JP4390898B2 - Method for producing discoloration-deposited printed matter - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a method for producing a color-changing deposition prints available for color changes anti-counterfeiting and decorative purposes by viewing angles observing.
[0002]
[Prior art]
Media and printed materials that have a rainbow-like color by spectrally reflecting reflected light using holograms and diffraction gratings are used as anti-counterfeiting and decorative printing techniques. In addition, a medium and printing ink whose color changes depending on an angle using a polarizing film or a scale-like pearl pigment used in a liquid crystal display device are used for the same purpose.
However, when producing holograms and diffraction gratings, the images taken on resist-coated plates subjected to interference exposure are etched to create irregularities to form diffraction patterns, or a stencil engraved using a cutting device is used. It takes time and effort to produce an image such as making a diffraction pattern by making a template with an unevenness drawn by an electron beam drawing apparatus, and it is necessary to duplicate this plate on a medium for making a medium.
As an example of a method for manufacturing a sheet having such a diffraction grating or hologram layer, there is a technique described in Japanese Patent Application Laid-Open No. 4-104188. However, it is necessary to duplicate the diffraction grating or hologram layer on one side of the sheet. There is a high cost.
[0003]
On the other hand, in the case of pearl printing, although the printed pattern is free, it is necessary to increase the thickness of the printing ink, which increases the cost and restricts the printing substrate and application. When a polarizing film for liquid crystal is used, there is a problem that the cost is high and it is difficult to form a pattern, and there are few applicable media types.
[0004]
[Problems to be solved by the invention]
In order to solve the above problems, an object of the present invention is to obtain an angle discoloration effect similar to that of a hologram and a diffraction grating, and to eliminate a time-consuming plate making / duplicating process from the medium manufacturing process.
[0008]
[Means for Solving the Problems]
For solving the above problems, a first method for producing discoloration deposition printed matter, a method for producing a color-changing deposition prints color by viewing angles observing changes, on the expansion and contraction less substrate, unsaturated The step of applying a radiation curable resin composition comprising 100 parts by weight of an unsaturated ethylene oligomer to 10 to 100 parts by weight of an ethylene monomer, and the extent that the applied resin composition is not completely cured Next , a process of changing the unsaturated bond ratio to a semi-cured resin layer in which the unsaturated bond ratio is less than 100% to 40% or more remaining in an uncured state by irradiating ultraviolet rays or an electron beam , metal deposition on the surface of the semi-cured resin layer A step of forming a layer, a step of heat-treating the entire base material and the semi-cured resin layer to completely cure the resin layer and forming a fine uneven shape on the resin layer and the metal vapor-deposited layer, metal Providing a printed layer on the wear layer, it is the print layer process for producing color-changing deposition printed matter characterized in that it comprises a step, etching the metal deposition layer as a resist, the. Since it is a manufacturing method of this discoloration vapor deposition printed matter, the vapor deposition printed matter which can be utilized for various uses, such as forgery prevention and a decoration purpose, can be manufactured easily.
[0009]
A second method for producing a color-changing vapor-deposited printed matter for solving the above-mentioned problems is the method for producing a color-changing vapor-deposited printed matter according to claim 1, wherein 10 to 100 weights of unsaturated ethylene monomer is formed on a substrate with little expansion and contraction. the step of applying a radiation-curable resin composition obtained by blending 100 parts by weight of the unsaturated ethylene oligomers relative parts, next to the, to the surface of the radiation curable resin composition step of transferring a hologram pattern, the It is in the manufacturing method of the color-change vapor deposition printed matter characterized by adding . Since it is a manufacturing method of this discoloration vapor deposition printed matter, the vapor deposition printed matter which can be utilized for various uses, such as forgery prevention and a decoration purpose, can be manufactured easily.
[0010]
A third method for producing a color-changing vapor-deposited printed matter for solving the above-mentioned problems is the method for producing a color-changing vapor-deposited printed matter according to claim 1, wherein 10 to 100 weights of an unsaturated ethylene monomer is formed on a substrate with little expansion and contraction. the step of transferring the step of applying an unsaturated ethylene oligomers by blending 100 parts by weight of the radiation curable resin composition, next to a diffraction grating pattern on the surface of the radiation curable resin composition with respect to parts, the method of manufacturing color-changing deposition printed matter characterized by comprising adding to, in.
