JP2003236915A - Method for manufacturing amorphous thermoplastic resin sheet - Google Patents
Method for manufacturing amorphous thermoplastic resin sheetInfo
- Publication number
- JP2003236915A JP2003236915A JP2002045216A JP2002045216A JP2003236915A JP 2003236915 A JP2003236915 A JP 2003236915A JP 2002045216 A JP2002045216 A JP 2002045216A JP 2002045216 A JP2002045216 A JP 2002045216A JP 2003236915 A JP2003236915 A JP 2003236915A
- Authority
- JP
- Japan
- Prior art keywords
- cooling drum
- resin
- thermoplastic resin
- sheet
- amorphous thermoplastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非晶性熱可塑性樹
脂シートの製造方法に関する。さらに詳しくは、本発明
は、厚みムラが少なく、表面平滑性が良好であり、位相
差が小さい光学特性に優れた非晶性熱可塑性樹脂シート
を安定して製造することができ、特に脂環式構造を有す
る樹脂のシートの製造に適した非晶性熱可塑性樹脂シー
トの製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an amorphous thermoplastic resin sheet. More specifically, the present invention is capable of stably producing an amorphous thermoplastic resin sheet excellent in optical characteristics having a small thickness unevenness, good surface smoothness, and a small retardation, and particularly an alicyclic ring. The present invention relates to a method for producing an amorphous thermoplastic resin sheet suitable for producing a resin sheet having a formula structure.
【０００２】[0002]
【従来の技術】近年、液晶ディスプレイ（ＬＣＤ）の軽
量化、薄型化、大画面化を目指して、ガラス基板のプラ
スチックフイルムによる代替が試みられている。また、
超ねじれネマチック（ＳＴＮ）には、位相差フィルムと
偏光フィルムが用いられ、薄膜トランジスタ（ＴＦＴ）
には、偏光フィルムが用いられる。液晶材料として用い
られるこれらのフィルムには、高度の表面平滑性と光学
特性が必要であり、ダイライン、フィッシュアイ、シル
バーストリーク、異物などのないフィルムが求められ
る。このために、光学特性に優れたプラスチック材料の
開発が進められるとともに、製膜技術についても種々の
改良が試みられている。例えば、特開２０００−２８０
２６８号公報には、位相差が小さくて優れた光学特性を
有し、表面平滑性が高く、光学シートとして好適な熱可
塑性樹脂シートの製造方法として、ダイスから押し出さ
れた溶融状態の熱可塑性樹脂を、キャストドラムと、キ
ャストドラムにその周方向に沿って圧接した金属製の無
端ベルトとの間に通過させることにより、熱可塑性樹脂
を挟圧して無端ベルトに圧着させる工程を有するシート
の製造方法であって、無端ベルトは当該無端ベルトを介
してキャストドラムに並ぶよう配置された駆動用ロール
を含む複数のロールよりなる保持ロール群によって、張
力が作用された状態で保持され、熱可塑性樹脂のガラス
転移温度をＴg（℃）としたとき、キャストドラムの表
面温度及び駆動用ロールの表面温度の各々がＴg〜Ｔg＋
５０（℃）である熱可塑性樹脂シートの製造方法が提案
されている。しかし、無端ベルトを有する製膜装置は、
ドラムのみからなる製膜装置に比べて構造が複雑で設備
費が高く、運転管理も複雑であり、さらにこの方法によ
っても膜厚精度の良好なシートを安定して製造すること
は困難である。また、特開２００１−３０３３７号公報
には、位相差むらが少なくて安定した光学特性を有する
透明樹脂シートを製造することができる方法として、環
状オレフィン系樹脂を溶融してダイスからシート状に押
し出し、表面が鏡面加工されてなる冷却ロールに密着さ
せて成形し、得られた樹脂シートを引取ロールによって
引き取る工程を有する透明樹脂シートの製造方法におい
て、冷却ロールと引取ロールとの間において樹脂シート
に作用する張力が±１０％の範囲内で一定となるように
制御される透明樹脂シートの製造方法が提案されてい
る。しかし、このような方法によっても、特にシートの
端部の厚みのばらつきが大きくなりやすく、膜厚精度の
良好なシートを安定して製造することは困難であった。2. Description of the Related Art In recent years, an attempt has been made to replace a glass substrate with a plastic film in order to make a liquid crystal display (LCD) lighter, thinner and have a larger screen. Also,
A super-twisted nematic (STN) uses a retardation film and a polarizing film to form a thin film transistor (TFT).
