JP2009285916A - Manufacturing process of shaped resin sheet - Google Patents
Manufacturing process of shaped resin sheet Download PDFInfo
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- JP2009285916A JP2009285916A JP2008139260A JP2008139260A JP2009285916A JP 2009285916 A JP2009285916 A JP 2009285916A JP 2008139260 A JP2008139260 A JP 2008139260A JP 2008139260 A JP2008139260 A JP 2008139260A JP 2009285916 A JP2009285916 A JP 2009285916A
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Abstract
Description
本発明は表面に規則的な形状を有する樹脂シートの製造方法に係り、特に、光学的に機能を発現する形状が付与された、歪が無く形状安定性に優れた賦型樹脂シートの製造方法に関する。 The present invention relates to a method for producing a resin sheet having a regular shape on the surface, and in particular, a method for producing a molded resin sheet having a shape that exhibits an optical function and having no distortion and excellent shape stability. About.
表面形状によって光学的機能を発現する樹脂シートとして、フレネルレンズ、レンチキュラーレンズおよびプリズムシート等が様々な分野で使用されている。このような樹脂シートの表面には、規則的な凹凸形状が形成されており、この凹凸形状により、フレネルレンズ、レンチキュラーレンズそしてプリズムとしてのそれぞれの光学的性能を発揮している。 Fresnel lenses, lenticular lenses, prism sheets, and the like are used in various fields as resin sheets that exhibit an optical function depending on the surface shape. A regular uneven shape is formed on the surface of such a resin sheet, and the optical performance as a Fresnel lens, a lenticular lens, and a prism is exhibited by the uneven shape.
このような樹脂シートを製造する方法として、これまでに各種の提案がなされている（特許文献１〜５参照）。これらの提案においては、いずれも、生産性向上の観点よりローラ成形方式が採用されている。たとえば、特許文献１は、樹脂シートをローラから剥離するまでの間の冷却手段に工夫を施すことにより、転写性の向上を図っている。特許文献２は、ローラに金型を巻き付けてフレネルレンズを製造する方法を開示している。特許文献３は、成形ローラの内部に熱緩衝部材を配して、生産性及び転写性の向上を図っている。特許文献４は、コロナ放電処理を採用することにより、転写性の向上、欠陥の低減を図っている。さらに特許文献５では、ダイから吐出されたシート状の溶融樹脂を型ロールと鏡面ロールで挟圧し賦型する工程を複数回行い、賦型形状の転写性を向上させている。
As a method for producing such a resin sheet, various proposals have been made so far (see
しかしながら、上記従来の提案は、いずれも、効率的に転写を行い形状の転写性を向上させる効果はあるが、高さ１００μｍ以下の微細形状を転写させた場合、微細賦型部分に歪が残存し、後工程にて賦型シートをガラス転移温度以上に加熱すると歪み緩和現象によって転写した賦型形状が変形・崩れなどが発生する。 However, each of the above-mentioned conventional proposals has an effect of efficiently transferring and improving the shape transferability. However, when a fine shape having a height of 100 μm or less is transferred, strain remains in the finely shaped portion. However, when the shaping sheet is heated to a temperature higher than the glass transition temperature in the subsequent process, the shaping shape transferred due to the strain relaxation phenomenon is deformed or collapsed.
本発明はこのような事情に鑑みてなされたもので、連続的に且つ効率的に微細な形状を転写賦型し、得られた賦型シートを後工程にてガラス転移温度以上まで加熱しても、賦型形状に変形が発生しない、賦型形状安定性に優れた導光板や各種光学素子に使用するのに好適な樹脂シートの製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and continuously and efficiently transfer-molds a fine shape, and heats the obtained shaped sheet to a glass transition temperature or higher in a subsequent step. Another object of the present invention is to provide a method for producing a resin sheet that is suitable for use in a light guide plate and various optical elements that do not cause deformation in the molded shape and that has excellent molded shape stability.
本発明の目的を達成する為には、ダイより押し出したシート状の溶融樹脂材料を第１の型ロールと該第１の型ローラに対向配置される第２の冷却ローラとで挟圧し、該第１の型ロール表面の凹凸形状を前記樹脂材料に転写し、転写後の前記樹脂材料を該第２の冷却ロールに巻き掛けることにより該第１の型ローラより剥離し、剥離後の前記樹脂材料を更に第２の冷却ロールと該第２の型ロールに対向配置される第３の冷却剥離ロールに巻き掛けることを特徴とした、賦型樹脂シートの製造方法が必要である。 In order to achieve the object of the present invention, a sheet-shaped molten resin material extruded from a die is sandwiched between a first mold roll and a second cooling roller disposed opposite to the first mold roller, The uneven shape on the surface of the first mold roll is transferred to the resin material, and the resin material after transfer is peeled off from the first mold roller by winding the resin material on the second cooling roll, and the resin after peeling There is a need for a method for producing a shaped resin sheet, in which the material is further wound around a second cooling roll and a third cooling peeling roll disposed opposite to the second mold roll.
