JP4501439B2 - Method for continuous replication of radiation curable resin and resin molding by the method - Google Patents

Description

  The present invention relates to a resin molding method for continuously replicating a large number of concave and convex patterns having a fine shape, and in particular, using a UV or electron beam curable resin and continuously from a planar original plate having a concave and convex pattern having a fine shape such as a relief hologram. The present invention relates to a continuous replication method of a radiation curable resin to be resin-molded and a resin molded product obtained by the method.

  Conventionally, for example, CD, DVD, relief hologram, diffraction grating, Fresnel lens plate and lenticular plate used for microlenses and screens, liquid crystal device backlights and diffusion plates, etc. The following are known as typical techniques for copying.

(1) Pressing method This method is a method of producing a molded product by pressing a thermoplastic resin using a heated stamper. However, since this pressing method uses a thermoplastic resin, the heat resistance is poor. In the case of a pattern with a corner, it is often rounded, and there is a problem that it may lack sharpness.

(2) Casting method This method is a method in which a melt-softened thermoplastic resin is applied or injected onto the uneven surface of a stamper, and the resin is solidified to produce a molded product. There is a problem that there is a general temperature deviation and distortion and curling are likely to occur.

(3) Radiation curable resin method In recent years, it is not a thermoplastic resin such as the above-mentioned pressing method or casting method, but a type that is cured by irradiation with ionizing radiation typified by ultraviolet rays (UV) or electron beams (EB). There is a method of producing a molded product using a resin. This method has good heat resistance and moldability, and is a method for solving the above problems. The present invention is a production method using this radiation curable resin method.

  Moreover, as a method for producing a roll-shaped metal original plate used for continuous replication, it is possible to directly cut a pattern on a metal roll with a lathe, but a fine pattern is cut on the surface of a metal roll that is a curved surface. That is a difficult technique. In order to form submicron-sized patterns, a method using a laser or an electron beam drawing apparatus is optimal, but to form on a metal roll, a resist is applied to the curved surface. The process of laser or electron beam drawing, further development on a curved surface, etching, resist removal, etc. must be performed, but there are problems such as pattern shift, drawing accuracy, various irregularities in each process, and it is used as an original for forming optical members It is not a level that can be done.

  On the other hand, as a method for producing the roll-shaped metal original plate, there is a method of making a metal original plate produced in a flat shape into a roll shape, and one of them is a flat metal original plate on a roll using an adhesive or an adhesive material. (For example, refer to Patent Document 1 and Patent Document 2) In addition to this, a convex portion is provided at the end of the planar metal original plate, a groove is formed on the roll, a concave portion is provided, and the roll is fitted. There is a method of attaching a planar metal original plate (for example, see Patent Document 3).

The above prior art documents are shown below.
JP-A-7-314567 Japanese Patent Laid-Open No. 2001-310340 Japanese Patent Laid-Open No. 5-135413

  However, there is a difficulty in applying the method of forming a planar metal original plate, which has been proposed in the above-described hot pressing method and casting method, into a roll-shaped resin method. Because, in the exfoliation of the replica from the original plate, the exfoliation becomes heavier in the order of the hot press method, casting method, and radiation curable resin method, and the plate cannot be fixed even by the method that could be used in the hot press method or casting method. Because. In general, the radiation curable resin method has a problem that since the material used for transfer is a low-viscosity liquid, it easily enters gaps and seams, and easily causes protrusion defects and peeling defects.

  In addition, the method of using the adhesive and the pressure-sensitive adhesive described above makes it difficult to reuse the shaft roll, and there is a problem that the cost is high when dealing with a large variety and a small lot. Further, the above-described method for fitting the uneven portion at the end of the flat original plate has a problem that the flat metal original plate is stretched by heat when cured by UV or the like and lacks a dimensional system.