A polarizing film is used for. These films used as a liquid crystal material are required to have a high degree of surface smoothness and optical characteristics, and a film free from die lines, fish eyes, silver streaks, foreign matters, etc. is required. For this reason, the development of plastic materials having excellent optical properties has been promoted, and various improvements have been attempted in film forming technology. For example, Japanese Patent Laid-Open No. 2000-280
As disclosed in Japanese Patent No. 268, a thermoplastic resin sheet having a small phase difference, excellent optical characteristics, high surface smoothness, and suitable as an optical sheet, which is suitable for an optical sheet, is a molten thermoplastic resin extruded from a die. , A method for producing a sheet having a step of pressing the thermoplastic resin to press it against the endless belt by passing it between the cast drum and a metal endless belt pressed against the cast drum along its circumferential direction. The endless belt is held in a state in which tension is applied by a holding roll group including a plurality of rolls including a driving roll arranged so as to be lined up with the cast drum via the endless belt, and the endless belt is made of a thermoplastic resin. When the glass transition temperature is Tg (° C), the surface temperature of the cast drum and the surface temperature of the driving roll are Tg to Tg +
A method for producing a thermoplastic resin sheet having a temperature of 50 (° C) has been proposed. However, a film forming apparatus having an endless belt is
Compared with a film forming apparatus consisting only of a drum, the structure is complicated, the equipment cost is high, and the operation management is complicated. Further, it is difficult to stably manufacture a sheet having a good film thickness accuracy even by this method. Further, JP-A-2001-30337 discloses a method for producing a transparent resin sheet having little phase difference unevenness and stable optical characteristics, by melting a cyclic olefin resin and extruding it into a sheet form from a die. , The surface is mirror-finished and molded by closely contacting with a cooling roll, in the method for producing a transparent resin sheet having a step of taking the obtained resin sheet by a take-up roll, to a resin sheet between the cooling roll and the take-up roll. A method for producing a transparent resin sheet has been proposed in which the applied tension is controlled to be constant within a range of ± 10%. However, even by such a method, the variation in the thickness of the end portion of the sheet is likely to be large, and it is difficult to stably manufacture the sheet having a good film thickness accuracy.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、厚みムラが
少なく、表面平滑性が良好であり、位相差が小さい光学
特性に優れた非晶性熱可塑性樹脂シートを安定して製造
することができ、特に脂環式構造を有する樹脂のシート
の製造に適した非晶性熱可塑性樹脂シートの製造方法を
提供することを目的としてなされたものである。DISCLOSURE OF THE INVENTION The present invention is capable of stably producing an amorphous thermoplastic resin sheet having a small thickness unevenness, a good surface smoothness, a small retardation and excellent optical characteristics. The object of the present invention is to provide a method for producing an amorphous thermoplastic resin sheet which is suitable for producing a sheet of a resin having an alicyclic structure.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく鋭意研究を重ねた結果、ダイスから押し
出された溶融状態の熱可塑性樹脂を複数の冷却ドラムの
周方向に沿って通過させる非晶性熱可塑性樹脂シートの
