could be clearly observed because the contrast with the background was improved. On the other hand, the volume hologram layer obtained in Comparative Example 3 was Immediately after the transfer or several hours later, the dye from the colored second heat seal layer migrated to the volume hologram layer, and the hologram image became very dark, making it difficult to observe.

(Example 7) Uncolored first in Example 6
Instead of the heat seal layer, “V-10” manufactured by Mitsui Chemicals, Inc.
0 "," V-200 "," EC manufactured by Chuo Rika Kogyo Co., Ltd.
-1200 "," MC-3800 "," MC-440 "
0 "," HA-1100 "," AC-3100 ", DI
A colored hologram transfer foil was prepared in the same manner as in Example 6 except that "AP-60LM" manufactured by C Co., Ltd. was similarly used, and transferred to a PVC sheet in the same manner.

The transferred volume hologram layer had a strong adhesive force to the adherend and tried to peel off from the adherend, but the volume hologram layer was broken. In addition, the hologram image was clearly observed because the contrast with the background was improved.

In place of the colored second heat seal layer in Example 6, "A-100" manufactured by Dainippon Ink and Chemicals, Inc. was used.
Z-4 "," M-720AH "," A-450A ",
A colored hologram transfer foil was prepared in the same manner as in Example 6 except that "A-928" was similarly used, and transferred to a PVC sheet in the same manner.

Further, in the obtained volume hologram layer, the hologram image could be clearly observed because the contrast with the background was improved. As the colored second heat seal layer, “M-720AH”, “A-
928 ", the volume hologram layer was tried to be peeled from the adherend, but the adhesion to the adherend was strong, and the volume hologram layer was broken.

(Comparative Example 4) After fixing the volume hologram in the laminate of the PET film / peelable protective layer / volume hologram layer / PET film prepared in Example 6 using a high-pressure mercury lamp. The PET film in contact with the volume hologram layer was peeled off, and a laminate having an uncolored first heat seal layer prepared as described below was used on the peeled surface.
Laminated at ℃.

(Laminate Having Uncolored First Heat-Seal Layer) 80 parts by weight of an ethylene-vinyl acetate copolymer resin (“M-720AH” manufactured by Dainippon Ink KK) were dissolved in 20 parts by weight of methyl ethyl ketone. Thereafter, a dry film thickness of 2 μm was formed on the peelable PET film using a gravure coater.
Thus, a laminate having an uncolored first heat seal layer of m was obtained.

Next, on the surface of the uncolored second heat seal layer, the colored second heat-sealable layer of the laminate D prepared in Example 6 was further added.
The heat seal layer surface was laminated at 100 ° C.

As a result, a colored hologram transfer foil of PET film / peelable protective layer / volume hologram layer / uncolored first heat seal layer / colored second heat seal layer / peelable PET film was obtained.

Using the obtained colored hologram transfer foil,
Similarly, the volume hologram layer was transferred to a PVC sheet, and the volume hologram layer was tried to be peeled from the adherend. However, the adhesive force to the adherend was strong, and the volume hologram layer was broken. (2) The dye from the heat seal layer migrated to the volume hologram layer, and the hologram image became very dark, making it difficult to observe.

(Example 8) (PET film / volume hologram recording material / peelability P)
First laminated body of ET film) Polyethylene terephthalate film (manufactured by Toray Industries, Inc.
Lumilar T-60, thickness 50 μm), as a hologram-forming material, a photosensitive resin composition for forming a volume hologram using a polymethyl methacrylate-based resin (Tg: 100 ° C.) as a basic binder: 60 weight Part: methyl ethyl ketone: 25 parts by weight Toluene: 15 parts by weight A gravure coat was applied to a dry film thickness of 10 μm, and a surface release treated PET film (“S
P-PET ”50 μm, manufactured by Tosero Co., Ltd.)
A first laminate was produced.

(2nd laminate of PET film / peelable protective layer) The following composition: polymethyl methacrylate resin (weight average molecular weight: 95,000) 96.7 parts by weight polyester resin (manufactured by Nippon Polyurethane Co., Ltd.) 0.3 parts by weight ・ Polyethylene wax (manufactured by Gifu Shellac Co., Ltd., weight average molecular weight: 8000 ″) 3 parts by weight are dissolved and dispersed in methyl ethyl ketone, and then PET film is manufactured by Toray Co., Ltd. ), Lumirror T-60, thickness 50μ
Using a gravure coater on m｝, dry film thickness 1μm
A second laminate having a releasable protective layer was obtained.

(Surface release treated PET film / third laminate of uncolored first heat seal layer) Ethylene-vinyl acetate copolymer (60 parts by weight of "EC1700" manufactured by Chuo Rika Co., Ltd.) was used as the aqueous thermoplastic resin. , Dissolved in 40 parts by weight of water, and then peeled PET film ("SP-PET" 50
μm, manufactured by Tocelo Co., Ltd.) using a gravure coater to obtain a third laminate having an uncolored first heat seal layer having a dry film thickness of 2 μm.

