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JP2005212259A - Continuous method for reproducing radiation curable resin and resin molding by the method - Google Patents

Continuous method for reproducing radiation curable resin and resin molding by the method Download PDF

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JP2005212259A
JP2005212259A JP2004021361A JP2004021361A JP2005212259A JP 2005212259 A JP2005212259 A JP 2005212259A JP 2004021361 A JP2004021361 A JP 2004021361A JP 2004021361 A JP2004021361 A JP 2004021361A JP 2005212259 A JP2005212259 A JP 2005212259A
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radiation curable
curable resin
roll
resin
original plate
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JP4501439B2 (en
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Manabu Watanabe
学 渡邉
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Toppan Inc
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Toppan Printing Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a continuous method for reproducing a radiation curable resin in which a minute shape pattern is excellent in sharpness and free of distortion and curling and which is a method for fixing a plane metal original plate bearable to reproduction using the radiation curable resin in the shape of a roll, can deal with high-mix low volume production, and does continuous reproduction by using the inexpensive roll-like metal original plate. <P>SOLUTION: The continuous method for reproducing the radiation curable resin comprises a process for applying the resin on a resin film, a process for sticking the film on an original plate roll by a nip roll, a process for curing the resin from the film side by a radiation irradiation machine, and a process for peeling the cured resin from the original plate roll by a peeling roll. As regards the original plate roll 9, the plane metal original plate 1 is wound onto the periphery of a tile-like metal support 3 which forms an approximately cylindrical shape when combined with another support 3. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、微細形状の凹凸パターンを連続に大量複製する樹脂成形方法に関するものであり、特に、紫外線又は電子線硬化樹脂を使用し、レリーフホログラム等微細形状の凹凸パターンを有する平面状原版から連続に樹脂成形する放射線硬化型樹脂の連続複製方法およびその方法により得られる樹脂成形物に関する。   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.

従来、例えばCD、DVD、レリーフホログラム、回折格子又はマイクロレンズやスクリーンなどに用いられるフレネルレンズ板やレンチキュラー板及び液晶装置のバックライトや拡散板などの微細形状パターンの樹脂成形物を連続的に大量複製するにあたり、代表的な手法として、以下のものが知られている。   Conventionally, for example, CD, DVD, relief hologram, diffraction grating, Fresnel lens plate and lenticular plate used for microlenses and screens, etc. Continuously a large amount of resin molded products with fine shape patterns such as backlights and diffusion plates of liquid crystal devices The following are known as typical techniques for copying.

(1)プレス法
この方法は、熱可塑性樹脂を、加熱されたスタンパを用いて押圧し、成型物を作製する手法であるが、このプレス法は熱可塑性樹脂を用いるため、耐熱性に乏しく、角のある形状のパターンの場合、丸みを帯びてしまうことが多く、シャープ性に欠ける危惧があるという問題点があった。
(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)キャスティング法
この方法は、溶融軟化された熱可塑性樹脂を、スタンパの凹凸形成面に塗布または注入し、前記樹脂を固化させて成型物を作製する手法であるが、このキャスティング法は局所的な温度偏りが存在し、歪みやカールが起こり易いという問題点があった。
(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)放射線硬化型樹脂法
近年では、上記プレス法やキャスティング法のような熱可塑性樹脂ではなく、紫外線(UV)や電子線(EB)等に代表される電離放射線の照射によって硬化するタイプの樹脂を使用し、成型物を作製する手法がある。この方法は耐熱性、成形性もよく、上記問題点を解決する手法で、本発明は、この放射線硬化型樹脂法を用いた製造方法である。
(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.

また、連続的複製に使用されるロール状の金属原版を作製する方法としては、直接金属ロールに旋盤でパターン切削することは可能であるが、曲面である金属ロールの表面に微細パターンを切削することは至難の技である。また、サブミクロンの大きさのパターンを形成するには、レーザーや電子線描画装置を使用した方法が最適ではあるが、金属ロール上に形成するには、曲面へのレジストを塗布、曲面でのレーザー又は電子線描画、さらに曲面での現像、エッチング、レジスト除去といった工程を行なわなければならないが、各工程でパターンずれ、描画精度、各種のムラ等問題があり、光学部材形成用の原版として使用できるレベルではない。   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 a submicron pattern, a method using a laser or an electron beam drawing apparatus is optimal. However, to form a pattern 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.