  The present invention solves such problems of the prior art, and the problem is that the obtained fine-shaped uneven pattern is excellent in sharpness, free from distortion and curl, and uses a radiation curable resin. A radiation-curing type that uses a low-cost roll-shaped metal precursor that can be used in a roll of a flat metal precursor that can withstand duplication, and that can be used for a wide variety of products and small lots. It is an object of the present invention to provide a continuous resin replication method and a resin molded product by the method.

In order to achieve the above object in the present invention, first, in the invention of claim 1, a step of applying a radiation curable resin on a resin film, and a film coated with the radiation curable resin with a nip roll, A step of closely adhering to an original roll having a cooling roll, a step of irradiating ultraviolet rays or an electron beam from the film side of the laminated film to cure a radiation curable resin, and a radiation curing on the cured film. A method of continuously replicating radiation curable resin comprising a step of peeling a mold resin from a master roll with a peeling roll, wherein the master roll has a cooling roll as a shaft roll and a plurality of combinations on the outer periphery of the shaft roll. mounting each metal support to form a substantially cylindrical shape, a planar metal precursor fine pattern on the outer periphery is formed of the metal support to form a the symbolic cylindrical shape That it is wrapped around fixed is obtained by a continuous method for duplicating a radiation-curable resin according to claim.

  According to a second aspect of the present invention, the outer peripheral surface of the metal support is a mirror surface, the inner peripheral surface is provided with a fixing jig for fixing both ends of the planar metal original plate, and the axial position of the fixing jig is provided at both ends. 2. A method for continuously replicating a radiation curable resin according to claim 1, further comprising a position adjusting jig for adjusting the position of the radiation curable resin.

  According to a third aspect of the present invention, the fixing jig is provided with a tension adjusting mechanism for adjusting the tension of the planar metal original plate and attaching it to the metal support. The radiation curable resin according to the second aspect of the present invention This is a continuous duplication method.

According to a fourth aspect of the present invention, the planar metal original plate has a thickness in the range of 50 to 500 μm, and is manufactured by an electroforming method comprising any one of nickel and an alloy thereof or a compound thereof. The radiation curable resin continuous replication method according to any one of claims 1 to 3, wherein the continuous replication method is a continuous replication method.

  According to a fifth aspect of the present invention, the resin film is a polyethylene terephthalate that has been subjected to an easy adhesion treatment by either a corona treatment or a plasma treatment, and the radiation curable type according to any one of the first to fourth aspects. This is a resin continuous replication method.

  In the invention of claim 6, the radiation curable resin is a liquid ultraviolet curable acrylic resin having a viscosity of 300 to 3000 mPa · s at room temperature. This is a continuous replication method of the radiation curable resin described in the above.

  Since this invention is the above structure, there exist the following effects.

  That is, according to the first aspect of the present invention, the original roll is wound and fixed by winding a planar metal original having a fine pattern formed on the outer periphery of each metal support that forms a substantially cylindrical shape by a plurality of combinations. This makes it possible to handle a large variety of small lots compared to the conventional method of attaching a flat metal master to a roll using an adhesive or pressure sensitive adhesive. It can be a method.

  Further, according to the second aspect of the present invention, the outer peripheral surface of the metal support is a mirror surface, the inner surface is provided with a fixing jig, and the both ends in the axial direction are provided with position adjusting jigs. It is possible to provide a continuous replication method of a radiation curable resin that can be finely adjusted in the axial direction by inserting both ends to give tension and screwing the fixing jig.

  Further, according to the invention according to claim 3, since the fixing jig is provided with the tension adjusting mechanism for adjusting the tension of the planar metal original plate and attaching it to the metal support, the convex portion is provided at the end of the planar metal original plate. Compared to the conventional method in which a groove is dug on a roll and a recess is formed and fitted, a continuous replication method of a radiation curable resin in which the planar metal original plate is not stretched or distorted by heat of irradiation such as UV can be obtained.

