JP2000264000A - Color-changing vapor deposition medium and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color-changing vapor deposition medium changing colors and a manufacturing method thereof. SOLUTION: Colors are changed by the visual angles to be observed for a color-changing vapor deposition transfer medium, and a cured radiation curable resin composition 13h and a metal vapor deposition layer 14 are formed successively in the above order on a base 11, and fine recessed and projected shape formed based on the difference of elongation of the base when the radiation curable resin composition is heated. An adhesive agent or a heat seal agent 15 can be applied on the metal vapor deposition layer, and hologram patterns or diffraction grating patterns can be formed overlappingly on the recessed and projected shape. The yellow magnetic radiation is emitted after applying a radiation curable resin composition on the base so that the resin composition is in the semi-cured state, and then the metal vapor deposition layer formed by heating and the fine recessed and projected shape thus formed is fixed on a vapor deposition layer to manufacture the color-changing vapor deposition transfer medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a discolorable vapor deposition medium whose color changes depending on the viewing angle at which it is observed and which can be used for forgery prevention and decoration purposes, and a method for producing the same.

[0002]

2. Description of the Related Art A medium or printed matter having a rainbow color by separating reflected light by a hologram or a diffraction grating is used as a technology for preventing forgery or for decorative printing. In addition, a polarizing film or a flake-shaped pearl pigment used for a liquid crystal display device and a medium or a printing ink whose color changes depending on an angle are used for the same purpose. However, when producing holograms and diffraction gratings, images taken on a resist-coated plate that has been subjected to interference exposure are etched to create irregularities and use them as a diffraction pattern, or a stencil engraved using a cutting device. It was troublesome to make an image, for example, by making a mold or by making a mold on which concavities and convexities were drawn by an electron beam drawing apparatus, and making a diffraction pattern, and it was necessary to duplicate this plate on a medium in order to make it into a medium. As an example of a method of manufacturing a sheet having such a diffraction grating or a hologram layer, Japanese Patent Application Laid-Open No.
There is a technique described in Japanese Patent No. 104188, but it is necessary to duplicate and form a diffraction grating or a hologram layer on one side of a sheet, which increases the cost.

[0003] On the other hand, in the case of pearl printing, the printing pattern is free, but a thick printing ink is required, which increases the cost and restricts the printing base material and application. When a polarizing film for liquid crystal is used, there is a problem that the price is high, the pattern is difficult to form, and there are few applicable media types.

[0004]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a medium capable of obtaining the same angular discoloration effect as a hologram and a diffraction grating. The purpose is to eliminate such plate making and duplicating steps.

[0005]

Means for Solving the Problems A first aspect of the discolorable deposition medium for solving the above-mentioned problems is a discolorable deposition medium whose color changes according to a viewing angle to be observed, and which is cured on a substrate. A radiation-curable resin composition and a metal-deposited layer are sequentially provided, and the metal-deposited layer has a fine structure based on a difference in elongation between the radiation-curable resin composition and a base material when the radiation-curable resin composition is heated. The discoloration deposition medium is characterized in that the irregular shape is formed. Since such a discolorable vapor deposition medium is used, it can be used for various applications such as forgery prevention and decorative purposes.

[0006] The second aspect of the discolorable vapor deposition medium for solving the above-mentioned problem is a discolorable vapor deposition medium whose color changes depending on the viewing angle at which it is observed. And a metal deposition layer are sequentially provided,
The metal vapor deposition layer is characterized in that a hologram pattern and a fine uneven shape based on a difference in elongation between the radiation-curable resin composition and the substrate when heated are formed so as to overlap with each other. Discolorable deposition media. Since such a discolorable vapor deposition medium is used, it can be used for various applications such as forgery prevention and decorative purposes.

A third aspect of the present invention is to provide a discolorable vapor deposition medium whose color changes depending on the viewing angle at which it is observed. The radiation curable resin composition is cured on a substrate. And a metal deposition layer are sequentially provided,
The metal deposition layer is characterized in that the diffraction grating pattern and the fine unevenness based on the difference in elongation with the substrate when the radiation-curable resin composition is heated are formed so as to overlap. Discolorable deposition medium. Since such a discolorable vapor deposition medium is used, it can be used for various applications such as forgery prevention and decorative purposes.

A first method for producing a discolorable vapor deposition medium for solving the above-mentioned problems is a method for producing a discolorable vapor deposition medium whose color changes depending on a viewing angle at which the medium is observed. A step of applying a radiation-curable resin composition,
A step of irradiating the applied resin composition to a degree that the resin composition is not completely cured to change the resin layer into a semi-cured state, a step of forming a metal-deposited layer on the surface of the semi-cured resin layer, a base material, and Heat-treating the entire resin layer in a semi-cured state to completely cure the resin layer and form fine irregularities on the resin layer and the metal deposition layer. Manufacturing method. Since the method for producing a discolorable deposition medium is used, a deposition medium that can be used for various purposes such as forgery prevention and decoration purposes can be easily produced.