一方、上記ロール状の金属原版を作製する方法として、平面状で作製された金属原版をロール状にする方法があり、その一つとして接着剤や粘着材を使用してロールに平面状金属原版を貼りつける方法があり(例えば、特許文献1及び特許文献2参照。)、この他に平面状金属原版の端に凸部を設け、ロール上に溝を掘り凹部を設け、嵌め合わせることでロールに平面状金属原版を取りつける方法がある(例えば、特許文献3参照。)。   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).

以下に上記先行技術文献を示す。
特開平7−314567号公報 特開平2001−310340号公報 特開平5−135413号公報
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

しかしながら、上記の熱プレス法やキャスティング法で提案されてきた平面状金属原版をロール状にする方法を、放射線硬化型樹脂法に適用するには困難な問題がある。なぜなら、原版から複製品の剥離において、熱プレス法、キャスティング法、放射線硬化型樹脂法の順に剥離が重くなり、熱プレス法やキャスティング法で使用できていた方法でも版の固定が不十分であるからである。また、一般に放射線硬化型樹脂法では、転写に使用する材料は低粘度の液体であるため、隙間や継ぎ目に容易に入り込み、突起欠陥や剥離不良を起こしやすいという問題点があった。   However, there is a difficult problem in applying the method of forming a planar metal original plate, which has been proposed in the above-described hot press method and casting method, into a roll-like 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.

また、上記で説明した接着剤や粘着剤を使用する方法では軸のロールの再利用は難しく、多品種少ロットの対応ではコスト高となってしまうという問題点があった。さらに上記平面状原版の端の凹凸部の嵌合法では、UV等で硬化させる時の熱で平面状金属原版が伸びたりし、寸法制度等に欠けるという問題点があった。   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.

本発明は、かかる従来技術の問題点を解決するものであり、その課題とするところは、得られる微細形状の凹凸パターンがシャープ性に優れ、かつ歪みやカールがなく、放射線硬化樹脂を使用した複製にも耐えうる平面状金属原版のロール状に固定する方法で、かつ多品種少ロットに対応できる低コストのロール状金属原版を用いて、微細形状の凹凸パターンを連続に複製する放射線硬化型樹脂の連続複製方法およびその方法による樹脂成形物を提供することにある。   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.

本発明に於いて上記課題を達成するために、まず請求項1の発明では、樹脂フィルム上に放射線硬化型樹脂を塗布する工程と、該放射線硬化型樹脂が塗布されたフィルムをニップロールで、内部に冷却ロールを有する原版ロールに密着貼り合わせる工程と、該貼り合わせられたフィルムのフィルム側から紫外線または電子線を照射し放射線硬化型樹脂を硬化せしめる工程と、該硬化されたフィルム上の放射線硬化型樹脂を原版ロールから薄利ロールで剥離する工程とでなる放射線硬化型樹脂の連続複製方法であって、前記原版ロールは、複数の組合わせで略円筒形状を形成する各金属支持体の外周に微細パターンが形成された平面状金属原版を巻き付け固定されていることを特徴とする放射線硬化型樹脂の連続複製方法としたものである。   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 thin roll, wherein the master roll is formed on the outer periphery of each metal support forming a substantially cylindrical shape by a plurality of combinations. This is a radiation curable resin continuous replication method characterized by winding and fixing a planar metal original plate on which a fine pattern is formed.

また、請求項2の発明では、上記金属支持体の外周面は鏡面でなり、内周面には平面状金属原版の両端を固定する固定冶具を備え、軸方向両端には該固定冶具の位置を調整する位置調整冶具を備えていることを特徴とする請求項1記載の放射線硬化型樹脂の連続複製方法としたものである。   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.

また、請求項3の発明では、上記固定冶具には、平面状金属原版を張力調整して金属支持体に取り付ける張力調整機構を備えていることを特徴とする請求項2記載の放射線硬化型樹脂の連続複製方法としたものである。   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.