4th of the manufacturing method of the color-changeable vapor-deposited printed matter for solving the said subject is a manufacturing method of the color-changeable vapor-deposited printed matter in any one of Claims 1-3, It peels previously on a base material with little expansion / contraction. A step of providing a layer, and a method for producing a color-changing vapor-deposited printed matter.
Since it is a manufacturing method of this discoloration vapor deposition printed matter, the vapor deposition printed matter which can be utilized for various uses, such as forgery prevention and a decoration purpose, can be manufactured easily.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, when the radiation curable resin is cross-linked to a low cross-linking density state, the semi-cured composition does not have sufficient heat resistance, and when high heat is applied, the semi-cured layer is heated. This is a phenomenon utilizing a phenomenon in which a fine concavo-convex shape is generated based on a difference in elongation from the substrate. That is, if unevenness occurs in the subsequent heat process of the base material and the resin layer, the resin layer is cured 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, if a metal vapor deposition film is formed on the surface of the resin layer, the uneven shape remains in the arrangement of the metal vapor deposition particles following the resin, so that a fine uneven shape pattern is generated and fixed.
Such a fine concavo-convex pattern has a regular streak shape with a pitch of about 1 to 2 μm, and thus has a characteristic that the color changes depending on the viewing angle, like the hologram pattern and the diffraction grating pattern. Furthermore, printing is performed on the metal vapor deposition layer, and the metal vapor deposition layer is partially etched away using the print layer as a resist, so that more specific decorative curing is exhibited. In addition, since such a medium can be continuously produced in large quantities under certain conditions, it can be directly produced as a seven-color angle-changeable vapor-deposited print without the need to prepare a duplicate plate or perform a duplication process, and can be used for various applications.
[0012]
If you apply heat sealant or adhesive to the surface of the angular discoloration deposited printed matter thus produced and process it on a transfer medium, etc., you can form a pattern with any foil pressing pattern, and similarly cut the heat sealant applied When a ribbon is formed, a free pattern can be formed, for example, by transfer using a thermal head. Such a metal-deposited surface has a natural diffractive color, but has a color effect similar to that of a hologram and is excellent as a decorative material, and is also useful as an anti-counterfeiting material because it is thin and fragile. In addition, by superimposing a hologram pattern or diffraction pattern on this radiation curable resin for duplication, even when a simple hologram pattern or the like is used, a pattern having a large color change effect can be formed by combining the two.
[0013]
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a perspective view showing the discoloration-deposited printed matter of the present invention and the state of use thereof. 1A is a perspective view of the medium, and FIG. 1B is a diagram illustrating a state when the medium is used.
As shown in FIG. 1 (A), the discoloration-deposited printed matter 1 of the present invention has a resin layer 13h obtained by curing a radiation-curable resin on a base material 11 with or without a release layer 12, and further a metal vapor-deposited layer. 14 and the printing layer 15 are provided, and the metal vapor deposition layer 14 has a shape synchronized with the printing layer 15. Finally, a heat sealant or adhesive 16 is provided on the outermost surface. In the case of applying an adhesive, a protective release paper (not shown) is further provided, and in the actual use, the protective release paper is peeled off, and the article etc. displayed in a state where the top and bottom are reversed from the state of FIG. In many cases, it is used as it is. Thus, when it sticks to an article | item and uses it in a label state, since it is desirable that the base material 11 and the hardened resin layer 13h are couple | bonded firmly, it is normal not to use the peeling layer 12. FIG.
[0014]
FIG. 1B is a diagram illustrating another method of using the color-changing vapor-deposited printed matter 1. In this case, the heat sealant 16 is heated and attached to the article, and then the substrate 11 is peeled off and used. This is often the case when used for vulnerable anti-counterfeiting media. The metal vapor-deposited layer 14 is formed with stripe-shaped fine irregularities that produce a light diffraction effect, and light incident on the irregular surface is diffracted separately for each color light. Since the portion where the metal vapor deposition layer has been removed does not produce a diffraction effect, the surface state of the article can be observed, and when the article is a printed matter, the design can be visually recognized.
When used as a ribbon for a thermal head, it is used in the same manner, and is heated with a thermal head from the side of the substrate 11, stuck on a paper surface or the like with an HS agent, and simultaneously transferred to the substrate 11.
[0015]
2 and 3 are cross-sectional views showing a process for producing a color-changing vapor-deposited printed matter, and FIG. 4 is a cross-sectional view showing a production process of another form of the color-changing vapor-deposited printed matter.