A second method for producing a discolorable vapor deposition medium for solving the above-mentioned problem is a method for producing a discolorable vapor deposition medium whose color changes depending on the viewing angle at which it is observed. A step of applying a radiation-curable resin composition,
Transferring the hologram pattern to the surface of the radiation-curable resin composition, irradiating the coated resin composition with radiation to such an extent that the resin composition is not completely cured, and changing the resin composition into a semi-cured resin layer; Step of forming a metal vapor deposition layer on the surface of the resin layer, heat-treating the entire substrate and semi-cured resin layer to completely cure the resin layer and to form fine irregularities on the resin layer and metal vapor deposition layer Forming a discolorable vapor deposition medium. Since the method for producing a discolorable deposition medium is used, a deposition medium that can be used for various purposes such as forgery prevention and decoration purposes can be easily produced.

A third method of manufacturing a discolorable vapor deposition medium for solving the above-mentioned problem is a method for producing a discolorable vapor deposition medium whose color changes depending on a viewing angle for observing. A step of applying a radiation-curable resin composition,
Transferring the diffraction grating pattern to the surface of the radiation-curable resin composition, irradiating the coated resin composition with radiation to such an extent that the resin composition is not completely cured, and converting the resin composition into a semi-cured resin layer, Step of forming a metal vapor deposition layer on the surface of the resin layer in the state, heat treatment of the entire base material and the resin layer in the semi-cured state completely cures the resin layer and fine irregularities on the resin layer and the metal vapor deposition layer A method for producing a discolorable vapor deposition medium, comprising a step of forming a shape. Since the method for producing a discolorable deposition medium is used, a deposition medium that can be used for various purposes such as forgery prevention and decoration purposes can be easily produced.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a method of producing a composition in which a radiation-curable resin is cross-linked to a low cross-link density state, and the composition in a semi-cured state has insufficient heat resistance. This utilizes a phenomenon in which a layer in a cured state is stretched by heat and a fine uneven shape is generated based on a difference in elongation from a substrate.
That is, if unevenness occurs in the subsequent thermal process of the base material and the resin layer, the resin layer is thermoset as it is or the unsaturated bond is saturated and lost, so that the resin layer is fixed without returning to the original planar state. At this time, when a metal vapor-deposited film is formed on the surface of the resin layer, the irregularities follow the resin and remain in the arrangement of the metal vapor-deposited particles. Such fine uneven pattern is 1-2.
Since it has a regular streak-like shape with a pitch of about μm, the color changes according to the viewing angle as in the case of the hologram pattern and the diffraction grating pattern. In addition, since such a medium can be continuously mass-produced under certain conditions, it can be directly manufactured as a seven-color angle-discoloring deposition medium without preparing a duplicate plate or performing a duplication step, and can be used for various purposes.

If a heat sealing agent or a pressure-sensitive adhesive is applied to the surface of the thus produced angle-discoloring deposition medium and processed into a transfer medium or the like, a pattern can be formed by an arbitrary foil pressing pattern. When the ribbon is cut into small pieces, a free pattern can be formed by, for example, transfer using a thermal head. Although such a metal-deposited surface has a natural diffraction color, it has a color effect similar to that of a hologram and is excellent as a decoration material, and is also useful as a forgery prevention material because of its thin and fragile properties. Also,
By superimposing and duplicating a hologram pattern or a diffraction pattern on this radiation-curable resin, even when a simple hologram pattern or the like is used, a pattern having a large discoloration effect can be formed by combining them.

An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 is a perspective view showing a discolorable vapor deposition medium of the present invention and a use state thereof. FIG. 1A is a perspective view of a medium,
FIG. 1B is a diagram showing a state when a medium is used. FIG.
As shown in (A), the discolorable deposition medium 1 of the present invention comprises a substrate 11
Has a cured resin layer 13h of a radiation-curable resin with or without a release layer 12, and further has a metal deposition layer 14
And a heat sealant or pressure-sensitive adhesive 15 on the outermost surface. In the case of applying an adhesive, a protective release paper (not shown) is further provided, and the protective release paper is peeled off in actual use, and an article or the like displayed upside down from the state of FIG. It is often used by sticking it directly to In the case where the base material 11 and the cured resin layer 13h are firmly bonded to each other when they are attached to an article and used in a label state as described above, the release layer 12 is usually not used because it is desirable that the hardened resin layer 13h be firmly bonded. FIG. 1B is a diagram showing another method of using the discolorable deposition medium. In this case, after the heat sealant 15 is heated and attached to the article, the base material 11 is peeled off and used.
This is often the case when used for vulnerable anti-counterfeit media. The metal deposition layer 14 is formed with a stripe-shaped fine unevenness that causes a light diffraction effect, and the light incident on the uneven surface is diffracted by being separated for each color light. It is used in the same way when used as a ribbon for thermal head,
The substrate 11 is peeled off at the same time that the substrate 11 is heated from the side of the substrate 11 by a thermal head, adhered to a paper or the like with an HS agent and transferred.