また、請求項4の発明では、上記平面状金属原版は、厚みが50〜500μmの範囲でなり、ニッケルおよびその合金またはその化合物のいずれかの材料からなる電鋳法で製造されていることを特徴とする請求項1乃至3のいずれかに記載の放射線硬化型樹脂の連続
複製方法連続複製方法としたものである。
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.

また、請求項5の発明では、上記樹脂フィルムはコロナ処理、プラズマ処理のいずれかによって易接着処理されたポリエチレンテレフタレートであることを特徴とする請求項1乃至4のいずれかに記載の放射線硬化型樹脂の連続複製方法としたものである。   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.

また、請求項6の発明では、上記放射線硬化型樹脂は、常温で粘度300〜3000mPa・sの範囲の液体状の紫外線硬化型アクリル系樹脂であることを特徴とする請求項1乃至5のいずれかに記載の放射線硬化型樹脂の連続複製方法としたものである。   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.

さらにまた、請求項7の発明では、上記請求項1乃至6のいずれかに記載の放射線硬化型樹脂の連続複製方法を用いた樹脂成形物としたものである。   Furthermore, the invention of claim 7 is a resin molded article using the radiation curable resin continuous replication method according to any one of claims 1 to 6.

本発明は以上の構成であるから、下記に示す如き効果がある。   Since this invention is the above structure, there exist the following effects.

即ち、上記請求項1に係る発明によれば、原版ロールを、複数の組合わせで略円筒形状を形成する各金属支持体の外周に微細パターンが形成された平面状金属原版を巻き付け固定されているものとすることによって、接着剤や粘着剤を用いて平面状金属原版をロールに貼り付ける従来の方法に比べ多品種小ロット対応が可能で、コストが嵩まない放射線硬化型樹脂の連続複製方法とすることができる。   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.

また、上記請求項2に係る発明によれば、金属支持体の外周面が鏡面で、内面には固定冶具を備え、軸方向両端には位置調整冶具を備えているので、平面状金属原版の両端を挿み張力を与え、固定冶具をネジ押し込みで軸方向への微調整を可能にする放射線硬化型樹脂の連続複製方法とすることができる。   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.

また、上記請求項3に係る発明によれば、固定冶具に、平面状金属原版を張力調整して金属支持体に取り付ける張力調整機構を備えているので、平面状金属原版の端に凸部を設け、ロール上に溝を掘り凹部を設け、嵌め合わせる従来の方法に比べ、UV等照射の熱で平面状金属原版が伸びたり歪んだりしない放射線硬化型樹脂の連続複製方法とすることができる。   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.

また、上記請求項4から6に係る発明によれば、平面状金属原版を、厚みが50〜500μmの範囲で、ニッケルおよびその合金またはその化合物のいずれかの材料からなる電鋳法で製造されているものを用い、樹脂フィルムを、コロナ処理、プラズマ処理のいずれかによって易接着処理されたポリエチレンテレフタレートを用い、放射線硬化型樹脂には、常温で粘度300〜3000mPa・sの範囲の液体状の紫外線硬化型アクリル系樹脂を用いているので、耐熱性に優れ、かつ剥離工程での剥離がし易い放射線硬化型樹脂の連続複製方法とすることができる。   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.

さらにまた、上記請求項7に係る発明によれば、上記請求項1乃至6のいずれかに記載の放射線硬化型樹脂の連続複製方法を用いて得られた樹脂成形物は、微細形状の凹凸パターンがシャープで歪みやカール等がなく、かつ低コストの樹脂成形物とすることができる。   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.

以下本発明を実施するための最良の形態を図面を用いて詳細に説明する。   The best mode for carrying out the present invention will be described below in detail with reference to the drawings.