First, as shown in FIG. 2 (A), a radiation curable resin composition 13 is applied to a base material 11 having high heat resistance and relatively little expansion / contraction with or without a release layer 12 interposed therebetween. It is not necessary to provide the release layer when the cured resin composition is easily peelable from the substrate or when the release is not intended as described above. In order to facilitate peeling, it is preferably formed in a thin layer of 2 to 3 μm or less. The coating thickness of the radiation curable resin composition 13 is preferably about 0.5 to 5.0 μm. The release layer 12 and the resin composition 13 can be applied by gravure coating, die coating, roll coating, bar coating, or the like.
Subsequently, as shown in FIG. 2B, 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. As a result, the resin layer becomes a semi-cured resin layer 13s. In order to obtain a semi-cured state, an irradiation amount of about 20 to 50% of normal curing conditions is sufficient.
[0016]
The cured state can be determined by analyzing the infrared absorption spectrum and looking at 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 fully cured state and the unsaturated bond ratio remains at 40% or more of the uncured state. . This is because when the unsaturated bond ratio is 40% or less, the curing proceeds so much that the elongation in the next thermal process does not occur sufficiently. Moreover, it is because it will take time to harden | cure and will not be stabilized as a coating film only by heating when not irradiating at all.
[0017]
Next, as shown in FIG. 2C, a metal vapor deposition layer 14 is provided on the curable resin layer 13. The metal vapor deposition may be performed using 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. The alloy is used for coloring or adjusting the reflectance of the thin film. In the case of using a metal compound, there is an effect that a transparent or semi-transparent vapor deposition layer can be formed by selection thereof. The thickness of the metal vapor-deposited layer 14 is about 100 to 2000 mm because it is preferable that the metal vapor-deposited layer 14 can reflect light. When the vapor deposition layer is a transparent or semi-transparent reflective vapor deposition layer, a special decorative effect can be seen through both the reflected light from the vapor deposition surface and the printed pattern on the lower surface through the vapor deposition layer. Can be demonstrated.
[0018]
In this state, the base material and the semi-cured resin layer formed thereon are introduced into a heating device such as an oven, and the temperature is about 100 ° C to 170 ° C, preferably about 120 ° C to 150 ° C. When the heat is ignited for about 1 minute, the radiation curable resin layer is also completely cured because it is also thermally cured. At this time, streaky fine irregularities having a certain direction are generated in the resin layer and the deposited metal layer. . The reason for this phenomenon has not been elucidated in detail, but the shape is generated even immediately after the heating load and before returning to room temperature. Since the elongation is larger than the elongation rate of the base material, it is understood that a fine uneven shape is formed in the resin layer (FIG. 2D).
[0019]
The pitch, shape, directionality and the like of the unevenness vary depending on the characteristics of the substrate, the presence or absence of the release layer, and the resin composition. Moreover, since it changes also with the extending | stretching characteristic of a base material, or the application | coating conditions of a composition, in order to set it as a fixed shape, it is necessary to manage those conditions.
In general, a base material stretched and heat-set has a small heat shrinkage, and a heat shrinkage is large when the base material is not stretched or is not heat-set even when stretched. Also in the case of stretching, a difference occurs in the direction of shrinkage depending on whether it is uniaxial stretching or biaxial stretching. The relationship between the elongation and shrinkage characteristics of the base material and the elongation rate of 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 how the uneven shape is generated in which direction. However, it is understood that not only the influence of the tension at the time of heating, but also the uneven shape occurs even when the same sheet is heat-treated in an unloaded tension state. As described above, there are various factors of change, but if a base material manufactured under a certain condition is used and a predetermined coating material is applied and processed under the same condition, a medium giving a substantially constant color change can be obtained. Therefore, there is no problem in industrial mass production.
[0020]
Even if the fine uneven shape is removed by heating and cooled to room temperature, the uneven shape of the resin layer remains as it is, so that the fine uneven shape 14p of the metal vapor deposition layer also maintains the uneven shape as it is, and has a crimped or streak fine uneven shape. Generate and settle.
Even this vapor deposition medium itself has a sufficient decorative effect. However, in the present invention, the following processing is additionally performed in order to provide a further decorative effect.