FIG. 2 is a cross-sectional view showing a manufacturing process of the discolorable deposition medium, and FIG. 3 is a cross-sectional view showing another embodiment of the discolorable deposition medium. First, as shown in FIG. 2A, a release layer 12 is formed on a substrate 11 having high heat resistance and relatively small expansion and contraction.
The radiation-curable resin composition 13 is applied with or without intermediary. The release layer does not need to be provided when the cured resin composition is easily peelable from the substrate or when the purpose of the release is not as described above. In order to facilitate peeling, it is preferable to form a thin layer having a thickness of 2 to 3 μm or less. The coating thickness of the radiation-curable resin composition 13 is 0.5 to
About 5.0 μm is preferable. Release layer 12 and resin composition 1
3 can be applied by gravure coating, die coating, roll coating, bar coating, or the like. Subsequently, FIG.
As shown in (B), radiation 5 such as ultraviolet rays and electron beams is applied to such an extent that the curable resin composition 13 is not completely cured.
As a result, the resin layer becomes a semi-cured resin layer 13s. In order to obtain a semi-cured state, a normal curing condition of 20
An irradiation dose of about 50% is sufficient.

[0015] The cured state can be determined by analyzing the infrared absorption spectrum and observing the decay of unsaturated bonds before and after irradiation. Experimentally, it has been confirmed that good results can be obtained when the crosslink density is insufficient compared to the completely cured state and the unsaturated bond ratio remains at least 40% of the uncured state. . If the unsaturated bond ratio is 40% or less, the curing proceeds excessively, and the elongation in the next thermal process does not sufficiently occur. In addition, if only heating without irradiation with radiation is performed, it takes a long time to cure, and the film is not stable.

Next, as shown in FIG. 2C, the curable resin layer 1
A metal deposition layer 14 is provided on 3. For the metal deposition, a bright single component metal such as aluminum, chromium, nickel or silver, or an alloy such as bronze, brass or white copper, or a metal compound such as oxide or sulfide can also be used. The alloy is used for coloring or adjusting the reflectance of the coating film. When a metal compound is used, there is an effect that a transparent or translucent deposited layer can be formed by its selection. The thickness of the metal deposition layer 14 is preferably about 100 to 2000 ° since it is sufficient that the metal evaporation layer 14 can reflect light and is preferably a thin layer. When the vapor deposition layer is a transparent or translucent reflective vapor deposition layer, both the reflected light from the vapor deposition surface and the printed pattern on the lower surface of the vapor deposition layer can be visually recognized together with a special decorative effect. Can be demonstrated.

In this state, the substrate and the resin layer in a semi-cured state formed thereon are introduced into a heating device such as an oven and heated to about 100 ° C. to 170 ° C., preferably 120 ° C.
When heated at a temperature of about 150 ° C. for about 1 minute, the radiation-curable resin layer is completely cured because it is also thermally cured,
At that time, fine streaky irregularities having a certain directionality are generated in the resin layer and the vapor-deposited metal layer. Although the reason for this phenomenon has not been elucidated in detail, since the shape occurs even immediately after the heating load and before returning to room temperature, the resin layer elongates during heating, It is understood that since the elongation is greater than the elongation of the base material, fine irregularities are formed in the resin layer (FIG. 2D).

The pitch, shape, directionality, etc. of the irregularities vary depending on the characteristics of the substrate, the presence or absence of a release layer, and the resin composition. In addition, since it changes depending on the stretching characteristics of the base material and the application conditions of the composition, it is necessary to manage those conditions in order to obtain a constant shape. In general, a substrate stretched and heat-set has a small heat shrinkage, and a large heat shrinkage occurs in an unstretched state or in a base material which is not heat-set even when stretched. In the case of stretching, there is a difference in the direction of shrinkage depending on whether the film is uniaxial or biaxial.
The relationship between the elongation and shrinkage characteristics of the base material and the elongation ratio with the semi-cured radiation-curable resin composition affects the uneven shape. Further, since there is a problem of the tension applied to the sheet during heating, it cannot be determined that the uneven shape is generated in any direction in any direction. However, even when the same sheet is heat-treated under a no-load tension state, an uneven shape is generated, so it is understood that the influence is not only the effect of the tension at the time of heating. Although there are various factors as described above, if a predetermined coating material is applied and processed under the same conditions using a base material manufactured under constant conditions, a medium that gives a substantially constant color change can be obtained. There is no problem in mass production industrially.

