JPH0690592B2 - Hologram sticker - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a seal in which a hologram is provided at a position visible from the outside, and more specifically, a hologram layer and a reflective metal thin film layer formed of a specific resin. Regarding the seal provided.

[Technical Background of the Invention and Problems Thereof] Various kinds of pictures or photographs are printed on the surface of a record jacket, a cover of a book, a bank passbook, etc. to give it a beautiful appearance. However, such a picture or photograph only gives a two-dimensional visual feeling, and lacks a three-dimensional visual feeling.
By providing a hologram on the surface of such a record jacket or the cover of a book, it is possible to give a three-dimensional visual feeling. In addition, an interesting thing can be obtained as a toy for children.

By the way, holography is a new technique for recording the wavefront of light from an object, and a hologram produced by this technique can reproduce a stereoscopic image and also enables multiple recording.

Further, as one method of recording a hologram, interference fringes corresponding to the wavefront of light from an object can be recorded on the surface of the material in a concavo-convex pattern, and this hologram can be easily mass-produced.

When such a hologram is provided on an article such as a record jacket or a cover of a book, a hologram having beauty and novelty can be obtained.

Conventionally, in order to provide a hologram on the surface of an article such as a record jacket, the duplicated hologram is attached to the surface of the article via an adhesive layer. By the way, in general, when an object on the surface of an article is adhered, it is often the case that heat is applied to shorten the adhesive time and obtain a strong adhesive force. However, since the conventional hologram is formed of a thermoplastic resin, if heat is applied at the time of sticking, the uneven pattern, which is an interference fringe corresponding to the wavefront of light from the object, partially disappears, which is a serious problem. was there.

At the same time, since the hologram is formed of a thermoplastic resin, there is a problem that it is generally inferior in hardness, the surface is easily scratched, and it does not have sufficient resistance to a solvent.

[Object of the Invention]

The present invention is intended to solve the problems associated with these conventional techniques, and has the following objects.

(A) To provide a hologram seal which can provide a hologram having excellent heat resistance and thus can be heated when attached.

(B) To provide a hologram sticker capable of providing a hologram having a hard surface and thus a hard surface.

(C) To provide a hologram sticker capable of providing a hologram having excellent solvent resistance.

[Outline of Invention]

The hologram seal according to the present invention is a hologram seal in which a reflective metal thin film layer and a hologram layer are provided on a heat-sensitive adhesive layer, wherein the hologram layer has thermoformability and is solid ultraviolet curable. A resin or electron beam curable resin film, and a hologram master plate having interference fringes corresponding to the wavefront of light from an object formed on the hologram in the form of unevenness on the surface, under the condition that the curable resin film is heated. It is characterized in that it is pressed so as to come into contact with the hologram original plate below to form irregularities on the curable resin film, and then is cured by irradiation with ultraviolet rays or an electron beam.

[Specific Description of the Invention]

 The present invention will be described below with reference to specific examples shown in the drawings.

The hologram sticker 1a according to the first aspect of the present invention has a cross-sectional view as shown in FIG.
The reflective metal thin film layer 4 and the hologram layer 5 are provided in this order via the adhesive layer 3. Hologram layer 5
In the above, the uneven pattern, which is an interference fringe corresponding to the wavefront of the light from the object, is provided on the side in contact with the reflective metal thin film layer 4. Further, an oversheet 6 may be provided on the hologram layer 5 if necessary. In some cases, an anchor layer 7 may be provided between the pressure-sensitive adhesive layer 3 and the reflective metal thin film layer 4 to enhance the adhesiveness between the two. In some cases, a protective sheet 8 that can be peeled off more easily can be provided on the oversheet 6.

As the release paper 2, used is a base material such as paper or film which is made of silicon resin, wax, paraffins, or the like.

As the pressure-sensitive adhesive layer, general pressure-sensitive adhesives such as acrylic type and rubber type can be widely used.