さらには、第１型ロールの表面温度を樹脂材料のガラス転移温度＋４０℃以上、第２冷却ロールおよび第３冷却剥離ロールの表面温度をガラス転移温度−５０℃以下に温度制御されることが好ましい。つまり、賦型部の残留歪みを低減させ形状安定性を発現させるには、第１型ロールの表面温度は好ましくはガラス転移温度＋４０℃以上、より好ましくはガラス転移温度＋６０℃以上であり、好ましくはガラス転移温度＋１００℃以下の範囲である。第１型ロール表面温度がガラス転移温度＋４０℃未満では、形状転写はされるが微細賦型部に残留歪が残存し、後の加熱工程などで形状変形が発生し易くなる。一方、第１型ロール表面温度がガラス転移温度＋１００℃を超えると、第１型ロールとシート状樹脂との離型時の応力により賦型形状が変形し易くなる。また、賦型部の残留歪みを低減させ形状安定性を発現させるには、第２冷却ロールおよび第３冷却剥離ロールの表面温度は好ましくはガラス転移温度−５０℃以下、より好ましくはガラス転移温度−６０℃以下であり、好ましくはガラス転移温度−１００℃以上の範囲である。 Furthermore, it is preferable that the surface temperature of the first-type roll is controlled to a glass transition temperature of the resin material + 40 ° C. or higher, and the surface temperatures of the second cooling roll and the third cooling peeling roll are controlled to a glass transition temperature of −50 ° C. or lower. . That is, in order to reduce the residual distortion of the shaping part and to exhibit shape stability, the surface temperature of the first mold roll is preferably a glass transition temperature + 40 ° C. or higher, more preferably a glass transition temperature + 60 ° C. or higher, preferably Is a range of glass transition temperature + 100 ° C. or lower. When the surface temperature of the first mold roll is less than the glass transition temperature + 40 ° C., the shape is transferred, but residual strain remains in the finely shaped portion, and shape deformation is likely to occur in the subsequent heating step. On the other hand, if the surface temperature of the first mold roll exceeds the glass transition temperature + 100 ° C., the molded shape is likely to be deformed by the stress at the time of mold release between the first mold roll and the sheet-like resin. Moreover, in order to reduce the residual distortion of a shaping | molding part and to express shape stability, the surface temperature of a 2nd cooling roll and a 3rd cooling peeling roll becomes like this. Preferably it is glass transition temperature -50 degrees C or less, More preferably, it is a glass transition temperature. It is -60 degrees C or less, Preferably it is the range of glass transition temperature -100 degrees C or more.
また、本発明において、微細な形状を転写賦型するには、挟圧が重要である。一般的に挟圧は線圧で表すことが出来るが、高さ１００μｍ以下の微細形状の転写には好ましくは５０ｋｇ／ｃｍ以上の線圧が必要である。より好ましくは１００〜２００ｋｇ／ｃｍの範囲である。２００ｋｇ／ｃｍを超えると、押しつぶしによってシートの厚み方向前面に歪が発生し易く、シートのカール、反りなどの原因となると共に圧力によるロール軸の歪みが発生し易く、幅方向の賦型程度に差が発生する原因となる。 In addition, in the present invention, pinching pressure is important in order to transfer and mold a fine shape. In general, the pinching pressure can be expressed by a linear pressure. However, a linear pressure of 50 kg / cm or more is necessary for transferring a fine shape having a height of 100 μm or less. More preferably, it is the range of 100-200 kg / cm. If it exceeds 200 kg / cm, the sheet is likely to be distorted on the front surface in the thickness direction due to crushing, causing curling and warping of the sheet, and also causing the distortion of the roll axis due to pressure, to the extent of forming in the width direction. It causes a difference.
本発明の製造方法では、第１から第３ロールが必要である。このような３本ロール構成としては、横向きのダイから樹脂を吐出し縦型３本ロールで製膜する方法、下向きのダイから樹脂を吐出し横型の３本ロールで製膜する方法があるが、本発明においては、第１型ロールと第２ロールとで挟圧する前に、第２冷却ロール上に予めシート状溶融樹脂を密着させ固化を進ませることが好ましい。シート状溶融樹脂を第２冷却ロール上に密着させる方法としては、高電圧を金属線にかけて、静電気を発生させ密着させる静電ワイヤー式、スリットから高圧空気を噴出し密着させるエアーナイフ式など非接触式の密着方法が望ましい。特に設備の設置しやすさ、シートの温度制御性から静電ワイヤー式が好適である。 In the production method of the present invention, first to third rolls are necessary. As such a three-roll configuration, there are a method of discharging a resin from a horizontal die and forming a film with a vertical three-roll, and a method of discharging a resin from a downward die and forming a film with a horizontal three-roll. In the present invention, it is preferable that the sheet-like molten resin is brought into close contact with the second cooling roll in advance and solidified before being clamped between the first mold roll and the second roll. There are non-contact methods, such as an electrostatic wire type that applies high voltage to a metal wire to generate static electricity, and an air knife type that ejects high pressure air from a slit to make the sheet-like molten resin adhere to the second cooling roll. A close contact method is desirable. In particular, the electrostatic wire type is suitable from the viewpoint of ease of installation of equipment and temperature controllability of the sheet.