Even if the fine irregularities are removed by heating and cooled to room temperature, the irregularities of the resin layer remain as they are, so that the fine irregularities 14p of the metal vapor deposition layer also maintain the irregularities as they are and the crepe-like fine irregularities are formed. Generate and fix. If a heat sealing agent or an adhesive 15 is applied to the metal-deposited surface in this state, it can be used as a transfer foil or label, and a pattern can be formed by pressing an arbitrary pattern simultaneously or after transfer. Further, if a heat sealing agent is applied and cut into a long ribbon having a width of several millimeters to several centimeters, it can be used as a thermal transfer ribbon by a thermal head (FIG. 2E).

FIG. 3 shows a manufacturing process in the case where a hologram pattern or a diffraction grating pattern is provided so as to be superimposed on the fine irregularities. In this case, after the radiation-curable resin composition 13 was applied on the base material 11 with or without the interposition of the release layer 12, a hologram exposure was performed on the photosensitive resin in another step in advance to form a pattern by etching. The hologram pattern is nickel-plated, the hologram micro-emboss is transferred, and the hologram pattern 16 produced by pressing is pressed (FIG. 3B), and the hologram pattern is copied. Since the radiation-curable resin is embossed in a hologram type in an uncured state, the composition 13 must have a soft surface hardness in order to correctly capture the hologram type, and the pencil hardness before curing is 6B. ~ 2B, after curing F ~
It is desirable to be 2H. In a continuous process, embossing of the hologram mold is performed between the roll-shaped mold and the pressing roll.

After copying the hologram mold, radiation 5 such as ultraviolet rays and electron beams is irradiated to such an extent that the curable resin composition 13 is not completely cured. Thus, the resin layer becomes a semi-cured resin layer 13s (FIG. 3C). Next, the resin layer 13
Metal deposition is performed on s. Metal deposition is performed in the same manner as in FIG. 2 (FIG. 3D). In this state, the substrate and the resin layer in a semi-cured state formed thereon are introduced into a heating device such as an oven and heated to 100 ° C. to 170 ° C., preferably 12 ° C.
By igniting at a temperature of about 0 ° C. to 150 ° C. for about 1 minute, a hologram pattern 16p formed by embossing and a fine uneven shape 14p appear on the surface of the metal deposition layer 14 and the cured resin layer 13 in a complex manner. (FIG. 3E). Subsequent steps are the same as in FIG. The same applies to a hologram pattern having a diffraction grating pattern. In this case, a diffraction grating type plate formed by grinding or the like is used.

FIG. 4 is a diagram showing the surface state of the fine unevenness when no release layer is provided. FIG. 4A is a plan view thereof, and FIG. 4B is an AF view between XY ends in FIG. 4A.
3 shows a surface unevenness chart measured by M (“Nanoscope 3” manufactured by Digital Instrument Co., Ltd.). In FIG. 4A, the distance between XY is 50 μm. FIG. 4B is a chart showing the unevenness of the surface state between the X and Y, and the average pitch between the unevenness of the fine unevenness is 1.953 μm.
m, the height difference between * 1 and * 2 has been measured to be 157.13 nm. The irregular shape has greater randomness than a diffraction grating pattern created by mechanical grinding or photo-etching technology, but appears to form a stripe pattern similar to a hologram pattern created by optical imaging. Can be However, the randomness in the depth direction tends to increase (control of the depth does not work).

FIG. 5 is a diagram showing a surface state when a release layer is provided. FIG. 5A is a plan view thereof, and FIG. 5B is a chart of the same measuring device between both ends of the PQ in FIG. 5A. In FIG. 5A, the distance between PQs is 58 μm. FIG. 5B is a chart showing the surface state unevenness between the PQs, and the average pitch between the unevennesses of the fine unevenness is 1.3.
67 μm, the height difference between * 3 and * 4 is 43.253 nm
Is measured. In the above, the conditions other than the thickness of the base material and the release layer are the same, and when there is a release layer, the tendency of the concave-convex pitch and the depth to decrease is recognized. Although the pitch interval of the unevenness is relatively uniform, it is difficult to control the depth as in FIG. The charts are for Examples 1 and 2 described below, but the thickness of the base sheet is 5
The polyester sheets of 0 μm (FIG. 4) and 25 μm (FIG. 5) are used, and the flow direction of the web-like raw material is parallel to the scanning direction of the chart.