The hologram layer 5 is composed of a thermosetting resin that is cured by ultraviolet rays or electron beams or a resin obtained by curing a thermosetting resin that has a thermoforming property, and a hologram is formed in an uneven pattern on the surface of these resins. As will be described later, this hologram layer 5 is formed by a duplication method using a hologram master plate on the surface of which interference fringes corresponding to the wavefront of light from an object are formed in an uneven pattern. The hologram layer 5 has a thickness of 0.1 to 50 μm, preferably 0.5 to 5 μm.

The resin for the hologram layer that can be used in the present invention can be thermoformed at the time of molding (reproduction) of the hologram, and after the hologram is formed, that is, at the time of transfer, it is necessary that it has heat resistance enough to withstand the heat at the time of transfer. is there. Examples of such resin include so-called ultraviolet curable resin, electron beam curable resin,
A thermosetting resin, a spontaneous curing type reactive resin layer, or the like may be used. In particular, when productivity is taken into consideration, a resin curable with ultraviolet rays or electron beams is suitable.

Specific examples of such a resin include methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate,
Propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isoamyl acrylate, isoamyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethylene glycol di Acrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane diacrylate , Trimethylolpropane dimethacrylate, / pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene glycol diglycidyl ether diacrylate, Ethylene glycol diglycidyl ether dimethacrylate, polyethylene glycol diglycidyl ether diacrylate, polyethylene glycol diglycidyl ether dimethacrylate, propyl glycol diglycidyl ether diacrylate, propyl glycol diglycidyl ether dimethacrylate,
Monomers having radically polymerizable unsaturated groups such as polypropylene glycol diglycidyl ether diacrylate, polypropylene glycol diglycidyl ether dimethacrylate, sorbitol tetraglycidyl ether tetraacrylate, and sorbitol tetraglycidyl ether tetramethacrylate may be used.

Further, in the present invention, an ultraviolet ray or electron beam curable resin having thermoformability can be used. As such a resin, a resin obtained by introducing a radical unsaturated group into a polymer obtained by polymerizing or copolymerizing the following compounds (1) to (2) described below is used.

Monomers having hydroxyl groups: N-methylol acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2- Hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, etc.

Monomers having a carboxyl group: acrylic acid, methacrylic acid, acryloyloxyethyl monosuccinate, etc.

Monomers having epoxy groups: glycidyl methacrylate and the like.

Monomers having an aziridinyl group: 2-aziridinylethyl methacrylate, allyl 2-aziridinylpropionate and the like.

Monomers having amino groups: acrylamide, methacrylamide, diacetone acrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like.

Monomer with sulfone group: 2-acrylamido-2-
Methyl propane sulfonic acid etc.

Monomers having isocyanate groups: 1,4-toluene diisocyanate and 2-hydroxyethyl acrylate, such as an adduct of 1 mol to 1 mol of diisocyanate and a radical-polymerizable monomer having active hydrogen.

Further, in order to control the glass transition point of the above copolymer or the physical properties of the cured film, the above compound and the following monomer copolymerizable with this compound are copolymerized. It can be polymerized. Examples of such a copolymerizable monomer include methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate and t-.
Examples thereof include butyl acrylate, t-butyl methacrylate, isoamyl acrylate, isoamyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and the like.

Next, the polymer obtained as described above is reacted according to the following methods (a) to (d) to introduce a radically polymerizable unsaturated group, whereby ultraviolet rays or electrons having thermoformability are obtained. A line curable resin is obtained.

(A) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as acrylic acid or methacrylic acid is subjected to a condensation reaction.

(B) In the case of a polymer or copolymer of a monomer having a carboxyl group or a sulfone group, the above-mentioned monomer having a hydroxyl group is subjected to a condensation reaction.

(C) In the case of a polymer or copolymer of a monomer having an epoxy group, an isocyanate group or an aziridinyl group, the above-mentioned monomer having a hydroxyl group or a monomer having a carboxyl group is subjected to an addition reaction.

