JP4235071B2 - Method and apparatus for duplicating fine uneven pattern - Google Patents

Description

  The present invention relates to a method and an apparatus for replicating a large number of fine uneven patterns on which relief holograms, diffraction gratings and the like are recorded.

  In the relief hologram and diffraction grating, interference fringes generated by interference of laser light are recorded as a fine uneven pattern. This fine concavo-convex pattern is formed as hundreds to thousands of fine ridges per 1 mm in length.

  When duplicating a fine concavo-convex pattern, copy the fine concavo-convex pattern by creating a duplicate plate material from the original plate on which the interference fringes of the laser beam are directly recorded, and shaping the concavo-convex pattern of the duplicate plate material into a resin material. Can do.

  As a conventional method for replicating a fine uneven pattern, for example, a hologram-forming film in which a thermoplastic and solid ultraviolet curable resin or electron beam curable resin layer is provided on a base film, and light from an object on the surface is provided. After the hologram original plate in which the interference fringes corresponding to the wavefront are formed on the hologram in the form of irregularities are pressed so that the cured resin of the hologram forming film is in contact with the original plate, to form irregularities on the cured resin, A method of curing a cured resin by irradiating with ultraviolet rays or an electron beam is known (see, for example, Patent Document 1).

  Moreover, as a copying apparatus for such a fine concavo-convex pattern, a paper feeding device for mounting a winding roll of a film for forming a hologram formed by providing a solid ultraviolet curable resin having thermoformability on a base film, and A transfer device comprising a heating device for heating the hologram forming film fed from the paper feeding device to soften the resin, and a pair of nip rollers for heating the hologram forming film heated by the heating device; The pair of nip rollers is a pressing device and a transfer device composed of an embossing roller provided with a hologram master on the surface, and a hologram forming film fed from the nip roller is irradiated with ionizing radiation to cure the resin. An apparatus comprising an irradiation device and a winding device for winding a hologram forming film is publicly available. Is (e.g., see Patent Document 2.).

  In addition, as a resin film used for replication of the fine uneven pattern, an ionizing radiation curable resin for forming an uneven pattern by heating and pressing in a solid state at room temperature is provided on the base film, and the base film and the An ionizing radiation curable resin film provided with a release layer that gives peelability to a curable resin is known as a hologram forming film (see, for example, Patent Document 3).

  A conventional method of replicating the relief concavo-convex pattern using a resin that is in a solid state at room temperature will be described with reference to FIG. 4 described in Patent Document 2. As shown in the figure, the hologram-forming film 101 is provided with a UV- or electron-beam curable resin layer 103 having thermoformability on a base film 102 such as polyethylene terephthalate. The resin 103 having thermoformability is solid at room temperature and can be wound up without sticking to the surface when provided on the base film 102. Further, the hologram master 104 records hologram information by unevenness, and is formed on the surface of the embossing roller 105. The embossing roller 105 is formed such that a pressing roller 106 is pressed against the embossing roller 106 side by a pressurizing mechanism. The pressing roller 106 includes a heating device.

  The hologram forming film 101 is guided to the embossing roller 105 and pressed with a constant pressure while being tensioned by the pressing roller 106 and the guide roller 107. Since the surface of the pressing roller 106 is heated, the resin layer 103 is softened and the unevenness of the hologram master 104 is transferred to the resin layer 103. Since the embossing roller 31 is rotating, the resin layer 103 with the unevenness is peeled off from the hologram master 104 in the vicinity of the guide roller 107 with the resin layer 103 in close contact with the hologram master 104. Since the emboss roller 107 is cooled, the resin layer 103 in a softened state is hardened to some extent, and unevenness at the time of transfer is formed in a state where the resin layer 103 is peeled off from the hologram master 104, so that the other state can be maintained. Thereafter, the hologram-forming film 1 having the resin layer 103 with the irregularities formed thereon is cured by irradiating ultraviolet rays or an electron beam to cure the resin layer 103 with the irregularities formed thereon, thereby reproducing the hologram irregularity pattern. A forming film is obtained.

Japanese Patent Publication No. 6-85103 (Claims) Japanese Patent Publication No. 6-85103 (Claims) Japanese Patent Publication No.7-104600 (Claims)

  The conventional duplication method has a problem that it is difficult to increase the duplication speed. In other words, since the duplication resin layer 103 is heated and pressed by the pressing roll 106, the time required for the pressing roll 106 and the resin layer to contact is shortened when the line speed is increased and the duplication is performed at high speed. Therefore, it is necessary to increase the amount of heating applied to the resin layer 103 and heat the resin layer from the pressing roll 106 in a short time.