As shown in FIG. 2E, a printing layer 15 made of printing color ink or transparent ink is applied on the metal vapor-deposited layer on which fine irregularities are formed, using printing ink durable to alkali treatment. The printing ink is usually on the side that is not directly visible in the transferred state, but if it is a transparent ink, the transparency of the entire printed matter can be improved, which is advantageous when a transparent vapor deposition film is used. Next, in order to etch the metal vapor deposition layer 14 using this printing ink or transparent ink 15 as a resist, when the entire film is passed through an alkaline hot water solution, the portion of the metal layer without the printing ink dissolves and disappears. Therefore, the metal vapor deposition layer has a pattern that is completely synchronized with the printing layer. As the alkaline solution, a bulk soda solution having a concentration of about 1 to several percent is usually used (FIG. 3F).
[0021]
In this state, if a heat sealant or adhesive 16 is applied to the metal vapor-deposited surface, it can be used as a transfer foil or label, and a pattern can be formed by foil-pressing an arbitrary picture simultaneously with or after transfer. Further, if a heat sealant is applied and chopped 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. 3G).
[0022]
FIG. 4 shows a manufacturing process in the case where a hologram pattern or a diffraction grating pattern is provided so as to overlap with a fine uneven shape. In this case, after applying the radiation curable resin composition 13 on the base material 11 with or without the release layer 12, the photosensitive resin was hologram-exposed in advance in another process and patterned by etching. A hologram plate 17 produced by nickel plating on the hologram plate surface and transferring the hologram micro-emboss is pressed (FIG. 4B) to copy the hologram pattern. Since the radiation-curable resin is embossed with a hologram mold in an uncured state, the surface hardness of the composition 13 needs to be soft in order to correctly copy the hologram mold, and the pencil hardness before curing is 6B. ˜2B, preferably F˜2H after curing. In a continuous process, embossing of the hologram mold is performed between a mold formed in a roll shape and a pressing roll.
[0023]
After replicating 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. As a result, the resin layer becomes a semi-cured resin layer 13s (FIG. 4C). Next, metal deposition is performed on the resin layer 13s. Metal vapor deposition is performed in the same manner as in FIG. 2 (FIG. 4D). In this state, the base material and the semi-cured resin layer formed thereon are introduced into a heating device such as an oven, and the temperature is about 100 ° C to 170 ° C, preferably about 120 ° C to 150 ° C. By igniting for about 1 minute, a hologram pattern 17p by embossing and a fine concavo-convex shape 14p appear in combination on the surface of the metal vapor-deposited layer 14 and the cured resin layer 13 (FIG. 4E). The subsequent steps are the same as those in FIG. 2 or FIG.
The hologram pattern is the same even if it is a diffraction grating pattern. In this case, a diffraction grating plate formed by grinding or the like is used.
[0024]
FIG. 5 is a diagram showing a surface state of fine irregularities when no release layer is provided. The state of the metal vapor deposition layer surface before a printing process is shown. 5A is a plan view, and FIG. 5B is a surface unevenness chart measured by AFM (“Nanoscope 3” manufactured by Digital Instrument Co., Ltd.) between both ends of XY in FIG. 5A. ing. In FIG. 5A, the distance between XY is 50 μm. FIG. 5B is a chart showing the surface state irregularities between the XY, and the average pitch between the irregularities of the fine irregularities is 1.953 μm, and the height difference between * 1 and * 2 is 157.13 nm. Yes. The uneven shape is more random than the diffraction grating pattern created by mechanical grinding or photoetching technology, but it appears to form a stripe pattern similar to the hologram pattern created by optical photography. It is done. However, the randomness in the depth direction tends to increase (depth control does not work).
[0025]
FIG. 6 is a diagram showing a surface state when a release layer is provided. 6A is a plan view thereof, and FIG. 6B is a chart of the same measuring device between both ends of the PQ in FIG. 6A. In FIG. 6A, the distance between PQs is 58 μm. FIG. 6B is a chart showing the surface state unevenness between the PQs. The average unevenness of the fine unevenness is 1.367 μm, and the height difference between * 3 and * 4 is 43.253 nm. .
The above conditions are the same except for the thickness of the base material and the release layer, and when there is a release layer, the uneven pitch and depth tend to be reduced. The pitch interval of the unevenness is relatively uniform, but the depth control seems to be difficult as in FIG.
In addition, although the said chart is a thing of Example 1 and Example 2 mentioned later, the thickness of 50 micrometer (FIG. 5) and a polyester sheet of 25 micrometers (FIG. 6) are used for a base material sheet, and a web-like raw fabric is used. The flow direction is parallel to the scanning direction of the chart.