Such a fine uneven shape produces an angle color change effect under almost the same conditions as a normal diffraction grating. In FIG. 4, the average uneven pitch interval is set to a lattice constant d (d = 1.95)
(3 μm), the following relational expression (1) is established at an angle at which a bright portion of the diffracted light is generated in relation to the wavelength λ, the incident angle θ, and the diffraction angle φ. d (sin θ−sin φ) = mλ (1) m = 1, λ = 550 × 10 ⁻⁹ m (green light), d = 1.9
53 × 10 ⁻⁶ m When white light is irradiated at an incident angle θ = 45 °, sin φ =
0.451, and the diffraction angle φ = 25.2 degrees. Similarly, for λ = 650 × 10 ⁻⁹ m (red light), φ = 22.0
Degree, λ = 450 × 10 ⁻⁹ m (blue light), φ = 28.
5 degrees.

The vapor deposition medium thus formed can be used as it is as a display label of an article without peeling the base material 11 or as a transfer foil by peeling the base material, for example, to a vinyl chloride card base material. , And an angle-dependent discolorable pattern having the same effect as hologram or pearl printing can be formed on a card. Further, when used as a transfer foil for a hot stamp, it is possible to provide a stamp in an arbitrary shape and simultaneously press the foil and simultaneously press a part of the concavo-convex shape or the hologram shape to eliminate the color-changed portion. Furthermore, a resin having a low glass transition point is used for the release layer 12 and the heat sealant 15,
By cutting the ribbon into a narrow width and processing the ribbon as described above, the ribbon can be used as a ribbon for a thermal transfer printer using a thermal head having a lower thermal condition than foil pressing.

<Example of Material> Base Sheet A hard base sheet having high heat resistance and relatively small expansion and contraction is preferable. For example, stretched or unstretched polyethylene terephthalate (PET), polyester resin such as polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer, polyolefin resin such as polypropylene, polymethylpentene, polyvinyl fluoride, polyvinylidene fluoride, poly Polyfluoroethylene resins such as tetrafluoroethylene, ethylene / 4-fluoroethylene copolymer, polyamides such as nylon 6, nylon 6,6, polyethylene naphthalate (PNT), polyimide, polysulfone, polycarbonate, triacetate, polyvinyl alcohol And the like. These sheets or films may be a single layer or a multilayer, and the thickness of the substrate is 10 to 100 μm.
m is preferable. When performing thermal transfer by a thermal head using a ribbon, it is preferable that the thickness is as thin as possible.
A thickness of about 25 μm can be recommended.

Release Layer Resin As the coating resin for the release layer, it is possible to select and use a material which maintains an adhered state to the above-mentioned base sheet in the manufacturing process and which is easily peelable when used. For example, if the substrate is a PET resin, a methyl methacrylate-based acrylic resin can be used by dissolving it in a toluene solvent.

Radiation-Curable Resin Composition The radiation-curable resin composition used in the present invention has a radical polymerizability and is a liquid unsaturated ethylenic monomer 10 at a normal pressure and a temperature of 20 ° C. to 100 ° C. It is characterized by comprising 0.05 to 10 parts by weight of a photo-radical polymerization initiator and a sensitizer and 100 parts by weight of an unsaturated ethylene-based oligomer with respect to 100 parts by weight. The unsaturated ethylenic monomer used in the radiation-curable resin composition of the present invention may be a normal pressure,
It is liquid at a temperature of 0 ° C. to 100 ° C. and has radical polymerizability, and is 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
Various acrylates such as tetrahydrofurfuryl acrylate, tetrahydroxyfurfuryl methacrylate, phenoxyethyl acrylate, tetrahydrofurfuryloxyethyl allylate, and tetrahydrofurfuryloxy hexanolide acrylate can be exemplified. Further, various urethane acrylates, epoxy acrylates, and acrylamides may be used. In addition, these oligomers having a low degree of polymerization can be used.

The above unsaturated ethylenic monomer can be used at room temperature,
Since it is necessary to maintain the monomer state when handling the photosensitive resin at normal pressure, it is necessary to be liquid at normal pressure and at a temperature of 20 ° C to 100 ° C. The radiation-curable resin composition used in the present invention does not need to be a hologram recording material with high sensitivity used for hologram photographing because it is not subjected to hologram exposure. That is, in the hologram recording material of high sensitivity, those which can be recorded by exposure at 10 to 100 mJ / cm ² are generally used. Of course, such a photosensitive material can also be used. In addition to those requiring extremely long exposures, those with low sensitivity are sufficient.

Next, examples of the photoradical polymerization initiator include aromatic ketones such as benzoin alkyl ethers, ketals, oxime esters, benzophenone, thioxanthone derivatives, quinone, and thioacridone;
Di (t-butyldioxylcarbonylbenzene), 3,
Peroxy acid esters such as 3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone;
Examples thereof include iodonium salts, dianine, rhodamine, safranine, alkyl or alkyl borates such as malachite green and methylene blue, iron-arene complexes, bisimidazoles, and N-arylglycine. As the sensitizer, various visible light sensitizers, for example, aromatic amines such as Michler's ketone, xanthene dyes, thiopyrylium salts, merosinin / quinoline dyes, coumarin / ketocoumarin dyes, acridine orange, benzoflavin, Examples thereof include dianine, phthalocyanine, porphine, rhodamine, safranine, malachite green, and methylene green.