本発明の目的である、歪が無く形状安定性に優れた微細形状を賦型するには、樹脂が軟化する高い温度および高い圧力で賦型し、その後、硬化する温度まで冷却する工程を、第２冷却ロール上で行なう必要がある。このとき、重要な点は、第１型ロールと第２冷却ロールで挟圧する前に、予めシート状溶融樹脂を冷却し固化層を第２冷却ロール側に生成させておく必要がある。この固化層の生成が不十分の場合、高圧で挟圧を行なうと、シート膜厚が薄くなるばかりで、微細賦型部に圧力が掛からず転写不良となる。また、固化層厚みが薄いとシート全体の剛性が低く柔軟の為、挟圧した場合、第１型ロール側にシートが部分粘着しシワ、賦型形状崩れの原因となる。一方、固化が進み、シート厚み方向全域でガラス転移温度以下まで温度が低下すると、第１型ロールからの熱だけでは、転写賦型に十分な熱量を得ることが出来ず、その結果転写不良となる。本発明において、この固化層の生成を制御することによって効果を得ることが可能である。固化層の調整には、ダイから吐出される樹脂温度、シートの厚みなどによって条件は変化するが、第２冷却ロール温度および、第２冷却ロールにシート状溶融樹脂が密着してから第１型ロールおよび第２冷却ロールで挟圧されるまでの時間によって制御することが可能である。この第２冷却ロールに密着してから第１型ロールと挟圧されるまでの時間は２秒以上が好ましい。より好ましくは２〜１０秒の範囲である。この時間は、ロールの外径と回転速度によって選択することが可能である。また、挟圧され形状を転写されたシート状樹脂材料が、第２冷却ロールに巻き掛けられている時間は４秒以上が好ましく、４〜１５秒の範囲がより好ましい。 In order to mold a fine shape with no distortion and excellent shape stability, which is the object of the present invention, a process of molding at a high temperature and high pressure at which the resin softens and then cooling to a curing temperature, It is necessary to carry out on the second cooling roll. At this time, the important point is that the sheet-like molten resin needs to be cooled in advance and a solidified layer must be generated on the second cooling roll side before being pinched by the first mold roll and the second cooling roll. If the formation of the solidified layer is insufficient, if the clamping is performed at a high pressure, not only the film thickness is reduced, but no pressure is applied to the finely shaped portion, resulting in a transfer failure. Further, if the thickness of the solidified layer is thin, the rigidity of the entire sheet is low and flexible, and therefore when the sheet is pressed, the sheet partially adheres to the first mold roll side and causes wrinkles and deformation of the molded shape. On the other hand, if solidification progresses and the temperature drops below the glass transition temperature throughout the sheet thickness direction, it is not possible to obtain a sufficient amount of heat for transfer molding only with the heat from the first mold roll, and as a result, transfer failure and Become. In the present invention, it is possible to obtain an effect by controlling the formation of the solidified layer. For adjustment of the solidified layer, the conditions vary depending on the resin temperature discharged from the die, the thickness of the sheet, etc., but the first mold after the sheet-like molten resin is in close contact with the second cooling roll temperature and the second cooling roll. It is possible to control according to the time until the pressure is sandwiched between the roll and the second cooling roll. The time from the close contact with the second cooling roll to the clamping with the first mold roll is preferably 2 seconds or more. More preferably, it is in the range of 2 to 10 seconds. This time can be selected according to the outer diameter and rotation speed of the roll. Further, the time for which the sheet-shaped resin material that has been sandwiched and transferred in shape is wound around the second cooling roll is preferably 4 seconds or more, and more preferably in the range of 4 to 15 seconds.
本発明によれば、微細な形状を正確に転写賦型でき、さらにはガラス転移温度以上に加熱しても形状が変形することのない微細な形状を連続的に転写賦型された熱可塑性樹脂シートを得ることが可能である。 According to the present invention, a thermoplastic resin capable of accurately transferring and molding a fine shape, and further continuously transferring and molding a fine shape that does not deform even when heated above the glass transition temperature. It is possible to obtain a sheet.
以下、添付図面に従って、本発明に係る樹脂シートの製造方法の好ましい実施の形態（第１実施形態）について詳説する。図１は、本発明に係る樹脂シートの製造方法が適用される、樹脂シートの製造ラインの例を示す構成図である。 Hereinafter, a preferred embodiment (first embodiment) of a method for producing a resin sheet according to the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is a configuration diagram showing an example of a resin sheet production line to which a resin sheet production method according to the present invention is applied.
この樹脂シートの製造ラインは、押出し機（図示略）によって溶融された樹脂材料をシート状に賦形するためのシート用のダイ（１）と、表面に凹凸形状が形成された第１型ロール（２）と、第１型ロール（２）に対向配置される第２冷却ロール（３）と、第２冷却ロール（３）と対向配置される第３剥離ロール（４）より構成される。 This resin sheet production line includes a sheet die (1) for shaping a resin material melted by an extruder (not shown) into a sheet shape, and a first die roll having a concavo-convex shape formed on the surface. (2), a second cooling roll (3) disposed opposite to the first mold roll (2), and a third peeling roll (4) disposed opposite to the second cooling roll (3).