上記請求項1に係る発明は、例えば図1の模式図に示すように、樹脂フィルム11上に
放射線硬化型樹脂10をコーター5で塗布する工程と、放射線硬化型樹脂11が塗布されたフィルムを気泡混入しないようにニップロール6の押圧で、内部に冷却ロール(図示せず)を有する原版ロール9に密着貼り合わせる工程と、該貼り合わせられたフィルムのフィルム側から紫外線または電子線を照射する放射線照射機7で放射線硬化型樹脂を硬化せしめる工程と、該硬化されたフィルム上の放射線硬化型樹脂を原版ロール9から剥離ロール8で剥離する工程とでなる放射線硬化型樹脂の連続複製方法であって、図2の模式図に示すように、原版ロール9は、二つの組合わせで略円筒形状を形成する瓦状金属支持体3の外周に微細パターンが形成された平面状金属原版1を巻き付け固定されている放射線硬化型樹脂の連続複製方法である。このような固定方法であれば、瓦状金属支持体3の内側で固定することが可能なため、転写表面側である外周には固定治具や原版端面のバリによる凹凸の影響がない。
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.

また、本発明に使用する瓦状金属支持体3は、円筒の半割だけではなく、3ツ割でも使用可能である。しかし、4ツ割以上になると瓦状金属支持体同士の継ぎ目が多くなることから適当ではない。   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.

また、図1に示すように、放射線硬化型樹脂10を使用した連続複製においては、樹脂の硬化時の反応熱や紫外線照射機からの熱が金属原版に蓄積され、ロングランを行なうと金属原版が高温になり、金属の線膨張係数にしたがって伸びてしまい、微細パターンの形状が変化するだけでなく、金属原版の寿命を縮めることになる。そこで図2に示すように、金属原版1を冷却することが必要となるが、本発明によれば、冷却ロール4を軸ロールとして使い、該軸ロールの外周に、金属原版1を固定した瓦状金属支持体3を取りつけるため、外部に冷却装置が不要となる。   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.

図3及び図4は、瓦状金属支持体3の内側にある原版固定治具13の周辺部を図示しており、図3に示すように、請求項3に係る発明では、固定冶具13に、平面状金属原版1を張力調整して瓦状金属支持体3に取り付ける張力調整機構を備えていて、この張力調整機構は張力調整ネジ14を矢印の方向に差し込み調整することで瓦状金属支持体3と金属原版1との隙間が少なく密着するようにする。この瓦状金属支持体3と金属原版1が密着せずに浮きが存在すると、連続複製中に金属原版1が微移動することを繰り返して金属疲労し、原版に穴が空き、最後には原版が切断されることになる。   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.

また、図2に示すような半割の瓦状金属支持体3を使用し、原版ロール9にするには2枚の平面状金属原版1が必要となる。2枚以上の金属原版を使用する際、原版同士の継ぎで隣接する原版のパターン配列を合わせたい場合が生じることがある。上記請求項2に係る発明では、例えば図4に示すように幅方向左右に微調整できる位置調整ネジ15が瓦状金属支持体3の両側面に設置するようにしたものである。   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.

上記本発明の放射線硬化型樹脂の連続複製方法に使用する放射線照射機とは、可視光、紫外線又は電子線の何れかを照射する装置をいい、また上記請求項6に係る発明の放射線硬化型樹脂とは、熱硬化樹脂とは異なり、可視光、紫外線(UV)、電子線(EB)等の放射線によって硬化する樹脂をいう。代表的なラジカル重合反応する樹脂として、分子中にアクリロイル基を有するアクリル樹脂であり、エポキシアクリレート系,ウレタンアクリレート系、ポリエステルアクリレート系、ポリオールアクリレート系のオリゴマー、ポリマーと単官能・2官能・あるいは多官能重合性(メタ)アクリル系モノマー、例えばテトラヒドロフルフリルアクリレート、2ーヒドロキシエチルアクリレート、2ーヒドロキシー3ーフェノキシプロピルアクリレート、ポリエチレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリトリトールトリアクリレート、ペンタエリトリトールテトラアクリレートなどのモノマー、オリゴマー、ポリマーなどの混合物が使用される。   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. A resin is a resin that is cured by radiation such as visible light, ultraviolet light (UV), or electron beam (EB), unlike a 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.