  Further, according to the inventions according to claims 4 to 6, the planar metal original plate is manufactured by an electroforming method having a thickness in the range of 50 to 500 μm and made of any one of nickel and an alloy thereof or a compound thereof. The resin film is made of polyethylene terephthalate that is easily adhered by either corona treatment or plasma treatment, and the radiation curable resin has a liquid state with a viscosity of 300 to 3000 mPa · s at room temperature. Since an ultraviolet curable acrylic resin is used, it is possible to provide a continuous replication method of a radiation curable resin that has excellent heat resistance and is easily peeled off in the peeling step.

  Furthermore, according to the invention according to claim 7, the resin molded product obtained by using the continuous replication method of the radiation curable resin according to any one of claims 1 to 6 has a fine uneven pattern. Is sharp, has no distortion or curl, and can be a low-cost resin molded product.

  The best mode for carrying out the present invention will be described below in detail with reference to the drawings.

The invention according to claim 1 includes a step of applying a radiation curable resin 10 on a resin film 11 with a coater 5 and a film coated with the radiation curable resin 11 as shown in the schematic diagram of FIG. A process of closely bonding to the original roll 9 having a cooling roll (not shown) inside by pressing the nip roll 6 so as not to mix bubbles, and radiation for irradiating ultraviolet rays or electron beams from the film side of the bonded film It is a continuous replication method of a radiation curable resin comprising a step of curing a radiation curable resin with an irradiator 7 and a step of peeling the radiation curable resin on the cured film from an original roll 9 with a release roll 8. As shown in the schematic diagram of FIG. 2, the master roll 9 has a fine pattern formed on the outer periphery of the tile-shaped metal support 3 that forms a substantially cylindrical shape by combining the two. And a continuous method for duplicating a planar metal plate 1 wound has been fixed radiation curable resin. With such a fixing method, it is possible to fix the inner side of the tile-shaped metal support 3, so that the outer periphery on the transfer surface side is not affected by unevenness due to a fixing jig or a burr on the end surface of the original plate.

  Further, the tile-like metal support 3 used in the present invention can be used not only in half of a cylinder but also in 30%. However, if it is more than 40%, the number of seams between the tile-shaped metal supports increases, which is not appropriate.

  In addition, as shown in FIG. 1, in continuous replication using a radiation curable resin 10, reaction heat at the time of curing of the resin and heat from an ultraviolet irradiator are accumulated in the metal original plate. It becomes high temperature and extends according to the linear expansion coefficient of the metal, which not only changes the shape of the fine pattern, but also shortens the life of the metal original plate. Therefore, as shown in FIG. 2, it is necessary to cool the metal original plate 1, but according to the present invention, the cooling roll 4 is used as a shaft roll, and the roof tile is fixed to the outer periphery of the shaft roll. Since the metal support 3 is attached, no external cooling device is required.

  3 and 4 show the peripheral portion of the original plate fixing jig 13 inside the tile-shaped metal support 3. As shown in FIG. 3, in the invention according to claim 3, A tension adjusting mechanism for adjusting the tension of the planar metal original plate 1 and attaching it to the tile-shaped metal support 3 is provided. This tension adjusting mechanism supports the tile-shaped metal by inserting and adjusting the tension adjusting screw 14 in the direction of the arrow. The gap between the body 3 and the metal original plate 1 is made small so as to be in close contact. If the tile-like metal support 3 and the original metal plate 1 are not in close contact with each other and there is a float, the metal original plate 1 is slightly moved during continuous replication to cause metal fatigue, resulting in a hole in the original plate, and finally the original plate. Will be disconnected.

  In addition, in order to use a half-shaped tile-shaped metal support 3 as shown in FIG. When using two or more metal original plates, there are cases where it is desired to match the pattern arrangement of adjacent original plates by joining the original plates. In the invention according to claim 2, for example, as shown in FIG. 4, position adjusting screws 15 that can be finely adjusted in the left and right directions in the width direction are installed on both side surfaces of the tile-like metal support 3.