[0026]
Such a fine concavo-convex shape produces an angle color change effect under substantially the same conditions as a normal diffraction grating. In FIG. 5, when the average concave / convex pitch interval is calculated as a lattice constant d (d = 1.953 μm), the angle (1) at which the bright part of the diffracted light is generated in relation to the wavelength λ, the incident angle θ, and the diffraction angle φ is (1 ) Is established.
d (sin θ−sin φ) = mλ (1)
m = 1, λ = 550 × 10 ⁻⁹ m (green light), d = 1.953 × 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, φ = 22.0 degrees at λ = 650 × 10 ⁻⁹ m (red light), and φ = 28.5 degrees at λ = 450 × 10 ⁻⁹ m (blue light).
[0027]
The vapor deposition medium thus formed can be used as it is without peeling off the base material 11 as a display label of an article, and the base material 11 is peeled off as a transfer foil, for example, with an arbitrary pattern on a vinyl chloride card base material. An angle-dependent discoloration pattern having the same effect as hologram or pearl printing can be formed on the card.
Further, when used as a transfer foil for hot stamping, it is possible to provide an arbitrary shape on the stamp and press a part of the concavo-convex shape or hologram shape at the same time as pressing the foil so that the color change portion disappears.
Furthermore, a resin having a low glass transition point is used for the release layer 12 and the heat sealant 16, and a thermal head having a lower thermal condition than foil pressing is used by cutting into a thin width and ribbon processing as described above. It can be used as a ribbon for thermal transfer printers.
[0028]
<Examples regarding materials>
(1) Base material sheet A hard base material sheet having high heat resistance and relatively little expansion and contraction is preferred. For example, stretched or unstretched polyethylene terephthalate (PET), polybutylene terephthalate, polyester resins such as polyethylene terephthalate / isophthalate copolymer, polyolefin resins such as polypropylene and polymethylpentene, polyvinyl fluoride, polyvinylidene fluoride, poly Polyfluorinated ethylene resins such as tetrafluoroethylene and ethylene / tetrafluoroethylene copolymers, polyamides such as nylon 6, nylon 6, 6, etc., polyethylene naphthalate (PNT), polyimide, polysulfone, polycarbonate, triacetate, polyvinyl alcohol Such as a sheet or film. These sheets or films may be a single layer or a multilayer, and the substrate thickness is preferably about 10 to 100 μm. When thermal transfer is performed using a thermal head after forming into a ribbon, a thin one is preferable, and a thickness of about 10 to 25 μm can be recommended.
[0029]
(2) Peeling layer resin As the coating resin for the peeling layer, a material that maintains an adhesive state in the production process and becomes easily peelable at the time of use can be selected and used. For example, if the substrate is a PET resin, a methyl methacrylate acrylic resin can be dissolved in a toluene solvent and used.
[0030]
(3) Radiation curable resin composition The radiation curable resin composition used in the present invention has radical polymerizability, and is an unsaturated ethylene monomer 10 which is liquid at normal pressure and a temperature of 20 ° C to 100 ° C. It is characterized by blending 0.05 to 10 parts by weight of a radical photopolymerization initiator and a sensitizer and 100 parts by weight of an unsaturated ethylene oligomer with respect to -100 parts by weight.
The unsaturated ethylenic monomer used in the radiation curable resin composition of the present invention is a liquid, radical polymerizable polymer at normal pressure and a temperature of 20 ° C. to 100 ° C., and includes 2-ethylhexyl acrylate, 2-hydroxy Various acrylates such as ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, tetrahydroxyfurfuryl methacrylate, phenoxyethyl acrylate, tetrahydrofurfuryloxyethyl arylate, tetrahydrofurfuryloxyhexanolide acrylate Can be illustrated. Various urethane acrylates, epoxy acrylates, and acrylamides may also be used.
As the oligomer, those having a low polymerization degree can be used.
[0031]
Since the unsaturated ethylene monomer needs to maintain a monomer state when handling the photosensitive resin at normal temperature and normal pressure, it needs to be liquid at normal pressure and a temperature of 20 ° C to 100 ° C. To do.