  In order to increase this heating amount, it is necessary to raise the temperature of the pressing roll 106. However, when the temperature of the pressing roll 106 is increased, damage to the base film 102 of the hologram forming film 101 in direct contact with the roll is increased. The damage caused by heat of the base film has a limit in increasing the heating temperature of the pressing roll 106, since the base film is deformed to cause an appearance defect.

  In order to heat the hologram forming resin layer 103, a means for heating the embossing roller 105 side is also conceivable. However, since the hologram master 104 is in a heated state, and the resin layer 103 after the formation of the unevenness is peeled off from the hologram master 104 in the vicinity of the guide roll 107, the resin layer 103 is not cooled sufficiently, There is a problem in that it is not fixed and does not peel off from the hologram master 104.

  Further, it is conceivable to reduce the thickness of the base film 102 of the hologram forming film 101 to improve the heat conduction from the pressing roll 106 to the hologram forming resin 103, and to efficiently heat the base film 102. There is a limit to reducing the thickness of the sheet, and that alone is not sufficient for high-speed replication.

  The present invention has been made in view of the above-mentioned drawbacks of the prior art, and an object of the present invention is to provide a method for duplicating a concave / convex pattern capable of high-speed duplication by increasing duplication speed. It is another object of the present invention to provide a concavo-convex pattern duplicating apparatus capable of reliably performing the above-described high-speed duplication.

The present invention
(1) Using a replication plate material provided with a relief layer corresponding to the concavo-convex pattern of the replication original plate, and having a photothermal conversion layer provided below the relief layer, a substrate is formed on the surface of the relief layer of the replication plate material Adhering the shaping resin layer of the concavo-convex pattern forming film provided with the shaping resin layer that is solid at room temperature and having thermoformability to the film, and irradiates the photothermal conversion layer of the duplicate plate material with light to heat Heating the shaping resin layer of the concavo-convex pattern forming film by converting, and shaping the concavo-convex pattern of the relief layer on the shaping resin layer to replicate the concavo-convex pattern of the original for duplication Reproduction method of uneven pattern,
(2) The concavo-convex pattern replication method according to (1) above, wherein the shaping resin layer has ionizing radiation curability, and the concavo-convex pattern is cured by irradiating the duplicated shaping resin layer with ionizing radiation,
(3) A concavo-convex pattern forming film supply device for supplying a concavo-convex pattern forming film provided with a base resin film that is solid at room temperature and has a moldable resin layer having thermoformability. A corresponding relief layer, a photothermal conversion layer provided below the relief layer, and the concavo-convex pattern forming film formed so as to be in close contact with the relief layer; and the photothermal conversion layer A concavo-convex pattern duplicating apparatus comprising: a shaping apparatus comprising a light irradiation apparatus for irradiating light; and a winding apparatus for winding the concavo-convex pattern forming film;
(4) The concavo-convex pattern duplicating device according to (3) above, wherein the shaping resin layer has ionizing radiation curability and includes an ionizing radiation irradiating device for irradiating the duplicated shaping resin layer with ionizing radiation,
Is a summary.

  In the replication method of the present invention, in order to heat the shaping resin layer of the film for forming an uneven pattern, the photothermal conversion layer under the relief layer of the duplicate plate material is irradiated with light to form the shaping resin layer from the relief layer side. Compared with the method of heating the shaping resin layer from the substrate sheet side of the film for forming an uneven pattern using a conventional pressing roller or the like, the heating resin is efficiently used to sufficiently heat the shaping resin layer. Heating is possible, and the speed of replication can be increased. That is, the light-to-heat conversion layer is provided below the relief layer, and only the portion of the light-to-heat conversion layer irradiated with spot light is selectively heated to a high temperature. Can be heated. As a result, even when the line speed is increased and duplication is performed at a high speed, the uneven pattern can be reliably formed on the forming resin layer. Furthermore, since the time during which heat is applied to the relief layer of the shaping apparatus can be shortened, the plate separation is improved.

  Furthermore, since the molding resin layer is heated from the relief layer side and the base film is not heated, the replication method of the present invention is applied to the base film like the conventional method of heating from the base film side with a pressing roll or the like. There is no risk of heat damage. Moreover, even if the thickness of the base film is increased, the shaping resin layer can be sufficiently heated. As a result, the stability of the base film can be improved, and the concave / convex pattern can be duplicated with high accuracy.

  Further, in the duplication method of the present invention, it is only necessary that the shaping resin layer of the film for forming a concavo-convex pattern is in close contact with the relief layer of the duplication plate material, and no conventional pressurization is required. Accordingly, since unnecessary pressure is not applied to the base film of the film for forming an uneven pattern, no damage is caused by pressure. Accordingly, even a material that is weak to heat and pressure that could not be used in the conventional duplication method can be used as a base film for a film for forming an uneven pattern, and the range of selection of the base film is widened.