また、上記放射線硬化型樹脂に配合されるものとして、光重合開始剤があり、この光重合開始剤は、EBで硬化させる場合は必要無いが、紫外線や可視光で硬化する場合は必要である。重合開始剤として例えばベンゾフェノン、ジエチルチオキサントン、ベンジルジメチルケタール、2−ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン、1−ヒドロキシシクロヘキシルフェニルケトン、2−メチル−1−〔4−(メチルチオ)フェニル〕−2−モリフォリノプロパン−1、アシルホスフィンオキサイドなどがあるが、光重合開始剤は100%反応するわけではなく、未反応のものが成形されたレンズの性能に悪影響を及ぼすことから、0.1〜7重量%の範囲、好ましくは0.5〜5重量%で、未硬化部が残らない程度に添加量をとどめるべきである。また、可視光で硬化させる場合は、光重合開始剤の他に色素を配合することがある。   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.

また、上記請求項6に係る発明の放射線硬化型樹脂の粘度が常温(25℃)で300mPa・sに満たない樹脂では、複製装置の幅方向に樹脂が広がることを制御が難しく、粘度が常温(25℃)で3000mPa・sを越える樹脂では、金属原版と樹脂塗布したフィルムの貼り合わせの際に強いニップ圧を必要とし、結果として金属原版の寿命を縮めることになる。よって本発明においては、粘度が常温(25℃)で300m〜3000mPa・sの範囲の放射線硬化型樹脂を使用することが好適である。   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.).

また、金属原版と放射線硬化型樹脂を塗布したフィルムをニップロールを介して貼り合わせし、紫外線又はEBで硬化させた後、金属原版から硬化樹脂を剥離する際に、未表面処理のフィルムでは、金属原版上に樹脂残りが発生することがある。そこで、上記請求項5に係る発明では、このフィルムとして、コロナ処理、プラズマ処理のいずれかによって易接着処理されたポリエチレンテレフタレートを使用することとしたもので、フィルムと樹脂の密着性を強くし、金属原版上の樹脂残りを防ぐようにすることができる。   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, and the adhesion between the film and the resin is strengthened. The resin residue on the metal original plate can be prevented.

また、上記本発明の放射線硬化型樹脂の連続複製方法に使用する微細形状の凹凸パターンを有する金属原版の作製方法は、例えばレーザーや電子線描画装置にてフォトレジストもしくは電子線(EB)レジストに微細形状のパターンを記録し、このパターン上に蒸着法やスパッタ法にて金属導電膜を形成し、この金属導電膜の表面に電鋳にて金属を電着させ、金属のみ剥離、洗浄して金属原版とするものである。   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.

上記電鋳法とは、電気分解による電着を利用し、鋳型で鋳物を作るように原形と同じものを精密に複製する方法をいい、物質の表面を金属薄膜で被覆する電気メッキ等の技術をいう。金属製原版の材料としては、ニッケル、その合金またはその化合物のうちいずれかの他、銅、銀、金、クロム、チタン、鉄、亜鉛のいずれか一種からなる金属、これら二種以上からなる合金またはこれらのうち少なくとも一種を含む化合物等が挙げられる。それら金属原版の材料の中でも、上記請求項4に係る発明では、電鋳適性や放射線硬化樹脂との剥離性を考慮するとニッケルやニッケル・コバルト合金が好適である。   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.

さらにまた、上記金属原版の厚みは、ロール状に曲げるためには、50μmに満たないと薄すぎて局所的な凹み等が簡単に発生してしまいハンドリングが悪く、また、500μmを越えると金属の剛性が顕著になることに加え、曲げるのに強い力を必要とするため本発明の放射線硬化型樹脂の連続複製方法においては、金属原版の厚みを50μm〜500μmの範囲とするのが好適である。   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. .

EB描画装置を使用して空間周波数1000本/mmの回折格子パターンをEBレジスト上に描画し、現像・洗浄した後、パターン上にニッケル蒸着により約200Å厚の導電膜を形成した。次にスルファミン酸ニッケルを主成分としたメッキ浴の電着層に入れ、3
00μm厚になるまで電着を行なった後、EBレジストから剥離して平面状金属原版とした。
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.

上記で得られた金属原版の裏面の平面性を高めるため、バグ研磨を行なった後、金属原版を2分割された瓦状金属支持体に固定し、金属原版の張り具合と幅方向の位置調整を行なった後、冷却ロールに取りつけて原版ロールとし、この原版ロールを紫外線照射複製装置に装備し、粘度1000mPa・sのアクリル系紫外線硬化樹脂(新中村化学社製)を使用し、コロナ処理されたPET(ポリエチレンテレフタレート)フィルムを用いて、10m/minの速度で連続複製を長さ1000mまで行なった。   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.