Since the radiation curable resin composition used in the present invention is not subjected to hologram exposure, it is not necessary to be a high-sensitivity hologram recording material used for hologram imaging. In other words, high-sensitivity hologram recording materials that can be recorded by exposure at 10 to 100 mJ / cm ² are generally used. Of course, such photosensitive materials can also be used. Other than those requiring extremely long exposure, low sensitivity is sufficient.
[0032]
Next, as radical photopolymerization initiators, benzoin alkyl ethers, ketals, oxime esters, benzophenone, thioxanthone derivatives, aromatic ketones such as quinone and thioacridone, 1,3-di (t-butyldioxylcarbonyl) Benzene), peroxyacid esters such as 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone, iodonium salts, alkyl or alkyl borates such as dianine, rhodamine, safranine, malachite green, methylene blue, Examples thereof include iron-arene complexes, bisimidazoles, and N-aryl glycines. Examples of the sensitizer include 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, benzoflavine, Examples include dianine, phthalocyanine, porphine, rhodamine, safranine, malachite green, and methylene green.
[0033]
The above radical photopolymerization initiator and sensitizer are generally most effective when used at a ratio of 0.05 to 10 parts by weight with respect to 100 parts by weight of the unsaturated ethylene monomer. If the blending amount is less than 0.05 parts by weight, the light absorption amount is small and not effective. If the blending amount exceeds 10 parts by weight, the light absorption becomes excessive, and the initiator is exposed to a peripheral high bridge even when irradiated with ultraviolet light for curing. This is because a problem arises in that the radical cannot be transferred due to being fixed in the formed molecule. However, in the production of the color-changing vapor-deposited printed matter of the present invention, it is not necessary to have a completely cured state at the time of curing with radiation. is there.
[0034]
(4) Heat sealant Various materials of hot melt type and thermoplastic type can be used. Epoxy resin-based, vinyl acetate-based, urethane-based, polyvinyl acetate-based resins and the like are generally used.
(5) Adhesives It is possible to use various adhesives such as solvent type and emulsion type in which tackifiers and plasticizers are added to butyl rubber, natural rubber, silicon, SBR, and polyisobutylene adhesive components. it can.
[0035]
【Example】
Embodiments of the present invention will be described below with reference to FIGS.
Example 1
An ultraviolet curable resin composition having the following composition was applied to a web-like biaxially stretched polyethylene terephthalate film (“Lumirror 50T60” manufactured by Toray Industries, Inc.) having a thickness of 50 μm without providing a release layer.
(composition)
Unsaturated ethylene monomer 20 parts by weight Unsaturated ethylene oligomer 80 parts by weight Sensitizer 0.3 part by weight Methyl ethyl ketone 30 parts by weight Viscosity at the time of application of this composition is 25 ° C as measured by Zaan Cup # 3 27 seconds.
After coating, the composition was brought into a semi-cured state by irradiating with ultraviolet light from a metal halide lamp at 500 mJ / cm ² . When the degree of crosslinking in the semi-cured state was measured with an FT-IR infrared spectrophotometer, it was revealed that 55% of the double bonds of the composition were in an uncrosslinked state.
[0036]
The aluminum vapor deposition layer 400 Å is formed on the semi-cured resin layer 13 s (FIG. 2C) and controlled to flow in a drying zone at 100 ° C. for 20 seconds or longer. As shown in FIG. 5 (A), streak-like fine irregularities almost perpendicular to the web flow occurred. The average pitch of the concavo-convex shape was 1.953 μm, and the average concavo-convex depth was 0.26 μm. This metal deposition surface has a seven-color diffraction color that naturally changes color depending on the angle.
A gravure pattern was printed on the metal vapor-deposited layer on which fine irregularities were formed using an alkali-resistant gravure ink (“VM-PEAL” manufactured by Dainichi Seika Kogyo Co., Ltd.) (FIG. 2E). Next, when this printing ink 15 was used as a resist and the entire film was passed through a 1% NaOH (loading soda) solution, the portion of the metal layer without the printing ink dissolved and disappeared (FIG. 3 (F)).
[0037]
Thereafter, an SBR pressure-sensitive adhesive was applied to the thickness of 25 μm on the aluminum vapor-deposited layer (FIG. 3G) to complete a vapor-deposited printed matter. The vapor-deposited printed material thus produced could be used as a label and exert a sufficient color change effect.