  Further, the duplication method of the present invention can simplify the apparatus because it is not necessary to provide a pressing device or a heating device on the pressing roller. Further, in the conventional method of heating by pressing a pressing roller heated by an electric heater or the like, it is necessary to energize the heater constantly to heat it, so that the power consumption is enormous. On the other hand, in the present invention, if the light irradiation is stopped, the heating can be stopped immediately. Therefore, it is sufficient to energize and irradiate the light only when heating, so that energy efficiency is good and an energy saving effect can be expected.

  The photothermal conversion layer is colored dark because carbon black or the like is used. In the present invention, the photothermal conversion layer is provided on the relief layer side, and the photothermal conversion layer is not provided on the shaping resin layer. Therefore, since the shaping resin layer is not colored in a dark color, the replicated product is not limited to a dark color system, and can be used for a wide range of products up to a light color system.

  Also, when heating the light-to-heat conversion layer by irradiating light, this light irradiation is irradiated in a pattern to heat the light-to-heat conversion layer in a pattern and heat the relief layer in a pattern, On-demand information can be recorded at the same time as the concavo-convex pattern is copied in large quantities.

  By adopting the above configuration, the replication apparatus of the present invention can reliably perform replication when the concavo-convex pattern is replicated at high speed.

  Hereinafter, the present invention will be described in detail with reference to the drawings. As shown in FIG. 1, the method for duplicating the concavo-convex pattern of the present invention is a duplication plate material in which a relief layer 1 corresponding to the concavo-convex pattern of the original plate is provided on the surface, and a photothermal conversion layer 2 is provided below the relief layer 1. 3 and a concavo-convex pattern forming film 6 in which a shaping resin layer 5 made of an ionizing radiation curable resin that is thermoformable at room temperature is provided on the surface of the base film 4 is used. In addition, a light irradiation device 7 for irradiating the photothermal conversion layer 2 of the duplicate plate material 3 with light 8 is provided.

  FIG. 2 is an explanatory diagram showing an outline of an example of the replication apparatus of the present invention. The duplicating apparatus shown in FIG. 2 is a concavo-convex pattern forming film that supplies a concavo-convex pattern forming film 6 provided with a shaping resin layer 4 that is solid at room temperature and has ionizing radiation curability on the surface of a base film 4 Supply device 20, relief layer 1 corresponding to the concave / convex pattern for replication is provided on the surface, photothermal conversion layer 2 is provided under the relief layer 1, and the concave / convex pattern forming film 6 can be in close contact with the relief layer 1 Forming device 30 comprising a replica plate material 3 formed and a light irradiation device 7 for irradiating the photothermal conversion layer 2 with light 8, a forming resin layer 2 of a film for forming a concavo-convex pattern formed with a concavo-convex pattern Are provided with an ionizing radiation irradiation device 50 for irradiating ionizing radiation to cure the shaping resin layer, and a winding device 60 for winding up the film for forming an uneven pattern.

  The duplicate plate material 3 of the shaping apparatus 30 is formed as a cylindrical cylinder, and the relief layer 1 is formed in a roll shape around the surface of the cylinder. Further, the shaping apparatus 30 includes guide rollers 9 and 10 for bringing the uneven pattern forming film 6 into contact with the relief layer 1 so as to be in close contact therewith. In addition, the duplicate plate material 3 of the compounding device 30 is configured to rotate in accordance with the feeding speed of the uneven pattern supply device 20 and the winding speed of the winding device 60.

  In order to form the concave / convex pattern of the replication master on the shaping resin layer, first, the concave / convex pattern forming film 6 is fed out from the concave / convex pattern forming film supply device 20 and sent to the shaping device 30 as shown in FIG. Next, as shown in FIG. 1, the shaping resin layer 5 of the concavo-convex pattern forming film 6 is brought into contact with the relief layer 1 of the shaping apparatus 3, and the concavo-convex pattern forming film 6 is weakly tensioned by the guide rolls 9 and 10, etc. In this way, the shaping resin layer 5 is brought into close contact with the relief layer 1.

  At this time, the shaping resin layer 5 may be in a state of being in close contact with the relief layer 3, and need not be pressurized. However, if air exists between the shaping resin layer 5 and the relief layer 3, the air becomes a heat insulating layer, and heat may not be transferred from the relief layer 3 to the shaping resin layer 5. Be careful not to. Therefore, it is a preferable means to suck the air between the shaping resin layer 5 and the relief layer 3 with a vacuum device or the like.