(Release sheet 5 / second heat seal layer 4 ″)
/ 4th laminate of colored layer 4 ') 100 parts by weight of a vinyl chloride-vinyl acetate copolymer resin ("A-100Z-4" manufactured by Dainippon Ink Co., Ltd.) is dissolved in 50 parts by weight of toluene, and then a release sheet is prepared. Using a gravure coater, a second heat seal layer 4 ″ having a dry film thickness of 2 μm was provided on (“SP-PET” 50 μm, manufactured by Tosello Co., Ltd.).

Next, on this second heat sealing layer 4 ″, the following composition: polyurethane resin (Nipporan 5138, manufactured by Nippon Polyurethane Industry Co., Ltd.): 30 parts by weight; black pigment (carbon black, Mitsubishi Chemical Corporation) )) 3 parts by weight-Diluent solvent ... 67 parts by weight of a colored layer forming ink, using a gravure coater, laminating a colored layer 4 'with a dry film thickness of 2 m to form a fourth laminate. I got

The first laminate having a hologram-forming layer has the following structure:
A Lippmann hologram was recorded using a laser beam having a wavelength of 514 nm, and heated at 100 ° C. for 10 minutes. After peeling off the peelable PET film of the first laminate on which the hologram was recorded, the peelable protective layer surface of the second laminate was thermally laminated at 80 ° C. on the peeled surface. Thus, a laminate of PET film / peelable protective layer / volume hologram layer / PET film was obtained.

Next, after fixing the volume hologram in this laminate using a high-pressure mercury lamp, the PET film in contact with the volume hologram layer was peeled off, and the uncolored first heat seal of the third laminate was peeled off on the peeled surface. 100 layers
C., and the peelable PET film was peeled off. Then, the fourth laminate was laminated on the surface of the uncolored first heat seal layer from the colored layer 4 'side, and thermally laminated at 100 ° C.

Thus, a colored hologram transfer foil of PET film / peelable protective layer / volume hologram layer / uncolored first heat seal layer / colored layer 4 '/ second heat seal layer 4 "/ peel sheet 5 was obtained. .

(Dye transfer test) The colored hologram transfer foil obtained in Example 8 was peeled off from the release sheet,
At 20 to 140 ° C., a volume hologram having a peelable protective layer on the surface was thermally transferred by laminating on a PVC card.

An attempt was made to peel the volume hologram layer from the adherend, but the adhesive force to the adherend was strong, and the volume hologram layer was broken. Further, the contrast with the background was improved as compared with the colored hologram transfer foil obtained in Example 6, so that the hologram image could be more clearly observed.

(Example 9) (PET film / volume hologram recording material / peelability P)
(First laminate of ET film) 3,500 to 500 parts by weight of polymethyl methacrylate resin (molecular weight: 200,000)
-Diethyl-3'-carboxymethyl-2,2'-thiacarbocyanine iodide 5 parts by weight, diphenyliodonium hexafluoroantimonate 60 parts by weight, 2,2
A hologram recording material comprising 800 parts by weight of -bis [4- (acryloxydiethoxy) phenyl] propane and 800 parts by weight of pentaerythritol polyglycidyl ether was placed on a PET film (50 µm, manufactured by Toray Industries, Inc.).
It is coated with a gravure coat so as to have a dry film thickness of 10 μm, and a surface release treated PET film (50 μm,
A first laminate comprising PET film / hologram recording material / peelable PET film was prepared.

(2nd laminate of PET film / peelable protective layer) PET film (Lumilar T-6, manufactured by Toray Industries, Inc.)
Using a gravure coater, Haclinis ("Hakurinis UVC-5W" manufactured by Showa Ink Industries, Ltd.) was obtained on a 50 µm thick layer to obtain a second laminate having a 1 µm dry film-thick release protective layer. Was.

(Surface release treated PET film / third laminate of uncolored first heat seal layer) Ethylene-vinyl acetate copolymer (60 parts by weight of "EC1700" manufactured by Chuo Rika Co., Ltd.) as an aqueous thermoplastic resin , Dissolved in 40 parts by weight of water, and then peeled PET film ("SP-PET" 50
μm, manufactured by Tocelo Co., Ltd.) using a gravure coater to obtain a third laminate having an uncolored first heat seal layer having a dry film thickness of 2 μm.

(Release sheet 5 / second heat seal layer 4 ″)
/ Fourth laminate of colored layer 4 ') ethylene-vinyl acetate copolymer ("AD1790-15" 5 manufactured by Toyo Morton Co., Ltd.)
After dissolving 0 parts by weight in 50 parts by weight of toluene, a peelable sheet (“SP-PET” 50 μm, manufactured by Tocelo Co., Ltd.)
Using a gravure coater, a second heat seal layer 4 ″ having a dry film thickness of 2 μm was provided thereon.

Then, aluminum was vacuum-deposited with a thickness of 100 nm on the second heat seal layer 4 ″, and a reflective metal thin film was laminated thereon to obtain a fourth laminate.