The photo-radical polymerization initiator and the sensitizer are added in an amount of 0.05 to 100 parts by weight of the unsaturated ethylenic monomer.
It is generally most effective to use it in a proportion of 10 to 10 parts by weight. If the amount is less than 0.05 parts by weight, the amount of absorbed light is small and no effect is obtained. If the amount is more than 10 parts by weight, light absorption becomes excessive, and even if ultraviolet light for curing is irradiated, the initiator is highly crosslinked around. This is because there is a problem in that the radicals cannot be moved because they are fixed in the molecule. However, in the production of the vapor deposition medium of the present invention, it is not necessary to bring the film into a completely cured state at the time of curing by radiation, but it is necessary to make the film move when heated, so that it is necessary to make the conditions incomplete.

Heat sealant Various materials of a hot melt type and a thermoplastic type can be used. Epoxy resin-based, vinyl acetate-based, urethane-based, vinyl chloride-vinyl acetate-based resins and the like are generally used. Pressure-Sensitive Agents Various pressure-sensitive adhesives such as solvent-type and emulsion-type adhesives obtained by adding a tackifier or a plasticizer to a butyl rubber-based, natural rubber-based, silicone-based, SBR-based, or polyisobutylene-based adhesive component can be used.

[0033]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to FIGS. (Example 1) An ultraviolet-curable resin composition having the following composition was formed to a thickness of 2 μm without providing a release layer on a biaxially stretched polyethylene terephthalate film having a thickness of 50 μm (“Lumirror 50T60” manufactured by Toray Industries, Inc.). Applied. (Composition) Unsaturated ethylenic monomer 20 parts by weight Unsaturated ethylenic oligomer 80 parts by weight Sensitizer 0.3 parts by weight Methyl ethyl ketone 30 parts by weight The viscosity of this composition at the time of coating was measured using a Zahn cup # 3 and 25. At 27C for 27 seconds. After the application, the composition was irradiated with ultraviolet light from a metal halide lamp at 500 mJ / cm ² to make the composition semi-cured. The degree of crosslinking in the semi-cured state is FT
Measurement by an IR spectrophotometer revealed that 55% of the double bonds in the composition were in an uncrosslinked state.

An aluminum vapor-deposited layer 400 ° is formed on the semi-cured resin layer 13s (FIG. 2C),
When the flow was controlled so as to flow into the drying zone of C for 20 seconds or more, fine streaks and irregularities almost perpendicular to the web flow were generated in the resin layer and the aluminum deposition layer as shown in FIG. 4A. The average pitch of the irregularities is 1.953 μm,
The average unevenness depth was 0.26 μm. The metal-deposited surface naturally came to have a seven-color diffraction color that changed color depending on the angle. Thereafter, an SBR-based pressure-sensitive adhesive was applied to a thickness of 25 μm on the aluminum deposition layer (FIG. 2E) to complete a deposition medium. The vapor deposition medium thus produced was able to exhibit a sufficient color change effect when used as a label.

Example 2 A 25 μm-thick, web-shaped biaxially stretched polyethylene terephthalate film (“Lumirror 25T60” manufactured by Toray Industries, Inc.) was used as a release layer. Coated. The same ultraviolet curable resin composition as in Example 1 was applied thereon to a thickness of 2 μm. The viscosity of the composition at the time of coating was the same as in Example 1. After the application, the composition was irradiated with ultraviolet light from a metal halide lamp at 500 mJ / cm ² to make the composition semi-cured. The degree of crosslinking in the semi-cured state was measured with an FT-IR infrared spectrophotometer, and it was found that 52% of the double bonds of the composition were in an uncrosslinked state.

On the semi-cured resin layer 13s, a substantially transparent metal vapor-deposited layer 14 of zinc sulfide was formed to a thickness of 400 ° (FIG. 2C). After that, when the flow was controlled so as to flow into the drying zone at 100 ° C. for 20 seconds or more, the resin layer and the transparent vapor-deposited layer had fine streaky irregularities almost perpendicular to the flow of the web as shown in FIG. 4A. . The average pitch of the irregularities is 1.367 μm, and the average depth of the irregularities is 0.3 μm.
It was 31 μm. Thereafter, a polyvinyl chloride-based heat sealant was applied to a thickness of 4.0 μm on the transparent reflective vapor deposition layer (FIG. 2).
(E)), a deposition medium was completed. The vapor deposition medium produced in this way was used as a transfer foil and transferred to a vinyl chloride card substrate with an arbitrary pattern and the substrate was peeled off. The angle-dependent color having the same effect as hologram and pearl printing on the card was obtained. A pattern could be made. Further, since the vapor deposition layer was a transparent reflection vapor deposition layer, the pattern on the card could be observed through the vapor deposition layer, and an excellent decorative effect was exhibited.