  Next, as shown in FIG. 1, the light-heat conversion layer 2 of the duplicate plate material 3 is irradiated with light 8 from the light irradiation device 7 while the shaping resin layer 5 is in close contact with the relief layer 1. In the photothermal conversion layer 2, the irradiated light is converted into heat energy and generates heat. The heat generation of the photothermal conversion layer 2 heats the relief layer 1 laminated on the photothermal conversion layer. When the relief layer 1 is heated, the heat is transmitted to the shaping resin layer 5 in contact with the relief layer 1, and the shaping resin layer 5 is thermally softened. The uneven pattern of the relief layer 1 in contact with the softened shaping resin layer 5 is shaped.

  The light 8 emitted from the light source of the light irradiation device 7 is, for example, when the spot-like light having a diameter of 100 μm or less is scanned in a line shape from one end to the other end in the width direction of the duplicate plate material 3, the relief layer 1 is duplicated. Since the printing plate 3 is rotating, the entire relief layer can be heated. The light irradiated in a line on the photothermal conversion layer 2 of the duplicate plate material 3 can cause the photothermal conversion layer 2 to generate heat in a very narrow line. The relief layer 1 in contact with the light-to-heat conversion layer 2 is heated to a narrow linear shape, and the molding resin layer 5 in close contact with the relief layer 1 can be thermally deformed into a narrow linear region. Heat up to instant. In this way, the light-to-heat conversion layer is irradiated with light to generate heat, and the adjacent relief layer is heated by the heat, so that only a very narrow area of the relief layer can be heated, and the portion not irradiated with light is not heated. If the irradiated part is passed, the temperature is lowered and the shaping state is fixed immediately.

  The light irradiation device 7 includes, as a light source, a laser light generation device such as a pulsed carbon dioxide laser, and a light irradiation source such as a halogen heater. The light irradiation device 7 includes a control mechanism that can adjust or turn on the output energy of the light source, an optical system such as a mirror and a lens for adjusting the optical path and focus of the light emitted from the light source, and a light source. A driving device or the like for movement can be provided. As the light irradiation device 7, for example, a laser marker or the like can be used.

  Usually, the light irradiation device 7 is arranged so as to irradiate the light-heat conversion layer 2 with light 8 from the uneven pattern forming film 6 side. Therefore, it is preferable to appropriately select a wavelength of light having a high transmittance with respect to the base film so as not to cause damage when passing through the base film. For example, when a laser beam is used as the light and a polyethylene terephthalate film (sometimes referred to as PET) is used as the base film, a laser beam close to visible light having a high transmittance with respect to PET is appropriately used. Just choose.

  Also, when heating the light-to-heat conversion layer by irradiating light, this light irradiation is irradiated in a pattern to heat the light-to-heat conversion layer in a pattern and heat the relief layer in a pattern, On-demand information can be recorded. As on-demand information, for example, unique information such as an individual ID number can be used. That is, a concave / convex pattern consisting of general information such as a company name or common information is recorded on the entire shaping resin layer, and the unique information is recorded from the gap portion other than the region where the concave / convex pattern is provided or from above the concave / convex pattern. Characters, symbols, and the like are directly drawn and recorded by laser beam scanning so as to form an uneven pattern. In this way, on-demand information can be recorded at the same time as copying a large number of concave and convex patterns of common information. The copy in which the unique information formed in this way is recorded can improve the security safety when it is used as a security card such as an ID card.

  As shown in FIG. 1, the concavo-convex pattern forming film 6 formed with the concavo-convex pattern is peeled off from the surface of the relief layer 1 in the vicinity of the guide roll 10 as the duplicate plate material 3 rotates. In the molding resin layer 5 in contact with and closely contacting the duplicate plate material 3, the portion of the photothermal conversion layer 2 that is irradiated with the light 8 is a narrow width region. It passes immediately. As soon as the shaping resin layer passes through the heating region, the temperature of the shaping resin layer is lowered, the thermoplasticity is lost, and the shaped uneven pattern is fixed. The relief layer 3 in the vicinity of the guide roller 10 is far from the irradiated portion of the light 8 and is sufficiently cooled. As a result, the shaping resin layer 5 loses plasticity and is sufficiently hard, and the shaped uneven pattern is securely held, and the shaping resin layer 5 peels well from the duplicate plate material 3, so that the plate It's also good.

  The uneven pattern forming film 6 that has passed through the guide roll 10 is sent to an ionizing radiation curing device 50 as shown in FIG. The ionizing radiation curing device 50 includes an irradiation source 51 and a cooling roll 52. The ionizing radiation curing device 50 irradiates the uneven pattern forming film 6 with ionizing radiation 53 from the irradiation source 51 to cure the shaping resin layer 5 on which the uneven pattern is shaped. Thereafter, the concavo-convex pattern forming film 6 is wound into a roll by a winding device.