製造方法において、前記ダイスから押し出されたシート
状溶融樹脂が最初に接触する第一冷却ドラムでの樹脂接
触時間をｔ（秒）、第一冷却ドラムを離れるときの樹脂
温度をＴ1（℃）、樹脂のガラス転移温度をＴg（℃）と
したとき、ｔ×（Ｔ1−Ｔg）を−５０〜＋２０（秒・
℃）に制御することにより、光学特性の良好なシートを
安定して製造し得ることを見いだし、この知見に基づい
て本発明を完成するに至った。すなわち、本発明は、
（１）押出機から押し出されたシート状溶融熱可塑性樹
脂を、第一冷却ドラム、第二冷却ドラムの２本のドラム
の周に沿って順に通過させる非晶性熱可塑性樹脂シート
の製造方法において、第一冷却ドラムでの樹脂接触時間
をｔ（秒）、第一冷却ドラムを離れるときの樹脂温度を
Ｔ1（℃）、樹脂のガラス転移温度をＴg（℃）としたと
き、ｔ×（Ｔ1−Ｔg）を、−５０〜＋２０（秒・℃）と
することを特徴とする非晶性熱可塑性樹脂シートの製造
方法、（２）樹脂が第一冷却ドラムを離れ、第二冷却ド
ラムに接触するまでの時間が０.３〜５（秒）であり、
かつ第二冷却ドラム接触開始時の樹脂温度がＴg−８０
〜Ｔg＋１０（℃）である第１項記載の非晶性熱可塑性
樹脂シートの製造方法、（３）第二冷却ドラムの表面温
度が、Ｔg−９０〜Ｔg−１０（℃）である第１項又は第
２項記載の非晶性熱可塑性樹脂シートの製造方法、
（４）第一冷却ドラムと第二冷却ドラムとの相対的位置
を変えることにより、第一冷却ドラムでの樹脂接触時
間、及び、第一冷却ドラムを離れ第二冷却ドラムに接触
するまでの時間を調整する第１項又は第２項記載の非晶
性熱可塑性樹脂シートの製造方法、（５）熱可塑性樹脂
が、脂環式構造を有する樹脂である第１項、第２項又は
第３項記載の非晶性熱可塑性樹脂シートの製造方法、及
び、（６）脂環式構造を有する樹脂が、ノルボルネン系
開環重合体水素添加物又はビニル脂環式炭化水素重合体
である第５項記載の非晶性熱可塑性樹脂シートの製造方
法、を提供するものである。Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a molten thermoplastic resin extruded from a die is spread along the circumferential direction of a plurality of cooling drums. In the method for producing an amorphous thermoplastic resin sheet to be passed through, the resin contact time at the first cooling drum with which the sheet-shaped molten resin extruded from the die first contacts is t (second), and the first cooling drum is When the resin temperature at the time of leaving is T 1 (° C.) and the glass transition temperature of the resin is T g (° C.), t × (T 1 −Tg) is −50 to +20 (sec.
It has been found that a sheet having good optical properties can be stably produced by controlling the temperature to be controlled to (° C.), and the present invention has been completed based on this finding. That is, the present invention is
(1) A method for producing an amorphous thermoplastic resin sheet, which comprises passing a sheet-shaped molten thermoplastic resin extruded from an extruder along the circumference of two drums of a first cooling drum and a second cooling drum in order. When the resin contact time on the first cooling drum is t (seconds), the resin temperature when leaving the first cooling drum is T 1 (° C.), and the glass transition temperature of the resin is Tg (° C.), t × ( T 1 -Tg) is -50 to +20 (sec · ° C.), a method for producing an amorphous thermoplastic resin sheet, (2) the resin leaves the first cooling drum, and the second cooling drum It takes 0.3 to 5 (seconds) to contact the
Moreover, the resin temperature at the start of contact with the second cooling drum is Tg-80.
To Tg + 10 (° C), the method for producing an amorphous thermoplastic resin sheet according to item 1, (3) the surface temperature of the second cooling drum is Tg-90 to Tg-10 (° C). Or a method for producing an amorphous thermoplastic resin sheet according to item 2,
(4) By changing the relative positions of the first cooling drum and the second cooling drum, the resin contact time at the first cooling drum and the time until the resin leaves the first cooling drum and contacts the second cooling drum. 1. The method for producing an amorphous thermoplastic resin sheet according to claim 1 or 2, wherein (5) the thermoplastic resin is a resin having an alicyclic structure, 1), 2) or 3). Item 5. The method for producing an amorphous thermoplastic resin sheet according to Item, and (6) the resin having an alicyclic structure is a norbornene-based ring-opening polymer hydrogenated product or a vinyl alicyclic hydrocarbon polymer. And a method for producing an amorphous thermoplastic resin sheet.