ダイ（１）のスリットサイズは、成形された溶融樹脂材料の幅が第１型ロール（２）の幅よりも広くなるように形成され、また、このダイ（１）から押し出される溶融樹脂材料が第２冷却ロール（３）の上部に押し出されるように配置されている。この溶融樹脂が第２冷却ロール（３）上部に接触する位置の上位に金属線（５）を配置し、静電気を発生させシート状溶融樹脂を第２冷却ロールに密着させる。 The slit size of the die (1) is formed so that the width of the molded molten resin material is wider than the width of the first mold roll (2), and the molten resin material extruded from the die (1) is It arrange | positions so that it may be extruded to the upper part of a 2nd cooling roll (3). The metal wire (5) is disposed above the position where the molten resin comes into contact with the upper part of the second cooling roll (3), and static electricity is generated to bring the sheet-shaped molten resin into close contact with the second cooling roll.
第１型ロール（２）の表面には、規則的な凹凸形状が形成されている。この規則的な凹凸形状は、たとえば、成形後の樹脂材料の反転形状とすることができる。
第１型ロール（２）の材質としては、各種鉄鋼部材、ステンレス鋼、銅、亜鉛、真鍮、これらの金属材料を芯金として、これらの金属材料にＨＣｒメッキ、Ｃｕメッキ、Ｎｉメッキ等のメッキを施したもの、セラミックス、及び各種の複合材料が採用できる。
A regular uneven shape is formed on the surface of the first type roll (2). This regular uneven | corrugated shape can be made into the reverse shape of the resin material after shaping | molding, for example.
As the material of the first type roll (2), various steel members, stainless steel, copper, zinc, brass, and these metal materials are used as a core metal, and these metal materials are plated with HCr plating, Cu plating, Ni plating or the like. , Ceramics, and various composite materials can be used.
型ロール表面の凹凸パターン形成方法としては、凹凸パターン（ピッチ、深さ、等）や型ローラ表面の材質にもよるが、一般的にはＮＣ旋盤による切削加工と仕上げバフ加工との組み合わせが好ましく採用できる。また、他の公知の加工方法（研削加工、超音波加工、放電加工、等）も採用できる。型ロール表面の表面粗さは、Ｒａで０．５μｍ以下とするのが好ましく、０．２μｍ以下とするのがより好ましい。 As a method for forming the concavo-convex pattern on the surface of the mold roll, although depending on the concavo-convex pattern (pitch, depth, etc.) and the material of the surface of the mold roller, a combination of cutting with an NC lathe and finishing buffing is generally preferred Can be adopted. In addition, other known processing methods (grinding processing, ultrasonic processing, electric discharge processing, etc.) can also be employed. The surface roughness of the mold roll surface is preferably 0.5 μm or less in terms of Ra, and more preferably 0.2 μm or less.
また型ロールは、ガラス転移温度以上の高温でシート状樹脂に接触する為、ロール表面への樹脂の粘着が発生する。その為、型ロール表面には何かしらの離型処理を行なうことが望ましい。離型処理としては、表面にフッ素系樹脂の焼付け塗布、シリコン系樹脂の焼付け塗布などが一般的であるが、微細形状表面に塗布することによって形状が変化してしまう恐れがあるので、好ましくは、彫刻された凹凸パターンの表面に、Ｎｉ−ＰＴＦＥのような離型効果の高いメッキを数μｍ程度メッキする方法。または、凹凸パターンにＴｉＮやＤＬＣのような蒸着を行なうことも有効である。型ロールは、図示しない駆動手段により、所定の周速度で回転駆動されるようになっている。また、型ロールには、温度調節手段が施されている。このような温度調節手段が設けられることにより、本発明の効果を発現する為、樹脂材料のガラス転移温度＋５０℃以上に加熱されている。温度調節手段の構成については、後述する。 In addition, since the mold roll comes into contact with the sheet-like resin at a temperature higher than the glass transition temperature, the resin sticks to the roll surface. Therefore, it is desirable to perform some mold release treatment on the mold roll surface. As the mold release treatment, baking coating of fluorine-based resin, baking coating of silicon-based resin, etc. are common on the surface, but there is a possibility that the shape may change by applying to the surface of fine shape, so preferably A method of plating the surface of the engraved concavo-convex pattern with a high release effect such as Ni-PTFE on the order of several μm. Alternatively, it is also effective to perform deposition such as TiN or DLC on the uneven pattern. The mold roll is driven to rotate at a predetermined peripheral speed by a driving means (not shown). The mold roll is provided with temperature adjusting means. By providing such temperature adjusting means, the resin material is heated to a glass transition temperature + 50 ° C. or higher in order to exhibit the effects of the present invention. The configuration of the temperature adjusting means will be described later.
第２冷却ロール（３）は、第１型ロール（２）に対向配置され、型ロールとにより樹脂材料を挟圧するためのロールである。
第３剥離ロール（４）は、第２冷却ロール（３）に対向配置され、第２冷却ロール（３）とにより樹脂材料を挟圧するとともに、樹脂材料を巻き掛けることにより樹脂材料を第２冷却ロール（３）より剥離させるためのローラである。
A 2nd cooling roll (3) is a roll for opposingly arrange | positioning a 1st type | mold roll (2), and clamping a resin material with a type | mold roll.
The third peeling roll (4) is disposed to face the second cooling roll (3), sandwiches the resin material with the second cooling roll (3), and winds the resin material to cool the resin material second. It is a roller for making it peel from a roll (3).