  Although not specifically shown, after the ion-implanted radiation 6 is irradiated to the uneven pattern forming film 6 to cure the shaping resin layer 5, the base film 4 is peeled off, and then the ionizing radiation is irradiated again to completely cure. It is also possible to wind only the shaping resin layer of the concavo-convex pattern forming film. At this time, the dose of ionizing radiation can be appropriately determined depending on the resin used.

  The timing of curing the shaping resin layer 5 may be performed immediately after the formation of the concavo-convex pattern, or once the concavo-convex pattern forming film is wound and stored in a roll shape, the mold is molded at an appropriate time. The resin layer 4 may be cured by irradiating the resin layer 4 with ionizing radiation.

  The material located between the light irradiation device 7 and the photothermal conversion layer 8, such as the base film 4, the shaping resin layer 5, and the relief layer 1 of the uneven pattern forming film 6, is substantially the light irradiation device 7. Any material can be used as long as it can transmit light so that the light irradiated from the light reaches the photothermal conversion layer 8.

  The relief layer 1 of the duplication plate material 3 can be formed as a concavo-convex pattern corresponding to the concavo-convex pattern by a known method from a replication original plate on which the concavo-convex pattern to be duplicated is formed. As the concavo-convex pattern to be replicated, a light diffractive structure such as a relief hologram or a diffraction grating, or a fine concavo-convex pattern such as a hairline is used. The details of the method of creating the relief layer 1 from the replica master and the uneven pattern for replicating will be described later.

  The photothermal conversion layer 2 absorbs the light 8 irradiated from the light irradiation device 7 and transmitted through the concavo-convex pattern forming film 6 and the reef layer 1 and converts it into heat to generate heat. This photothermal conversion layer 2 can be composed of a layer in which a pigment such as carbon black is dissolved or dispersed in a binder resin such as a thermoplastic resin or a thermosetting resin.

  The thickness of the photothermal conversion layer 2 is usually 1 to 5 μm, preferably 2 μm.

  As the dye used in the photothermal conversion layer 2, various pigments other than carbon black can be used depending on the light used. For example, those suitable for semiconductor lasers include cyanine and pyrylium polymethine dyes, phthalocyanine dyes such as copper phthalocyanine, naphthalocyanine dyes, dithiol metal complex dyes, naphthoquinone dyes, anthraquinone dyes, triphenylmethane System dyes, aluminum dyes, diimonium dyes, and the like. The photothermal conversion layer 2 can be formed by a known coating means or the like.

  Examples of the binder resin used for the photothermal conversion layer 2 include polyester, acrylic, epoxy, butyral, acetal, vinyl chloride vinyl acetate copolymer, urethane, and phenoxy. A preferred resin is polyester.

  The uneven pattern forming film 6 is obtained by forming the shaping resin layer 5 on the surface of the base film 4 by a known means. A release layer (not shown) may be provided between the base film 4 and the shaping resin layer 5.

  As the base film 4 of the concavo-convex pattern forming film 6, a film-like material can be used without particular limitation as long as it is a film material. Specifically, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyethylene terephthalate / polyethylene naphthalate co-extruded film, etc. Polyester resins, nylon resins such as nylon 6, nylon 6,6, nylon 610, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, vinyl resins such as polyvinyl chloride, polyacrylate, polymethacrylate, poly Acrylic resins such as methyl methacrylate, imide resins, polyarylate, polysulfone, polyethersulfone, polyphenylene ether, polyphenylene Engineering plastics such as polysulfide (PPS), polyaramid, polyetherketone, polyethernitrile, polyetheretherketone, polyethersulfide, styrene resins such as polycarbonate, ABS resin, cellophane, cellulose triacetate, cellulose diacetate, nitrocellulose And polymer films (plastic film) such as cellulose film. The plastic film may be a stretched film or an unstretched film, but a film stretched in a uniaxial direction or a biaxial direction is preferable from the viewpoint of improving strength.

  In addition to the plastic film, the base film 4 can be a metal film such as paper, synthetic paper, iron, or aluminum. A plastic film is preferable from the viewpoint of light transmittance. The above film may be used alone or as a laminate of two or more. The film thickness of the base film 4 can usually be about 5 to 2000 μm. As the base film 4, a polyester film such as polyethylene terephthalate or polyethylene naphthalate is preferably used because it has heat resistance, dimensional stability, and ionizing radiation resistance, and polyethylene terephthalate is most suitable.

  In addition, the base film 4 is subjected to corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer treatment (also referred to as an anchor coat, adhesion promoter, or easy adhesive) on the coated surface prior to application of the shaping resin layer. Further, easy adhesion treatment such as pre-heat treatment, dust removal treatment, and alkali treatment may be performed. In addition, additives such as a filler, a plasticizer, a colorant, and an antistatic agent may be added to the base film 4 as necessary.