[0038]
(Example 2)
A methyl methacrylate acrylic resin was diluted with toluene as a release layer on a web-like biaxially stretched polyethylene terephthalate film (“Lumirror 25T60” manufactured by Toray Industries, Inc.) having a thickness of 25 μm and applied to a thickness of 1 μm.
On top of that, the same ultraviolet curable resin composition as in Example 1 was applied to a thickness of 2 μm. The viscosity of the composition at the time of coating was also the same as in Example 1.
After coating, the composition was brought into a semi-cured state by irradiating with ultraviolet light from a metal halide lamp at 500 mJ / cm ² . When the degree of crosslinking in the semi-cured state was measured with an FT-IR infrared spectrophotometer, it was revealed that 52% of the double bonds in the composition were in an uncrosslinked state.
[0039]
On the semi-cured resin layer 13s, a substantially transparent metal vapor deposition layer 14 made of zinc sulfide was formed to a thickness of 400 mm (FIG. 2C). After that, when it was controlled to flow for 20 seconds or more in a drying zone at 100 ° C., streaky fine irregularities almost perpendicular to the web flow occurred in the resin layer and the transparent vapor deposition layer as shown in FIG. . The average pitch of the concavo-convex shape was 1.367 μm, and the average concavo-convex depth was 0.31 μm.
A gravure pattern is printed on the metal vapor-deposited layer on which fine irregularities are formed using alkali-resistant gravure transparent ink ("VM-PEAL" manufactured by Dainichi Seika Kogyo Co., Ltd.) (Figure 2 (E)). The alkali treatment was performed in the same manner as in Example 1 (FIG. 3F). Thereafter, a vinyl chloride heat-sealing agent was applied to the transparent reflective vapor-deposited layer to a thickness of 4.0 μm (FIG. 3 (G)) to complete a vapor-deposited printed matter.
The vapor-deposited printed material produced in this way is used as a transfer foil, transferred to a vinyl chloride card substrate with an arbitrary pattern, and the substrate is peeled off. The angle-dependent color has the same effect as hologram or pearl printing on the card. The handle could be made. Moreover, since the vapor deposition layer became a transparent reflective vapor deposition layer, the pattern on a card | curd could be observed through a vapor deposition layer, and the outstanding decoration effect was exhibited.
[0040]
(Example 3)
A methyl methacrylate acrylic resin was diluted with toluene and applied as a release layer to a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm (“Lumirror 16S28” manufactured by Toray Industries, Inc.).
On top of that, the same ultraviolet curable resin composition as in Example 1 was applied to a thickness of 2 μm.
The viscosity of the composition at the time of coating was also the same as in Example 1. After coating, the composition was brought into a semi-cured state by irradiating with UV light from a UV metal halide lamp at 500 mJ / cm ² . When the degree of crosslinking in the semi-cured state was measured with an FT-IR infrared spectrophotometer, it was revealed that 50% of the double bonds in the composition were in an uncrosslinked state.
Subsequently, hologram resist was printed on the resist resin in a separate process, and the hologram mold plate patterned by etching was nickel-plated, and hologram hologram embossing 17 was transferred to the plated surface, and the hologram mold plate 17 was pressed to replicate the hologram. Later (FIG. 4B), the coating resin was irradiated with 500 mJ / cm ² of UV light from a UV metal halide lamp to be in a semi-cured state. When the degree of crosslinking in the semi-cured state was measured with an FT-IR infrared spectrophotometer, it was revealed that 50% of the double bonds in the composition were in an uncrosslinked state.
[0041]
On the semi-cured resin layer 13s, an aluminum vapor deposition layer 14 was formed to a thickness of 400 mm (FIG. 4D). After that, when it was controlled to flow in a drying zone at 100 ° C. for 20 seconds or longer, streaky fine irregularities almost perpendicular to the web flow were generated in the resin layer and the aluminum vapor deposition layer (FIG. 4E). . The average pitch of the concavo-convex shape was 1.654 μm, and the average concavo-convex depth was 0.29 μm.
A gravure pattern is printed on the metal vapor-deposited layer on which the fine concavo-convex shape is formed using an alkali-resistant gravure ink ("VM-PEAL" manufactured by Dainichi Seika Kogyo Co., Ltd.) and subjected to alkali treatment in the same manner as in Example 1. went. Thereafter, a vinyl chloride-based HS agent was applied to a thickness of 4.0 μm on the aluminum vapor-deposited layer to complete a vapor-deposited printed matter.