冷却ロール及び剥離ロールの表面は鏡面状に加工されていることが好ましい。このような表面とすることにより、成形後の樹脂材料の裏面を良好な状態にできる。そして、冷却ロール及び剥離ロール表面の表面粗さは、Ｒａで０．５μｍ以下とするのが好ましく、０．２μｍ以下とするのがより好ましい。 The surfaces of the cooling roll and the peeling roll are preferably processed into a mirror surface. By setting it as such a surface, the back surface of the resin material after shaping | molding can be made into a favorable state. And the surface roughness of the surface of a cooling roll and a peeling roll is preferably 0.5 μm or less in Ra, and more preferably 0.2 μm or less.
冷却ロール及び剥離ロールの材質としては、各種鉄鋼部材、ステンレス鋼、銅、亜鉛、真鍮、これらの金属材料を芯金として、表面にゴムライニングしたもの、これらの金属材料にＨＣｒメッキ、Ｃｕメッキ、Ｎｉメッキ等のメッキを施したもの、セラミックス、及び各種の複合材料が採用できる。 As the material of the cooling roll and the peeling roll, various steel members, stainless steel, copper, zinc, brass, those metal materials as a cored bar, a rubber lining on the surface, these metal materials are HCr plated, Cu plated, Ni-plated or other plated materials, ceramics, and various composite materials can be used.
冷却ロール及び剥離ロールは、いずれも、図示しない駆動手段により、所定の周速度で回転駆動されるようになっている。なお、剥離ロールに駆動手段を設けない構成も可能であるが、樹脂材料の裏面を良好な状態にできる点より、駆動手段を設けることが好ましい。
各ロールに駆動手段を設ける場合に、それぞれの駆動速度を可変とする構成が好ましく採用できる。
Both the cooling roll and the peeling roll are rotationally driven at a predetermined peripheral speed by a driving means (not shown). In addition, although the structure which does not provide a drive means in a peeling roll is also possible, it is preferable to provide a drive means from the point which can make the back surface of a resin material a favorable state.
In the case where a driving means is provided for each roll, a configuration in which the respective driving speeds can be preferably adopted.
型ロール、冷却ロール及び剥離ロールには、いずれも、図示しない加圧手段が設けられており、型ロール、冷却ロール及び剥離ロールとの間の樹脂材料を所定の圧力で挟圧できるようになっている。この加圧手段は、いずれも、型ロール、冷却ロール及び剥離ロールとの接触点における法線方向に圧力を印加する構成のもので、モータ駆動手段、エアシリンダ、油圧シリンダ等の公知の各種手段が採用できる。本発明においては、好ましくは線圧５０ｋｇ／ｃｍ以上が必要となる為、シート幅が８００ｍｍの場合４０００ｋｇ以上加圧力が必要なことから油圧シリンダが好ましい。 Each of the mold roll, the cooling roll, and the peeling roll is provided with a pressing means (not shown), and the resin material between the mold roll, the cooling roll, and the peeling roll can be clamped at a predetermined pressure. ing. These pressurizing means are all configured to apply pressure in the normal direction at the point of contact with the mold roll, cooling roll and peeling roll, and various known means such as motor drive means, air cylinders, hydraulic cylinders, etc. Can be adopted. In the present invention, since a linear pressure of 50 kg / cm or more is required, a hydraulic cylinder is preferable because a pressurizing force of 4000 kg or more is required when the seat width is 800 mm.
型ロール、冷却ロール及び剥離ロールには、挟圧力の反力による撓みが生じにくくなるような構成を採用することもできる。このような構成としては、冷却ロール及び剥離ロールに、クラウン形状（中高形状とする）を採用する構成、ローラの軸方向中央部の剛性が大きくなるような強度分布を付けたローラの構成、及びこれらを組み合わせた構成等が採用できる。 The mold roll, the cooling roll, and the peeling roll may be configured to be less likely to bend due to the reaction force of the clamping pressure. As such a configuration, a configuration in which a crown shape (middle and high shape) is adopted for the cooling roll and the peeling roll, a configuration of a roller with a strength distribution that increases the rigidity of the central portion in the axial direction of the roller, and A combination of these can be employed.
型ロール、冷却ロール及び剥離ロールのそれぞれのロール温度調節手段としては、ロール内部に温度調節したオイルを循環させる構成が好ましく採用できる。このオイルの供給と排出は、ローラの端部にロータリージョイントを設ける構成により実現できる。
他の温度調節手段としては、たとえば、ローラの内部にシースヒータを埋め込む構成、ローラの近傍に誘電加熱手段を配する構成等、公知の各種手段が採用できる。
As each roll temperature adjusting means of the mold roll, the cooling roll, and the peeling roll, a configuration in which the temperature-controlled oil is circulated inside the roll can be preferably employed. This supply and discharge of oil can be realized by a configuration in which a rotary joint is provided at the end of the roller.
As other temperature adjusting means, for example, various known means such as a structure in which a sheath heater is embedded in the roller and a structure in which a dielectric heating means is disposed in the vicinity of the roller can be adopted.