(Example 3) A web-like 2 having a thickness of 16 μm
As a release layer, a methyl methacrylate acrylic resin was diluted with toluene and applied to an axially stretched polyethylene terephthalate film (“Lumirror 16S28” manufactured by Toray Industries, Inc.). The same ultraviolet curable resin composition as in Example 1 was applied thereon to a thickness of 2 μm. The viscosity of the composition at the time of coating was the same as in Example 1. After application, U
UV light by V metal halide lamp is 500mJ /
The composition was semi-cured by irradiation with cm ² . The degree of crosslinking in the semi-cured state was measured with an FT-IR infrared spectrophotometer, and it was revealed that 53% of the double bonds in the composition were in an uncrosslinked state. Then, in another step, the hologram was exposed to the resist resin in another step, and the hologram template formed by patterning by etching was nickel-plated. After (Fig. 3
(B)) The coating resin was irradiated with ultraviolet rays from a UV metal halide lamp at 500 mJ / cm ² to be in a semi-cured state. The degree of crosslinking in the semi-cured state was measured with an FT-IR infrared spectrophotometer, and it was found that 50% of the double bonds in the composition were in an uncrosslinked state.

On the semi-cured resin layer 13s, an aluminum deposited layer 14 was formed to a thickness of 400 °. Then 100 ° C
When the resin layer and the aluminum vapor-deposited layer 14 were controlled so as to flow in the drying zone for 20 seconds or more, fine streaky irregularities almost perpendicular to the web flow were generated (FIG. 3).
(E)). The average pitch of the uneven shape is 1.654 μm.
m, and the average depth of irregularities was 0.29 μm. In addition, this medium had a seven-color diffraction color that naturally changed color depending on the angle, and a complicated color change pattern was formed in a portion superimposed on the hologram pattern. Using the vapor deposition medium produced in this way as a transfer foil and transferring the desired pattern to the vinyl chloride card base material and peeling the base material,
An angle-dependent color pattern with the same effect as hologram and pearl printing was produced on the card. Further, when it was cut into a narrow width of 10 mm and used as a ribbon for thermal transfer, an angle-dependent color pattern could be transferred.

[0039]

As described above, the discolorable deposition medium of the present invention utilizes the fact that the radiation-curable resin composition is heated in a semi-cured state to produce a diffraction grating-like fine irregularities on the surface. By fixing the shape to the metal vapor deposition layer in this way, it was possible to obtain a discolorable vapor deposition medium in which a color change occurs due to a change in viewing angle. Such a vapor deposition medium can be used as various decorative materials and a forgery prevention medium. The conventional method of manufacturing such a medium is obtained through a process of forming a diffraction grating pattern or a hologram pattern and a duplication step, so that the manufacturing cost is high. According to the method for producing a discolorable deposition medium of the present invention, a discolorable deposition medium exhibiting the same effect can be produced in a large amount at low cost by a method completely different from the conventional method.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a discolorable vapor deposition medium of the present invention and a use state thereof.

FIG. 2 is a cross-sectional view illustrating a manufacturing process of the discolorable deposition medium of the present invention.

FIG. 3 is a cross-sectional view illustrating a manufacturing process of another embodiment of the discolorable deposition medium of the present invention.

FIG. 4 is a diagram illustrating a surface state when a release layer is not provided.

FIG. 5 is a diagram showing a surface state when a release layer is provided.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Discoloration vapor deposition medium 11 Substrate 12 Release layer 13 Radiation curable resin 13s Semi-cured resin layer 13h Cured resin layer 14 Metal vapor deposited layer 14p Fine unevenness 15 Heat sealant or adhesive 16 Hologram type plate

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C005 HA01 HA19 JB08 JB09 LA19 LA20 LA30 2H113 AA04 BA21 BA28 BB32 CA37 CA39 DA04 DA47 EA02 EA09 FA05 FA09 FA29 FA42 2K008 AA00 AA13 BB00 DD14 EE04 FF14 GG05

Claims (22)