  The ionizing radiation curable resin that is solid at room temperature and has thermoformability used for the shaping resin layer 5 is composed of a thermoplastic substance having a radical polymerizable unsaturated group. Specifically, there are the following two types (1) and (2).

(1) Those having a radical polymerizable unsaturated group in a polymer having a glass transition temperature of 0 to 250 ° C. More specifically, the polymer is a polymer obtained by polymerizing or copolymerizing the following compounds i) to viii) and introducing a radically polymerizable unsaturated group by the methods (a) to (d) described later.

i) Monomers having a hydroxyl group: N-methylolacrylamide, 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, and the like.
ii) Monomers having a carboxyl group: acrylic acid, methacrylic acid, acryloyloxyethyl monosuccinate and the like.
iii) Monomers having an epoxy group: glycidyl methacrylate and the like.
iv) Monomers having an aziridinyl group: 2-aziridinylethyl methacrylate, allyl 2-aziridinylpropionate, and the like.
v) Monomers having an amino group: acrylamide, methacrylamide, diacetone acrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like.
vi) Monomers having a sulfonic group: 2-acrylamido-2-methylpropane sulfonic acid and the like.
vii) Monomer having an isocyanate group: an adduct of a radial polymerizable monomer having an active hydrogen and a diisocyanate such as a 1 mol to 1 mol adduct of 2,4-toluene diisocyanate and 2-hydroxyethyl acrylate.
viii) Further, in order to adjust the glass transition point of the above-mentioned polymer or copolymer, or to adjust the physical properties of the cured film, the above-mentioned compound can be copolymerized with this compound as shown below. A monomer can also be copolymerized. Examples of such copolymerizable monomers 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 and the like.

The following methods (a) to (d) show methods for introducing a radical polymerizable unsaturated group into the above polymer.
(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 aforementioned 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 monomer having a carboxyl group is subjected to an addition reaction.
(D) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, a monomer having an epoxy group, a monomer having an aziridinyl group or a diisocyanate compound and a hydroxyl group-containing acrylate ester Addition reaction of 1 to 1 mole adduct of the body.
In order to perform the above reaction, it is preferable to add a trace amount of a polymerization inhibitor such as hydroquinone and feed dry air.

(2) A compound having a melting point of 0 to 250 ° C. and having a radically polymerizable unsaturated group. Specific examples include stearyl acrylate, stearyl methacrylate, triacryl isocyanurate, cyclohexanediol diacrylate, cyclohexanediol dimethacrylate, spiroglycol diacrylate, and spiroglycol dimethacrylate.

  In addition, as the resin for the shaping resin layer 5, the above (1) and (2) can be mixed and used, and a radical polymerizable unsaturated monomer can be added to them. This radically polymerizable unsaturated monomer improves crosslink density and improves heat resistance upon irradiation with ionizing radiation, and in addition to the aforementioned monomers, ethylene glycol diacrylate, ethylene glycol dimethacrylate, Polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol tetraacrylate, penta Erythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipenta Lithritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene glycol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether dimethacrylate, polyethylene glycol diglycidyl ether diacrylate, polyethylene glycol diglycidyl ether dimethacrylate, propylene glycol diglycidyl ether diacrylate , Propylene glycol diglycidyl ether dimethacrylate, polypropylene glycol diglycidyl ether diacrylate, polypropylene glycol diglycidyl ether dimethacrylate, sorbitol tetraglycidyl ether tetraacrylate, sorbitol tetraglycidyl ether tetramethacrylate, etc. Come against solid content 100 parts by weight of the copolymer mixture described above, it is preferable to use at 0.1 parts by weight.

  The ionizing radiation curable resin can be sufficiently cured by an electron beam. However, when it is cured by ultraviolet irradiation, a photopolymerization initiator such as acetophenones, benzophenones, Michler benzoylbenzoate, α-amino is used. A photopolymerization initiator such as oxime ester, tetramethylmeurum monosulfide, or thioxanthone, and a photosensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine are added as necessary.

  The ionizing radiation curable resin can also be cured by heat energy if an appropriate catalyst is present.

  The ionizing radiation curable resin which is used for the shaping resin layer 5 and is solid at room temperature and has thermoformability is usually 0.1 to 50 μm on the base film 4 when replicating a hologram as an uneven pattern, for example. Preferably, it is formed with a film thickness of 0.5 to 5 μm. This film thickness varies depending on the intended use of the uneven pattern to be replicated.

  The shaping resin layer 5 can be formed on the base film 2 by a known coating method such as spin coating, knife coating, roll coating, or bar coating. Moreover, when it is going to form the shaping resin layer 5 partially on a support body, general printing techniques, such as screen printing and gravure printing, can be used, or a transfer method can be used.