以上説明した各ロール、及び、樹脂材料の各箇所の表面温度がモニターできるように、表面温度測定手段（図示略）を設けることが好ましい。このような表面温度測定手段としては、赤外線温度計、放射式温度計等の公知の各種測定手段が採用できる。
次に、図１に示される樹脂シートの製造ラインによる樹脂シートの具体的製造方法について説明する。
It is preferable to provide surface temperature measuring means (not shown) so that the surface temperature of each roll described above and each part of the resin material can be monitored. As such surface temperature measuring means, various known measuring means such as an infrared thermometer and a radiation thermometer can be employed.
Next, a specific method for producing a resin sheet by the resin sheet production line shown in FIG. 1 will be described.
本発明に適用される樹脂材料としては、熱可塑性樹脂を用いることができ、たとえば、ポリメチルメタクリレート樹脂（ＰＭＭＡ）、ポリカーボネート樹脂、ポリスチレン樹脂、ＭＳ樹脂、ＡＳ樹脂、ポリプロピレン樹脂、ポリエチレン樹脂、ポリエチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、熱可塑性エラストマー、又はこれらの共重合体、シクロオレフィンポリマー等が挙げられるが、本明細では、ガラス転移温度約１２０℃のポリエチレンナフタレートを用いた賦型シートの製造方法について例示する。 As the resin material applied to the present invention, a thermoplastic resin can be used. For example, polymethyl methacrylate resin (PMMA), polycarbonate resin, polystyrene resin, MS resin, AS resin, polypropylene resin, polyethylene resin, polyethylene terephthalate Resin, polyethylene naphthalate resin, thermoplastic elastomer, or a copolymer thereof, cycloolefin polymer, and the like. In the present specification, a method for producing a shaped sheet using polyethylene naphthalate having a glass transition temperature of about 120 ° C. It illustrates about.
以下実施例により本発明をさらに詳細に説明する。本発明はこれらの実施例に限定されるものではない。なお、実施例に記載した種々の特性値は、次に示す方法により測定したものである。 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Various characteristic values described in the examples are measured by the following methods.
（固有粘度 ＩＶ）
テトラクロロエタン：フェノール＝４：６の混合溶媒を用いて、３５℃で測定した。
（ガラス転移温度 Ｔｇ）
セイコー電子工業（株）製ＤＳＣ（示差走査熱量計）２２０を用いて測定した。ＤＳＣの測定条件は次の通りである。試料フィルム１０ｍｇをＤＳＣ装置にセットし、昇温速度２０℃／分で加熱し、３００℃の温度で溶融した後、液体窒素中に急冷する。この急冷試料を１０℃／分で昇温し、ガラス転移点を検知する。
(Intrinsic viscosity IV)
It measured at 35 degreeC using the mixed solvent of tetrachloroethane: phenol = 4: 6.
(Glass transition temperature Tg)
This was measured using a DSC (differential scanning calorimeter) 220 manufactured by Seiko Denshi Kogyo Co., Ltd. The DSC measurement conditions are as follows. 10 mg of a sample film is set in a DSC apparatus, heated at a temperature rising rate of 20 ° C./min, melted at a temperature of 300 ° C., and then rapidly cooled in liquid nitrogen. The rapidly cooled sample is heated at 10 ° C./min, and the glass transition point is detected.
［実施例１］
２，６−ナフタレンジカルボン酸ジメチルエステル１００重量部とエチレングリコール５１重量部を酢酸コバルト四水和物０．０１０重量部（１０ミリモル％）、酢酸マンガン０．０３０重量部（３０ミリモル％）の存在下、定法によりエステル交換反応を行いメタノール溜出２０分後に三酸化アンチモン０．０１２重量部（１０ミリモル％）を添加し、エステル交換反応終了前に正リン酸０．０２０重量部（５０ミリモル％）を添加した。次いで２９５℃、１．３×１０２Ｐａ以下の高真空下で重縮合反応を行い固有粘度０．４７ｄｌ／ｇのポリエチレン−２，６−ナフタレートプレポリマーを得た。さらにこのプレポリマーを用いて定法により固相重合を行い、固有粘度０．６８ｄｌ／ｇ、ガラス転移温度１２５℃のポリエチレン−２，６−ナフタレートペレットを得た。
[Example 1]
Existence of 100 parts by weight of 2,6-naphthalenedicarboxylic acid dimethyl ester and 51 parts by weight of ethylene glycol in 0.010 parts by weight (10 mmol%) of cobalt acetate tetrahydrate and 0.030 parts by weight (30 mmol%) of manganese acetate Then, a transesterification reaction was carried out by a conventional method, and 0.012 part by weight (10 mmol%) of antimony trioxide was added 20 minutes after the distillation of methanol. ) Was added. Subsequently, a polycondensation reaction was performed at 295 ° C. under a high vacuum of 1.3 × 10 2 Pa or less to obtain a polyethylene-2,6-naphthalate prepolymer having an intrinsic viscosity of 0.47 dl / g. Furthermore, solid phase polymerization was performed by a conventional method using this prepolymer, and polyethylene-2,6-naphthalate pellets having an intrinsic viscosity of 0.68 dl / g and a glass transition temperature of 125 ° C. were obtained.