[0042]
This vapor-deposited printed material has seven-color diffraction colors that naturally change color depending on the angle, and a complicated color change pattern is formed in a portion overlapping the hologram pattern. Using the vapor-deposited printed material thus produced as a transfer foil, it is transferred to a vinyl chloride card substrate with an arbitrary pattern and the substrate is peeled off, and the angle-dependent color has the same effect as hologram or pearl printing on the card. The handle could be made.
Moreover, when it was cut into a narrow width of 10 mm and used as a thermal transfer ribbon, an angle-dependent color pattern could be transferred with a thermal head.
[0043]
【The invention's effect】
As described above, the discolorable vapor-deposited printed matter of the present invention is obtained by forming a diffraction grating-like fine uneven shape on the surface when the radiation-curable resin composition is heated in a semi-cured state, and the shape is converted into a metal. By fixing to the vapor deposition layer, it was possible to obtain a color-changeable vapor-deposited printed matter that causes a color change due to a change in viewing angle. Such a vapor-deposited printed material can be used as various decorative materials and anti-counterfeit media.
Since the conventional method for manufacturing such a medium is obtained through the formation of a diffraction grating pattern or a hologram pattern and a replication process, the manufacturing cost is high. In the method for producing a color-changing vapor-deposited printed matter of the present invention, a color-changing vapor-deposited printed matter that exhibits the same effect can be produced in a large amount and at a low cost by a completely different method from the conventional method.
[Brief description of the drawings]
FIG. 1 is a perspective view showing a color-changing vapor-deposited printed material according to the present invention and a use state thereof.
FIG. 2 is a cross-sectional view showing a process for producing a color-changeable vapor-deposited print according to the present invention.
FIG. 3 is a cross-sectional view illustrating a process for producing a color-changing vapor-deposited print according to the present invention.
FIG. 4 is a cross-sectional view showing a manufacturing process of another embodiment of the discolorable vapor-deposited printed matter of the present invention.
FIG. 5 is a diagram showing a surface state when no release layer is provided.
FIG. 6 is a diagram showing a surface state when a release layer is provided.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Color change vapor deposition printed material 11 Base material 12 Release layer 13 Radiation hardening type resin 13s Semi-hardened resin layer 13h Hardened resin layer 14 Metal vapor deposition layer 14p Fine uneven | corrugated shape 15 Print layer 16 Heat seal agent or adhesive 17 Hologram type plate

Claims (4)

A method for producing a color-changing vapor-deposited printed matter whose color changes depending on the viewing angle to be observed, and 100 parts by weight of an unsaturated ethylene oligomer on 10 to 100 parts by weight of an unsaturated ethylene monomer on a base material with little stretching The step of applying the radiation curable resin composition to be blended, to the extent that the applied resin composition is not completely cured, is irradiated with ultraviolet rays or electron beams , the unsaturated bond ratio is in an uncured state The step of changing to a semi-cured resin layer that is less than 100% to 40% or more , the step of forming a metal vapor deposition layer on the surface of the semi-cured resin layer, the entire base material and the semi-cured resin layer are heat-treated The step of completely curing the resin layer and forming a fine uneven shape on the resin layer and the metal vapor deposition layer, providing a print layer on the metal vapor deposition layer, and using the print layer as a resist, the metal vapor deposition layer Method of manufacturing a color-changing deposition printed matter characterized in that it comprises the step of etching, the. The method of manufacturing a color-changing deposition printed matter according to claim 1, stretch less substrate on radiation curing type obtained by blending 100 parts by weight of the unsaturated ethylene oligomers relative to 10 to 100 parts by weight of the unsaturated ethylene monomer A method for producing a color-changing vapor-deposited printed matter, comprising adding a step of transferring a hologram pattern onto the surface of a radiation curable resin composition , followed by a step of applying a resin composition. The method of manufacturing a color-changing deposition printed matter according to claim 1, stretch less substrate on radiation curing type obtained by blending 100 parts by weight of the unsaturated ethylene oligomers relative to 10 to 100 parts by weight of the unsaturated ethylene monomer A method for producing a color-changing vapor-deposited printed matter, comprising adding a step of transferring a diffraction grating pattern to the surface of a radiation curable resin composition , followed by a step of applying a resin composition. The method for producing a color-changing vapor-deposited printed matter according to any one of claims 1 to 3, further comprising a step of providing a release layer in advance on a base material with little expansion and contraction. Production method.

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