In the first laminate having the hologram forming layer,
A Lippmann hologram was recorded using a laser beam having a wavelength of 514 nm, and heated at 100 ° C. for 10 minutes. After peeling off the peelable PET film of the first laminate on which the hologram was recorded, the peelable protective layer surface of the second laminate was thermally laminated at 80 ° C. on the peeled surface. Thus, a laminate of PET film / peelable protective layer / volume hologram layer / PET film was obtained.

Next, after fixing the volume hologram in this laminate using a high-pressure mercury lamp, the PET film in contact with the volume hologram layer was peeled off, and the peeled surface was subjected to the first non-colored first heat seal in the third laminate. 100 layers
C., and the peelable PET film was peeled off. Next, a fourth laminate was laminated on the surface of the uncolored first heat seal layer from the reflective metal thin film 4 'side, and thermally laminated at 100 ° C.

Thus, a colored hologram transfer foil of PET film / peelable protective layer / volume hologram layer / uncolored first heat seal layer / deposition layer 4 '/ second heat seal layer 4 "/ peel sheet 5 was obtained. .

(Dye transfer test) After the release sheet was peeled off from the obtained colored hologram transfer foil, 120 to 100%
At 140 ° C, a volume hologram having a peelable protective layer on the surface was thermally transferred by laminating on a PVC card.

An attempt was made to separate the volume hologram layer from the adherend, but the adhesion to the adherend was 3000 gf / inch.
Above, the volume hologram layer was broken. Further, compared with the colored hologram transfer foil obtained in Example 6, the hologram image could be observed more clearly because the contrast with the background was improved. In addition, problems such as disorder of the hologram image and cracking of the deposited layer due to lamination of the deposited layers were not observed.

[0161]

The hologram transfer foil of the present invention is a hologram transfer foil which enables a volume hologram to be attached to an arbitrary adherend by applying heat and pressure. Since material destruction of the layer and adherend occurs, it is effective in preventing forgery,
By using a colored hologram transfer foil, a hologram image having a high contrast can be given, and the influence of the coloring component on the volume hologram layer can be reliably prevented.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining an example of a hologram transfer foil of the present invention in a sectional view thereof.

FIG. 2 is a diagram for explaining an example of a hologram transfer foil of the present invention in a sectional view thereof.

FIG. 3 is a diagram for explaining an example of the hologram transfer foil of the present invention in a sectional view thereof.

FIG. 4 is a diagram for explaining an example of a hologram transfer foil of the present invention in a sectional view thereof.

[Explanation of symbols]

1 is a hologram transfer foil, 2 is a volume hologram layer, 3 is a first heat seal layer, 4 is a second heat seal layer or a colored second heat seal layer, 4 ′ is a colored layer, and 4 ″ is a second heat seal layer. A seal layer, 5 is a peelable sheet, 6 is a peelable protective layer, and 7 is a base material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) G09F 3/10 G09F 3/10 C (31) Priority claim number Japanese Patent Application 2001-86936 (P2001-86936) ( 32) Priority Date March 26, 2001 (March 26, 2001) (33) Priority Country Japan (JP) (72) Inventor Kenji Ueda 1-1-1 Ichigaya Kagamachi, Shinjuku-ku, Tokyo Large F-term in Nippon Printing Co., Ltd. (reference) 2C005 HA02 HB01 HB09 JB08 2K008 AA13 AA15 AA16 DD13 DD14 FF03 FF17 3B005 EA12 EB01 EC25 FB09 FB21 FB42 FB47 FF00 FF06 GA02 GB01

Claims (8)

[Claims] 1. A substrate, a volume hologram layer having a volume hologram in a cured resin layer, the volume hologram layer having a volume hologram in a cured resin layer, a first heat seal layer,
A hologram transfer foil, wherein a second heat seal layer is sequentially laminated. 2. From the upper layer to the lower layer, a base material, a surface protective layer releasably laminated with the base material, a volume hologram layer having a volume hologram in a cured resin layer, a first heat seal layer, 2. A hologram transfer foil, wherein two heat seal layers are sequentially laminated. 3. The method according to claim 1, wherein the second heat seal layer is used by being adhered to the adherend from the side thereof, wherein the adhesive force between the volume hologram layer and the adherend is greater than the material breaking force of the volume hologram layer or the adherend. The hologram transfer foil according to claim 1 or claim 2, wherein 4. The method according to claim 1, wherein the first heat sealing layer comprises a transparent aqueous first
4. The heat seal layer, wherein the second heat seal layer is a colored second heat seal layer.
The hologram transfer foil according to the above. 5. The hologram transfer foil according to claim 4, wherein the colored second heat seal layer is a laminated body of a colored layer and a second heat seal layer sequentially from the first heat seal layer side. 6. The hologram transfer foil according to claim 5, wherein the colored layer is an ink layer for forming a colored layer. 7. The hologram transfer foil according to claim 5, wherein the coloring layer is a layer made of a metal or a metal oxide. 8. The hologram transfer foil according to claim 1, wherein a release sheet is laminated on the surface of the second heat seal layer.