ペレット状の樹脂を１７５℃で５時間熱風乾燥させてからスクリュ径３０ｍｍの同方向２軸押出し機にて３００℃で溶融し、幅３００ｍｍのＴダイより吐出させた。この溶融したシート状樹脂を、ロール径４００ｍｍΦ、ハードクロムメッキされ鏡面を有する第２冷却ロール（３）の上部に落下させ、設置された線形０．２ｍｍのステンレス線に１０ｋｖの高電圧をかける静電密着（ピンニング）法によってシート状溶融樹脂を第２冷却ロール（３）に密着させた。その後、第２冷却ロールと対向する位置に設置された、円周方向に連続な底辺５０μｍ、高さ２５μｍ、頂角９０°のＶ溝を有する第１型ロール（２）と、第２冷却ロール（３）とで挟圧を行なった。第１型ロールは、通常の２０ｍｍΦ鋼管ロール表面に０．５ｍｍのＣｕメッキを行なった後、上記のＶ溝を切削加工行い、その表面にＮｉ−ＰＴＦＥメッキを６μｍ程度のせた。 The pellet-shaped resin was dried with hot air at 175 ° C. for 5 hours, melted at 300 ° C. with a twin screw extruder having a screw diameter of 30 mm, and discharged from a T die having a width of 300 mm. This molten sheet-like resin is dropped on the upper part of the second cooling roll (3) having a roll diameter of 400 mmΦ and hard-chromium plated and having a mirror surface, and a static voltage for applying a high voltage of 10 kv to the installed linear 0.2 mm stainless steel wire. The sheet-like molten resin was brought into close contact with the second cooling roll (3) by an electro-adhesion (pinning) method. Then, the 1st type | mold roll (2) which was installed in the position facing a 2nd cooling roll, and has the V groove | channel of 50 micrometers of bases continuous in the circumferential direction, 25 micrometers in height, and 90 degrees of apex angles, and 2nd cooling roll Clamping was performed in (3). In the first type roll, 0.5 mm of Cu plating was performed on the surface of a normal 20 mmφ steel pipe roll, and then the above V-groove was cut, and Ni-PTFE plating was applied on the surface to about 6 μm.
その後、シート状樹脂は、半周冷却ロール上を沿わせた後、更に第２冷却ロール（３）と対向する位置に設置されたロール径４００ｍｍΦで表面がＣｒメッキされ鏡面処理された第３剥離ロール（４）に巻き掛け賦型樹脂シートを得た。このときの、各ロール温度は、第１型ロール（２）は油温調機によって２１０℃に加熱し、第２冷却ロールおよび第３剥離ロールについては、水温調機によって６０℃に表面温度を制御した。第１型ロールの軸には油圧シリンダが設置され、第２冷却ロールに対し押し付けることが可能である。この押付圧は３００ｍｍ幅のロールに対し３ｔｏｎの力で押付け、線圧１００ｋｇ／ｃｍを得た。一方、同様に第３剥離ロールを第２冷却ロールに線圧１０ｋｇ／ｃｍにて押付けた。シート引取り速度３ｍ／ｍｉｎとし、シート厚みが２００μｍになるように押出機吐出量を調整した。 After that, after the sheet-like resin is placed on the half-cooling roll, the third peeling roll whose surface is Cr-plated and mirror-finished with a roll diameter of 400 mmΦ installed at a position facing the second cooling roll (3). (4) was wound around to obtain a molded resin sheet. At this time, each roll temperature is heated to 210 ° C. by the oil temperature controller for the first type roll (2), and the surface temperature is adjusted to 60 ° C. by the water temperature controller for the second cooling roll and the third peeling roll. Controlled. A hydraulic cylinder is installed on the shaft of the first roll and can be pressed against the second cooling roll. This pressing pressure was pressed against a 300 mm wide roll with a force of 3 tons to obtain a linear pressure of 100 kg / cm. On the other hand, the third peeling roll was similarly pressed against the second cooling roll at a linear pressure of 10 kg / cm. The discharge rate of the extruder was adjusted so that the sheet take-up speed was 3 m / min and the sheet thickness was 200 μm.
このとき、シート状溶融樹脂が第２冷却ロールに密着してから、第１型ロールとで挟圧されるまでの時間は６．２秒、更に、第１ロールと挟圧されてから、第３剥離ロールへまきかえられるまでの時間は１２．４秒であった。このようにして、製造された賦型シートの賦型形状を、キーエンス社レーザー顕微鏡（ＶＫ−９７００）を用いて測定したところ、頂角９０°高さ２３μｍのプリズム形状が正確に転写賦型されていた。またこのシートを、ガラス転移温度以上の１４０℃に加熱した後、同様に賦型形状を測定したところ、頂角および高さ共に変化は見られなかった。 At this time, the time from when the sheet-like molten resin is in close contact with the second cooling roll until it is clamped with the first mold roll is 6.2 seconds, and after being clamped with the first roll, It took 12.4 seconds to roll up to 3 peeling rolls. Thus, when the shaping shape of the produced shaping sheet was measured using a Keyence Corporation laser microscope (VK-9700), the prism shape having a vertex angle of 90 ° and a height of 23 μm was accurately transferred and shaped. It was. Moreover, after heating this sheet | seat to 140 degreeC more than a glass transition temperature, when the shaping | molding shape was measured similarly, neither change was seen in the apex angle and height.