[Claims] 1. A discolorable vapor deposition medium whose color changes according to a viewing angle for observation, wherein a cured radiation-curable resin composition and a metal vapor deposited layer are sequentially provided on a base material. A discolorable vapor deposition medium, wherein a fine uneven shape based on a difference in elongation with a substrate when the radiation-curable fat composition is heated is formed in the metal vapor deposition layer. 2. A discolorable deposition medium whose color changes according to a viewing angle for observation, wherein a cured radiation-curable resin composition and a metal deposition layer are sequentially provided on a base material, Discoloration characterized in that a hologram pattern and a fine uneven shape based on a difference in elongation with a substrate when the radiation-curable resin composition is heated are superimposed on the metal deposition layer. Vapor deposition medium. 3. A discolorable deposition medium whose color changes according to a viewing angle for observation, wherein a cured radiation-curable resin composition and a metal deposition layer are sequentially provided on a base material, The metal deposition layer is characterized in that a diffraction grating pattern and a fine uneven shape based on a difference in elongation with the substrate when the radiation-curable resin composition is heated are formed so as to overlap with each other. Discoloration deposition medium. 4. A radiation-curable resin composition comprising 100 parts by weight of an unsaturated ethylene-based oligomer per 10 to 100 parts by weight of an unsaturated ethylene-based monomer. The discolorable deposition medium according to claim 3. 5. The discolorable deposition medium according to claim 1, further comprising a release layer between the substrate and the cured radiation-curable resin composition. 6. The discolorable vapor deposition medium according to claim 1, further comprising a pressure-sensitive adhesive layer provided on the metal vapor deposition layer. 7. The discolorable vapor deposition medium according to claim 1, further comprising a heat sealing agent layer provided on the metal vapor deposition layer. 8. The discoloring deposition medium according to claim 1, wherein the metal of the metal deposition layer has a single metal composition. 9. The discoloring deposition medium according to claim 1, wherein the metal of the metal deposition layer is made of an alloy. 10. The discoloring deposition medium according to claim 1, wherein the metal deposition layer is made of a metal compound. 11. The color-changing evaporation medium according to claim 1, wherein the metal evaporation layer is a transparent reflection evaporation layer. 12. The discolorable vapor deposition medium according to claim 7, wherein the discolorable vapor deposition medium is cut into a ribbon shape so as to be thermally transferred by a thermal head. 13. A method for producing a discolorable vapor deposition medium whose color changes according to a viewing angle for observation, comprising: a step of applying a radiation-curable resin composition on a base material having little expansion and contraction; A step of irradiating radiation to such an extent that the composition is not completely cured to change into a semi-cured resin layer, a step of forming a metal deposition layer on the surface of the semi-cured resin layer, a substrate and a semi-cured resin layer A process of completely curing the resin layer by heat-treating the entire surface of the resin layer and forming fine irregularities on the resin layer and the metal deposition layer. 14. A method for producing a discolorable vapor deposition medium whose color changes according to a viewing angle for observation, comprising a step of applying a radiation-curable resin composition on a base material having little expansion and contraction, Transferring the hologram pattern to the surface of the resin layer, irradiating the coated resin composition with radiation to such an extent that the resin composition is not completely cured, and converting the resin composition into a semi-cured resin layer; A step of forming a vapor-deposited layer, a step of heat-treating the entire base material and the resin layer in a semi-cured state, thereby completely curing the resin layer and forming fine irregularities on the resin layer and the metal-deposited layer. A method for producing a discolorable deposition medium, comprising: 15. A method for producing a discolorable vapor deposition medium whose color changes according to a viewing angle for observation, comprising: a step of applying a radiation-curable resin composition on a base material having little expansion and contraction; Transferring the diffraction grating pattern to the surface of the resin layer, irradiating the coated resin composition with radiation to such an extent that the resin composition is not completely cured, and converting the resin composition into a semi-cured resin layer, A step of forming a metal vapor deposited layer, a step of heating the entire base material and the resin layer in a semi-cured state, thereby completely curing the resin layer and forming fine irregularities on the resin layer and the metal vapor deposited layer, A method for producing a discolorable deposition medium, comprising: 16. The radiation-curable resin composition comprises 100 parts by weight of an unsaturated ethylene-based oligomer per 10 to 100 parts by weight of an unsaturated ethylene-based monomer. The method for producing a discolorable deposition medium according to any one of claims 1 to 15. 17. The method according to claim 1, wherein a release layer is provided between the substrate and the cured radiation-curable resin composition.
The method for producing a discolorable deposition medium according to any one of claims 3 to 16. 18. The method according to claim 13, wherein the metal of the metal deposition layer has a single metal composition. 19. The method according to claim 13, wherein the metal of the metal deposition layer is made of an alloy. 20. The method according to claim 13, wherein the metal deposition layer is made of a metal compound. 21. The method according to claim 13, wherein the metal deposition layer is a transparent reflection deposition. 22. The method according to claim 13, wherein the heat treatment is performed at 100 ° C. for 20 seconds or more.
A method for producing the discolorable deposition medium according to the above.