  The radiation irradiator used in the continuous replication method of the radiation curable resin of the present invention refers to an apparatus that irradiates any one of visible light, ultraviolet light, and electron beam, and the radiation curable type of the invention according to claim 6. The resin is a resin that is cured by radiation such as visible light, ultraviolet light (UV), and electron beam (EB), unlike the thermosetting resin. A typical radical polymerization reaction resin is an acrylic resin having an acryloyl group in the molecule, and is an epoxy acrylate, urethane acrylate, polyester acrylate, polyol acrylate oligomer, polymer and monofunctional, bifunctional, or polyfunctional. Functional polymerizable (meth) acrylic monomers such as tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate , Mixtures of monomers, oligomers, polymers, etc., such as pentaerythritol tetraacrylate.

  Moreover, as what is mix | blended with the said radiation curable resin, there exists a photoinitiator, This photoinitiator is not required when making it harden | cure by EB, However, when hardening by an ultraviolet-ray or visible light, it is required. . Examples of polymerization initiators include benzophenone, diethylthioxanthone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio). Phenyl] -2-morpholinopropane-1, acylphosphine oxide, etc., but the photopolymerization initiator does not react 100%, and the unreacted one adversely affects the performance of the molded lens. In the range of 0.1 to 7% by weight, preferably 0.5 to 5% by weight, the addition amount should be kept to the extent that no uncured part remains. Moreover, when making it harden | cure with visible light, a pigment | dye may be mix | blended other than a photoinitiator.

  In addition, when the viscosity of the radiation curable resin of the invention according to claim 6 is less than 300 mPa · s at room temperature (25 ° C.), it is difficult to control the spread of the resin in the width direction of the duplicating apparatus, and the viscosity is room temperature. When the resin exceeds 3000 mPa · s at (25 ° C.), a strong nip pressure is required for bonding the metal original plate and the resin-coated film, and as a result, the life of the metal original plate is shortened. Therefore, in the present invention, it is preferable to use a radiation curable resin having a viscosity in the range of 300 m to 3000 mPa · s at room temperature (25 ° C.).

  In addition, when the cured film is peeled off from the metal original plate after the metal original plate and the film coated with the radiation curable resin are bonded through a nip roll and cured with ultraviolet rays or EB, Resin residue may occur on the original. Therefore, in the invention according to claim 5, the film is made of polyethylene terephthalate that has been subjected to easy adhesion treatment by either corona treatment or plasma treatment, thereby enhancing the adhesion between the film and the resin, The resin residue on the metal original plate can be prevented.

  In addition, a method for producing a metal original plate having a fine-shaped uneven pattern used in the above-described continuous replication method of the radiation curable resin of the present invention can be applied to a photoresist or an electron beam (EB) resist using, for example, a laser or an electron beam drawing apparatus. A fine pattern is recorded, a metal conductive film is formed on the pattern by vapor deposition or sputtering, and metal is electrodeposited on the surface of the metal conductive film, and only the metal is peeled off and washed. It is a metal master.

  The above-mentioned electroforming method uses electrodeposition by electrolysis and refers to a method of precisely replicating the same as the original shape so as to make a casting with a mold, and a technique such as electroplating that covers the surface of the material with a metal thin film Say. The material of the metal original plate is nickel, an alloy thereof, or a compound thereof, copper, silver, gold, chromium, titanium, iron, zinc, or a metal composed of any two or more of these. Or the compound etc. which contain at least 1 type among these are mentioned. Among the materials of the metal original plate, in the invention according to the fourth aspect, nickel or nickel-cobalt alloy is preferable in consideration of electroforming suitability and peelability from the radiation curable resin.

  Furthermore, if the thickness of the metal original plate is less than 50 μm in order to bend into a roll shape, it is too thin and local dents and the like easily occur, resulting in poor handling. In addition to the remarkable rigidity, a strong force is required to bend, and therefore, in the continuous replication method of the radiation curable resin of the present invention, it is preferable that the thickness of the metal original plate is in the range of 50 μm to 500 μm. .