［比較例１］
前記特許文献３（特開２００３−５３８３４号公報）に一例として記載されている、従来の賦型設備での実施形態について、本発明の比較として図２に示し詳細を説明する。
図２に示す、従来のプロセスでは、ダイ（１）から吐出されたシート状樹脂は、金属冷却ロール（６）と対向に位置する型ロール（７）との接触面に落下させ挟圧され賦型される。そして、型ロール（７）上で冷却されたシートは、型ロール（７）と対向の位置に設置された剥離ロール（８）に巻添えられる。このときの、各ロール材質、溶融樹脂押出、Ｔダイなどは上記実施例１と同様とした。このとき、冷却ロール（６）、型ロール（７）共に、１３０℃を超えるとロール剥離困難となり、型ロール（７）と剥離ロール（８）でシート面にシワが発生する。その為、シワの無いシートを得る為には、冷却ロール（６）を１００℃、型ロール（７）を１２０℃、剥離ロール（８）を６０℃とした。この温度で得られた賦型シートの賦型形状を観察したところ、頂角９０°高さ２１μｍとほぼプリズム形状が転写賦型されているが、このシートを１４０℃加熱処理すると、賦型形状は頂角が消滅し半円状となり、高さは１１μｍと著しく変形した。
[Comparative Example 1]
An embodiment of a conventional shaping facility described as an example in Patent Document 3 (Japanese Patent Laid-Open No. 2003-53834) will be described in detail with reference to FIG. 2 as a comparison of the present invention.
In the conventional process shown in FIG. 2, the sheet-like resin discharged from the die (1) is dropped on the contact surface between the metal cooling roll (6) and the mold roll (7) located opposite to the sheet-shaped resin and pressed. Typed. And the sheet | seat cooled on the type | mold roll (7) is wound around the peeling roll (8) installed in the position facing a type | mold roll (7). Each roll material, molten resin extrusion, T-die, and the like at this time were the same as those in Example 1. At this time, when both the cooling roll (6) and the mold roll (7) exceed 130 ° C., the roll peeling becomes difficult, and the mold roll (7) and the peeling roll (8) are wrinkled on the sheet surface. Therefore, in order to obtain a sheet without wrinkles, the cooling roll (6) was set to 100 ° C, the mold roll (7) was set to 120 ° C, and the peeling roll (8) was set to 60 ° C. When the molded shape of the molded sheet obtained at this temperature was observed, the apex angle was 90 ° and the height was 21 μm, and almost the prism shape was transferred, but when this sheet was heat treated, the molded shape was The apex angle disappeared and became semicircular, and the height was remarkably deformed to 11 μm.
［参考例１］
実施例１と同様の設備、条件にて、シート引取り速度を１５ｍ／ｍｉｎに変更して、厚み１５０μｍのシートを得た。シート状溶融樹脂が第２冷却ロールに密着してから、第１型ロールとで挟圧されるまでの時間は１．３秒であった。その時、第１型ロール（２）との挟圧によって、シート全体が第１型ロール間で剥離不良が発生し、その結果シートが第１型ロールに取られて、シート面にシワが発生した。
[Reference Example 1]
A sheet having a thickness of 150 μm was obtained by changing the sheet take-up speed to 15 m / min under the same equipment and conditions as in Example 1. The time from when the sheet-like molten resin was in close contact with the second cooling roll to when it was nipped with the first mold roll was 1.3 seconds. At that time, due to the clamping force with the first mold roll (2), the entire sheet was poorly peeled between the first mold rolls, and as a result, the sheet was taken up by the first mold roll and wrinkles were generated on the sheet surface. .
［参考例２］
実施例１と同様の設備、条件にて、第１型ロール（２）の温度を１５０℃に変更して、厚み２００μｍのシートを得たが、得られたシートの賦型形状は、頂角９０°高さ２３μｍと正確にプリズム形状が転写賦型されていたが、そのシートを１４０℃に加熱処理を行なったところ、プリズム形状は変形し、頂角が消滅し円形となり、高さは１３μｍとなった。
[Reference Example 2]
In the same equipment and conditions as in Example 1, the temperature of the first mold roll (2) was changed to 150 ° C. to obtain a sheet having a thickness of 200 μm. The prism shape was accurately transferred and molded at 90 ° height of 23 μm, but when the sheet was heated to 140 ° C., the prism shape was deformed, the apex angle disappeared and became circular, and the height was 13 μm. It became.
１：ダイ
２：第１型ロール
３：第２冷却ロール
４：第３剥離ロール
５：静電密着用ワイヤー
６：冷却ロール
７：型ロール
８：剥離ロール
1: Die 2: First mold roll 3: Second cooling roll 4: Third peeling roll 5: Electrostatic adhesion wire 6: Cooling roll 7: Mold roll 8: Peeling roll
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| JP2013208831A (en) * | 2012-03-30 | 2013-10-10 | Toppan Cosmo Inc | Method of manufacturing embossed clear sheet |
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| CN115230244A (en) * | 2022-05-11 | 2022-10-25 | 株洲时代华先材料科技有限公司 | Roller type hot-pressing device and hot-pressing process thereof |
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