  The concavo-convex pattern-forming film 6 in which the shaping resin layer 5 is formed on the base film 4 is formed so that the shaping resin layer 5 is formed in a solid state at room temperature, and is apparently formed in a dry touch state. Therefore, when the film 6 is once wound up in a roll shape, it can be stored well without sticking the shaping resin layer 5. The stored film 6 is installed and used in the uneven pattern film supply device 20 as necessary.

  When a release layer is formed between the base film 4 and the shaping resin layer 5 on the concavo-convex pattern forming film 6, the release layer between the base film 4 and the shaping resin layer 5 can be peeled off and wear resistant. And printability can be provided. As the release layer, conventionally known ones such as acrylic resins, cellulose resins, vinyl resins, polyester resins, urethane resins, olefin resins, amide resins, and epoxy resins can be widely used. The thickness of the release layer is usually 0.05 to 10 μm, preferably 0.2 to 2 μm.

  As shown in FIG. 2, the shaping resin layer 5 on which the concave / convex pattern is formed peels off from the relief layer 1 of the duplicate plate material 3 in the vicinity of the guide roll 10, and then the concave / convex pattern forming film 6 is irradiated with ionizing radiation. It is sent to the apparatus 50, and the shaping resin layer 5 is irradiated with ionizing radiation from the irradiation source 51 to cure the shaping resin layer 5 three-dimensionally. The shaping resin layer 5 on which the concavo-convex pattern is formed is imparted with heat resistance and solvent resistance. A replica of the concavo-convex pattern is obtained by peeling the substrate film 4 from the concavo-convex pattern forming film 6 which has been irradiated with ionizing radiation to cure the shaping resin layer.

  Further, if necessary, ultraviolet rays or electron beams can be further irradiated after peeling. In that case, the shaping resin layer can be sufficiently cured, and the hardness, heat resistance, solvent resistance and the like can be further improved.

  As the ionizing radiation for curing the shaping resin layer 5, all ultraviolet rays (UV-A, UV-B, UV-C), visible rays, gamma rays, X-rays, electron beams, etc. can be used. Or an electron beam is suitable. As the ionizing radiation irradiation device 50, an ultraviolet lamp such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, or a metal halide lamp is used as a light source when ultraviolet rays are irradiated as ionizing radiation. The wavelength of the ultraviolet light is usually about 200 to 400 nm, and the wavelength may be selected according to the composition of the resin layer. Moreover, the irradiation amount can also be irradiated according to the composition of the resin layer, the output of the ultraviolet lamp and the processing speed.

  When irradiating an electron beam as ionizing radiation, various electron beam accelerators such as Cockloft Walton type, Bande graph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, high frequency type, etc. A device capable of irradiating an electron beam by an electro curtain method, a beam scanning method, or the like is used. Preferably, an “electro curtain” (trade name) capable of irradiating a uniform electron beam in a curtain form from a linear filament can be used. The electron beam is irradiated with electrons having an energy of 100 to 1,000 keV, preferably 100 to 300 keV, with an irradiation amount of about 0.5 to 20 Mrad. The atmosphere during irradiation is performed at an oxygen concentration of 500 ppm or less, and it is usually preferable to perform the irradiation at about 200 ppm.

  In order to form the relief layer 1 of the duplication plate material 3 from the duplication master on which the concavo-convex pattern is formed, a conventionally known method can be used. For example, first of all, an intermediate plate material of several generations is made from a replication master plate (parent) on which a concavo-convex pattern is formed, and an appropriate one of the intermediate plate material is relieved as a copy plate material (also called a printing plate or a stamper). It can be used as layer 1. The replica plate material is made of resin, and is continuously wound on the shaping resin layer of the film for forming a concavo-convex pattern by winding it around the cylinder surface of a duplicating machine formed in a cylinder shape. It is possible to carry out commercial large-scale duplication work inexpensively and easily.

  The relief layer 1 is produced by ionizing radiation after pressing the concave / convex pattern of the replication master on the surface of the ionizing radiation curable resin described in JP-B-6-85103, or simultaneously with the forming. A hologram duplication method (called semi-dry duplication method) that peels off by irradiating and applying a liquid ionizing radiation curable resin to the surface of the original for duplication, and after stretching and shaping, it is irradiated with ionizing radiation For example, a photopolymerization method (referred to as 2P method) in which a stamper is obtained by curing and peeling from a replica master can be used.