(D) In the case of a monomer or copolymer having a hydroxyl group or a carboxyl group, 1 of an epoxy group-containing monomer, an aziridinyl group-containing monomer or a diisocyanate compound and a hydroxyl group-containing acrylate monomer The addition reaction may be carried out with an adduct of 1 mol.

Further, the above-mentioned monomer and the above-mentioned moldable ultraviolet ray or electron beam curable resin may be mixed and used.

Further, although the above-mentioned ones can be sufficiently cured by electron beams, when they are cured by irradiation with ultraviolet rays, benzoquinone, benzoin, benzoin ethers such as benzoin methyl ether, halogenated acetophenones, piertyls as sensitizers. Those that generate radicals by irradiation with ultraviolet rays, such as, can also be used.

The reflective metal thin film layer 4 is for providing reflectivity to the hologram layer 5, and is made of Cr, Ti, Fe, Co, Ni, Cu, Ag, Au, Ge, A.
It is formed by using a metal such as l, Mg, Sb, Pb, Pd, Cd, Bi, Sn, Se, In, Ga, Rb and the oxides and nitrides thereof alone or in combination of two or more. Of these metals, Al, Cr, Ni, Ag,
Au and the like are particularly preferable.

The thickness of the reflective metal thin film layer 4 is preferably 10 to 10,000Å, more preferably 200 to 2000Å.

Although this reflective metal thin film layer 4 may not be necessary, it is preferably present.

The oversheet 6 serves to protect the hologram layer 5 and increase the mechanical strength of the entire card, and is preferably made of a highly transparent material in order to keep the hologram layer 5 visible from the outside. . As the oversheet 6, polyvinyl chloride, polyester acrylic resin, epoxy resin, amide resin, urethane resin or the like can be used. The thickness of the oversheet 6 is preferably 0.2 to 200 μm.

The anchor layer 7 plays a role of enhancing the adhesiveness between the reflective metal thin film layer 4 and the adhesive layer 3. As the anchor layer 7, conventionally known ones such as vinyl chloride-vinyl acetate copolymer, acrylic resin, urethane resin, epoxy resin and polyester resin can be widely used. The thickness of this anchor layer is 0.02 to 10 μm, preferably 0.2 to 2
It is preferably μm.

As the protective sheet 8, various kinds of weakly adhesively processed films are used.

Next, the hologram seal 1b according to the second aspect of the present invention will be described. This hologram seal 1b has a reflective metal thin film layer 4 and a hologram layer 5 provided in this order on a heat-sensitive adhesive layer 9 as shown in the sectional view of FIG. In the hologram layer 5, the uneven pattern is provided on the side in contact with the reflective metal thin film layer 4. If necessary, an oversheet 6 may be provided on the hologram layer 5, and an anchor for improving the adhesiveness between the heat-sensitive adhesive layer 9 and the reflective metal thin film layer 4 may be provided. Layer 7 may be provided. In some cases, a protective sheet 8 that can be peeled off more easily can be provided on the oversheet 6.

As the heat-sensitive adhesive layer 9, a conventionally known one such as an olefin resin, a vinyl resin, an acrylic resin, an amide resin, a polyester resin, a rubber resin, or a styrene copolymer resin can be used.

The reflective metal thin film layer 4, the hologram layer 5, the oversheet 6, and the anchor layer 7 are the same as those of the hologram seal 1a according to the first aspect of the present invention.

Next, an example of the method for manufacturing the hologram seal according to the present invention will be described.

The hologram seal of the first aspect is formed as follows. That is, on the hologram transfer substrate sheet,
A hologram forming film is formed by providing the above-mentioned resin through a peeling layer and an overprint layer as necessary, and the hologram forming film and the hologram original plate are contacted so that the resin layer of the film contacts the hologram original plate. Then, the resin is cured by irradiating ultraviolet rays or electron beams or by further applying heat while heating and pressing the resin to form an uneven pattern on the surface of the resin.