上記で得られた複製品と金属原版のパターンは、格子深さ、格子形状、ラインピッチともにほぼ一致する結果となった。また、使用済みの金属原版は、瓦状金属支持体から容易に取り外すことが可能であり、再度、利用可能であることを確認した。   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.

本発明の放射線硬化型樹脂の連続複製方法の一実施の形態を模式的に示す説明図である。It is explanatory drawing which shows typically one Embodiment of the continuous replication method of the radiation curable resin of this invention. 本発明の放射線硬化型樹脂の連続複製方法に使用する原版ロールの一事例を模式的に示す説明図である。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. 本発明の放射線硬化型樹脂の連続複製方法に使用する原版ロールの作製の一事例を模式的に示す拡大図である。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. 本発明の放射線硬化型樹脂の連続複製方法に使用する原版ロールの作製の他の一事例を模式的に示す拡大図である。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.

符号の説明Explanation of symbols

1‥‥金属原版
2‥‥固定ネジ
3‥‥瓦状金属支持体
4‥‥冷却ロール
5‥‥コーター
6‥‥ニップロール
7‥‥放射線照射機
8‥‥剥離ロール
9‥‥原版ロール
10‥‥放射線硬化型樹脂
11‥‥樹脂フィルム
12‥‥巻き取りロール
13‥‥固定冶具
14‥‥張力調整ネジ
15‥‥位置調整ネジ
DESCRIPTION OF SYMBOLS 1 ... Metal original plate 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 (7)

樹脂フィルム上に放射線硬化型樹脂を塗布する工程と、該放射線硬化型樹脂が塗布されたフィルムをニップロールで、内部に冷却ロールを有する原版ロールに密着貼り合わせる工程と、該貼り合わせられたフィルムのフィルム側から紫外線または電子線を照射し放射線硬化型樹脂を硬化せしめる工程と、該硬化されたフィルム上の放射線硬化型樹脂を原版ロールから剥離ロールで剥離する工程とでなる放射線硬化型樹脂の連続複製方法であって、前記原版ロールは、複数の組合わせで略円筒形状を形成する各金属支持体の外周に微細パターンが形成された平面状金属原版を巻き付け固定されていることを特徴とする放射線硬化型樹脂の連続複製方法。   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 step of 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. In the duplication method, the original roll is wound and fixed on 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. Continuous replication method of radiation curable resin. 上記金属支持体の外周面は鏡面でなり、内周面には平面状金属原版の両端を固定する固定冶具を備え、軸方向両端には該固定冶具の位置を調整する位置調整冶具を備えていることを特徴とする請求項1記載の放射線硬化型樹脂の連続複製方法。   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. 上記固定冶具には、平面状金属原版を張力調整して金属支持体に取り付ける張力調整機構を備えていることを特徴とする請求項2記載の放射線硬化型樹脂の連続複製方法。   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. 上記平面状金属原版は、厚みが50〜500μmの範囲でなり、ニッケルおよびその合金またはその化合物のいずれかの材料からなる電鋳法で製造されていることを特徴とする請求項1乃至3のいずれかに記載の放射線硬化型樹脂の連続複製方法連続複製方法。   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. 上記樹脂フィルムはコロナ処理、プラズマ処理のいずれかによって易接着処理されたポリエチレンテレフタレートであることを特徴とする請求項1乃至4のいずれかに記載の放射線硬化型樹脂の連続複製方法。   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. 上記放射線硬化型樹脂は、常温で粘度300〜3000mPa・sの範囲の液体状の紫外線硬化型アクリル系樹脂であることを特徴とする請求項1乃至5のいずれかに記載の放射線硬化型樹脂の連続複製方法。   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. 上記請求項1乃至6のいずれかに記載の放射線硬化型樹脂の連続複製方法を用いた樹脂成形物。   A resin molded article using the radiation curable resin continuous replication method according to any one of claims 1 to 6.
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