  For example, as shown in FIG. 3, the relief layer 1 is formed by sequentially laminating a primer layer 12 and an ionizing radiation curable resin layer 13 on the surface of a substrate 11, and the ionizing radiation curable resin layer 13 is provided with unevenness of an original for duplication. An uneven pattern corresponding to the pattern can be formed and configured. The material of the substrate 11 can be metal, glass, plastic film, etc., but when the shaping apparatus is a shaping roll formed as a cylindrical cylinder as shown in FIG. 1, the surface of the shaping roll is Since the relief layer 1 can be wound and it is easy to substantially transmit the light irradiated from the light irradiation device, a plastic film is preferably used.

  As the plastic film used for the substrate 11, for example, the plastic film exemplified as the substrate film 4 of the uneven pattern forming film 6 can be used.

  For the ionizing radiation curable resin layer 13, a known resin containing a compound having a radical polymerizable unsaturated double bond that is polymerized (cured) by irradiation with ionizing radiation can be used.

  Various uneven patterns such as holograms and diffraction gratings to be replicated by the replication method of the present invention will be described. As an image of a hologram, symbols, letters, numbers, illustrations, etc. can be used in addition to an image obtained by photographing the actual object. The hologram image itself can be used to calculate hologram diffraction gratings, calculate digital images captured with digital cameras, 2D or 3D image data obtained from computer graphics, holographic stereograms, etc. It can also be created by an appropriate means. The diffraction grating can express an image such as a character by its outline.

  As the relief hologram, a hologram or diffraction grating in which the intensity distribution of the interference fringe light due to the interference between the object beam and the reference beam is recorded in a concavo-convex pattern can be applied. Examples of the relief hologram include Fresnel holograms, Fraunhofer holograms, lensless Fourier transform holograms, laser reproduction holograms such as image holograms, and white light reproduction holograms such as rainbow holograms, color holograms utilizing these principles, computer holograms, There are hologram displays, multiplex holograms, holographic stereograms, holographic diffraction gratings, and the like.

  As a diffraction grating, in addition to a holographic diffraction grating using a hologram recording means, a precision lathe, an electron beam drawing apparatus, etc. are used to create a diffraction grating mechanically and in a drawing manner. It is possible to increase the diffraction grating from which the diffraction grating can be obtained.

  These holograms and diffraction gratings may be recorded singly, in multiple recordings, or in combination. In addition, the diffraction grating is an assembly having a plurality of regions having different peak directions and / or peak intervals and / or uneven shape and / or uneven height, that is, a plurality of regions having different diffraction directions are regularly arranged. Or, when combined in a random manner, unique glitter with a design property can be obtained.

It is explanatory drawing which shows the outline of an example of this invention replication method. It is explanatory drawing which shows the outline of an example of this invention duplication apparatus. It is principal part sectional drawing which shows the one aspect | mode of a relief layer. It is explanatory drawing which shows the conventional replication method.

Explanation of symbols

1 Relief layer
2 Photothermal conversion layer
3 Duplicate plate material
4 Base film
5 Molding resin layer
6 Uneven pattern forming film
7 Light irradiation device
8 light
20 Film supply device for forming uneven patterns
30 Molding equipment
60 Winding device

Claims (4)

  Using a replication plate material provided with a relief layer corresponding to the concavo-convex pattern of the replication original plate and provided with a photothermal conversion layer under the relief layer, the surface of the relief layer of the replication plate material has a normal temperature on the substrate film In the solid state, the molding resin layer of the film for forming a concavo-convex pattern provided with a molding resin layer having thermoformability is adhered, and the photothermal conversion layer of the duplicate plate material is irradiated with light and converted into heat. The concavo-convex pattern of the concavo-convex pattern is characterized by: heating the shaping resin layer of the concavo-convex pattern forming film at, and shaping the concavo-convex pattern of the relief layer on the shaping resin layer to replicate the concavo-convex pattern of the original for duplication. Duplication method.   2. The method for replicating a concavo-convex pattern according to claim 1, wherein the shaping resin layer has ionizing radiation curability, and the concavo-convex pattern is cured by irradiating the duplicated shaping resin layer with ionizing radiation.   An uneven pattern forming film supply device for supplying an uneven pattern forming film provided with a moldable resin layer that is solid at room temperature and has thermoformability on a base film, and a relief corresponding to an uneven pattern for duplication And a light-to-heat conversion layer is provided below the relief layer, and the concavo-convex pattern forming film is formed so as to be in close contact with the relief layer, and light is applied to the light-to-heat conversion layer. An apparatus for duplicating a concavo-convex pattern, comprising: a shaping apparatus comprising a light irradiation apparatus for irradiating; 4. The concavo-convex pattern duplicating device according to claim 3, wherein the shaping resin layer has ionizing radiation curability, and includes an ionizing radiation irradiating device for irradiating the duplicated shaping resin layer with ionizing radiation.

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