When the hologram original plate and the hologram forming film are heated and pressure-bonded, a heating and pressure-bonding means such as a heating roll can be used. At this time, the temperature of the heating roll is the type of resin to be used, the material of the base film, the thickness, etc. Although it varies greatly depending on the temperature, it is generally suitable that the temperature is 100 to 200 ° C. Further, the hologram original plate and the hologram forming film are 0.1 kg / cm ² or more, preferably 1 kg / c
It is preferable to perform the pressure contact under a pressure of m ² or more.

At this time, in the case of irradiating with an ultraviolet ray or an electron beam, the irradiation intensity may be irradiated again after peeling the film having the irregularities of the hologram of the hologram master plate formed thereon from the plate, so that the resin can be sufficiently cured. preferable. Ultraviolet rays,
The irradiation dose of the electron beam needs to be appropriately determined according to the resin used.

When forming a hologram using a thermoformable ultraviolet ray or electron beam curable resin, in the same manner as when using a conventional general thermoplastic resin, the unevenness of the hologram is formed under heating and pressure contact in that state. After cooling, the film may be peeled off to duplicate the hologram, and then the resin may be cured by irradiation with ultraviolet rays or electron beams.

Next, the reflective metal thin film layer 4 is applied. This reflective metal thin film layer can be provided on the hologram layer by a sputtering method, an ion plating method, a vacuum vapor deposition method or the like.

Next, an anchor layer is provided on the reflective metal thin film layer 4 if necessary, and then an adhesive layer is provided to prepare a hologram transfer sheet.

Next, by transferring this hologram transfer sheet onto the release paper 2, the hologram seal of the first aspect of the present invention can be obtained.

The hologram seal of the second aspect is formed as follows. That is, in the same manner as the hologram seal of the first aspect, a peeling layer,
A hologram transfer sheet may be prepared by forming the overprint layer, the resin, the reflective metal thin film layer and the anchor layer, and the hologram transfer sheet may be transferred onto the heat-sensitive adhesive layer.

Incidentally, the type of ultraviolet curable resin and electron beam curable resin that have been conventionally used are generally in a liquid state, and thus are extremely sticky when applied on a substrate film, and therefore, the conventional type on the substrate film A hologram-forming film formed by applying a UV or electron beam curable resin cannot be wound up and stored, and the UV curable resin is applied on the base material film just before contact with the hologram master plate. Although there is a problem that a hologram forming film has to be formed, the hologram forming film according to the present invention is formed of a specific resin, does not become sticky, and can be wound and stored. It has the advantage of

〔The invention's effect〕

Since the hologram layer of the hologram seal according to the present invention is made of a specific resin, the following effects can be obtained.

(A) A hologram having excellent heat resistance is provided, and it can be formed by applying heat during attachment.

(B) A hologram having a hard surface and hardly scratched can be obtained.

(C) A hologram having excellent solvent resistance can be obtained.

[Brief description of drawings]

1 and 2 are sectional views of the hologram seal according to the present invention. 1 ... Hologram seal, 2 ... Release layer, 3 ... Adhesive layer, 4 ... Reflective metal thin film layer, 5 ... Hologram layer, 6
…… Oversheet, 7 …… Anchor layer, 8 …… Protective layer, 9 …… Heat sensitive adhesive layer.

Claims (1)

[Claims] 1. A hologram seal having a reflective metal thin film layer and a hologram layer provided on a heat-sensitive adhesive layer, wherein the hologram layer has thermoformability and is solid ultraviolet curable resin or electron. A linear curable resin film, and a hologram master in which interference fringes corresponding to the wavefront of light from an object are formed on the hologram in the form of irregularities on the surface, under the condition that the curable resin film is heated, A hologram seal, wherein the hologram master plate is pressed and brought into contact with the hologram master plate to form concavities and convexities on the curable resin film, and then cured by being irradiated with an ultraviolet ray or an electron beam.