A diffraction grating pattern having a spatial frequency of 1000 lines / mm was drawn on an EB resist using an EB drawing apparatus, developed and washed, and then a conductive film having a thickness of about 200 mm was formed on the pattern by nickel deposition. Next, it is put in an electrodeposition layer of a plating bath mainly composed of nickel sulfamate.
Electrodeposition was performed until the thickness became 00 μm, and then peeled off from the EB resist to obtain a planar metal original plate.

  In order to improve the flatness of the back side of the metal original plate obtained above, bug polishing is performed, and then the metal original plate is fixed to a tile-shaped metal support divided into two parts, and the tension of the metal original plate and the position adjustment in the width direction are adjusted. After that, the original roll is attached to a cooling roll, and this original roll is equipped with an ultraviolet irradiation duplicator, and an acrylic ultraviolet curing resin (made by Shin-Nakamura Chemical Co., Ltd.) having a viscosity of 1000 mPa · s is used for corona treatment. Using a PET (polyethylene terephthalate) film, continuous replication was performed up to a length of 1000 m at a speed of 10 m / min.

  The pattern of the replica and the metal original plate obtained as described above almost matched the lattice depth, the lattice shape, and the line pitch. Moreover, it was confirmed that the used metal original plate can be easily removed from the tile-shaped metal support and can be used again.

It is explanatory drawing which shows typically one Embodiment of the continuous replication method of the radiation curable resin of this invention. It is explanatory drawing which shows typically an example of the original roll used for the continuous replication method of the radiation curable resin of this invention. It is an enlarged view which shows typically an example of preparation of the original roll used for the continuous replication method of the radiation curable resin of this invention. It is an enlarged view which shows typically another example of preparation of the original roll used for the continuous replication method of the radiation curable resin of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Metal master 2 ... Fixing screw 3 ... Tile-shaped metal support 4 ... Cooling roll 5 ... Coater 6 ... Nip roll 7 ... Radiation irradiation machine 8 ... Peeling roll 9 ... Original roll 10 ... Radiation curable resin 11 ... Resin film 12 ... Winding roll 13 ... Fixing jig 14 ... Tension adjusting screw 15 ... Position adjusting screw

Claims (6)

A step of applying a radiation curable resin on a resin film, a step of closely bonding a film coated with the radiation curable resin to a master roll having a cooling roll inside with a nip roll, and A continuous radiation curable resin comprising a step of irradiating ultraviolet radiation or an electron beam from the film side to cure the radiation curable resin and a step of peeling the radiation curable resin on the cured film from the original roll with a release roll. A duplication method,
The master roll has a cooling roll as an axial roll, and a plurality of combinations of metal supports that form a substantially cylindrical shape are attached to the outer periphery of the axial roll, and the outer periphery of each metal support that forms the substantially cylindrical shape. A continuous replication method of a radiation curable resin, characterized in that a planar metal original plate on which a fine pattern is formed is wound and fixed.   The outer peripheral surface of the metal support is a mirror surface, the inner peripheral surface is provided with a fixing jig for fixing both ends of the flat metal original plate, and the axial end is provided with a position adjusting jig for adjusting the position of the fixing jig. The method for continuous replication of a radiation curable resin according to claim 1.   3. The method for continuous replication of radiation curable resin according to claim 2, wherein the fixing jig is provided with a tension adjusting mechanism for adjusting the tension of the planar metal original plate and attaching it to the metal support.   The planar metal original plate has a thickness in a range of 50 to 500 µm, and is manufactured by an electroforming method made of any one of nickel and an alloy thereof or a compound thereof. A continuous replication method of the radiation curable resin according to any one of the above.   The method for continuous replication of a radiation curable resin according to any one of claims 1 to 4, wherein the resin film is polyethylene terephthalate subjected to easy adhesion treatment by either corona treatment or plasma treatment. 6. The radiation curable resin according to claim 1, wherein the radiation curable resin is a liquid ultraviolet curable acrylic resin having a viscosity of 300 to 3000 mPa · s at room temperature. Continuous replication method.

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