【０００５】[0005]
【発明の実施の形態】本発明の方法は、押出機から押し
出されたシート状溶融熱可塑性樹脂を、第一冷却ドラ
ム、第二冷却ドラムの２本のドラムの周方向に沿って順
に通過させる非晶性熱可塑性樹脂シートの製造方法にお
いて、第一冷却ドラムでの樹脂接触時間をｔ（秒）、第
一冷却ドラムを離れるときの樹脂温度をＴ1（℃）、樹
脂のガラス転移温度をＴg（℃）としたとき、ｔ×（Ｔ1
−Ｔg）を−５０〜＋２０（秒・℃）、より好ましくは
−４０〜＋１５（秒・℃）とすることを特徴とする。ｔ
×（Ｔ1−Ｔg）が−５０（秒・℃）未満であると、膜厚
精度が低下し、傷が多発するおそれがある。ｔ×（Ｔ1
−Ｔg）が＋２０（秒・℃）を超えると、位相差が大き
くなり、傷が多発するおそれがある。本発明の方法を適
用してシートを製造する非晶性熱可塑性樹脂に特に制限
はなく、例えば、ポリエチレン、プロピレン−エチレン
共重合体、ポリスチレン、テレフタル酸−エチレングリ
コール−シクロヘキサンジメタノール共重合体、ポリカ
ーボネート、脂環式構造を有する樹脂などを挙げること
ができる。これらの中で、本発明の方法は、脂環式構造
を有する樹脂のシートの製造に好適に適用することがで
きる。脂環式構造を有する樹脂とは、重合体繰り返し単
位中に脂環式構造を含有するものであり、脂環式構造と
しては、シクロアルカン構造、シクロアルケン構造など
が挙げられる。脂環式構造含有重合体樹脂の具体例とし
ては、ノルボルネン環構造を有するモノマー（以下、ノ
ルボルネン系モノマーという。）の開環重合体及びその
水素添加物、ノルボルネン系モノマーの付加重合体及び
その水素添加物、ノルボルネン系モノマーとビニル化合
物との付加共重合体及びその水素添加物などのノルボル
ネン系重合体；スチレンなどビニル芳香族炭化水素化合
物の重合体の芳香環までを含めた水素添加物、ビニル脂
環式炭化水素化合物の重合体などのビニル脂環式炭化水
素重合体；が挙げられる。本発明の方法は、上記のノル
ボルネン系モノマーの開環重合体水素添加物及びビニル
脂環式炭化水素重合体のシートの製造に特に好適に適用
することができる。図１は、本発明方法におけるシート
と冷却ドラムとの接触方式の例としての２態様の説明図
である。図１(ａ)に示すＡ法においては、ダイス１から
シート状に押し出された溶融状態の熱可塑性樹脂２は、
第一冷却ドラム３の下方、第二冷却ドラム４の上方にお
いて、それぞれ冷却ドラムと接触して冷却され、シート
６として引き取られる。図１(ａ)の一実施態様では樹脂
は、第一冷却ドラムにおいて、ドラムと例えば中心角１
４０度の円周部分で接触し、第二冷却ドラムにおいて、
ドラムと例えば中心角５０度の円周部分で接触する。図
１(ｂ)に示すＢ法においては、ダイス１からシート状に
押し出された溶融状態の熱可塑性樹脂２は、第一冷却ド
ラム３の下方、第二冷却ドラム４の下方において、それ
ぞれ冷却ドラムと接触して冷却され、シート６として引
き取られる。図１(ｂ)の一実施態様では樹脂は、第一冷
却ドラムにおいて、ドラムと例えば中心角９０度の円周
部分で接触し、第二冷却ドラムにおいて、ドラムと例え
ば中心角５０度の円周部分で接触する。尚、本発明の方
法は、各ドラムの配置、樹脂の通過経路によって制限さ
れない。図１以外のものとして、例えば、Ｌ型、Ｚ型な
どの公知のドラム配置においても適用可能である。BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, a sheet-shaped molten thermoplastic resin extruded from an extruder is passed sequentially along the circumferential direction of two drums, a first cooling drum and a second cooling drum. In the method for producing an amorphous thermoplastic resin sheet, the resin contact time on the first cooling drum is t (seconds), the resin temperature when leaving the first cooling drum is T 1 (° C.), and the glass transition temperature of the resin is When Tg (° C.), t × (T 1
It is characterized in that -Tg) is -50 to +20 (seconds / ° C), more preferably -40 to +15 (seconds / ° C). t
If x (T 1 −Tg) is less than −50 (sec · ° C.), the film thickness accuracy may be reduced and scratches may occur frequently. t × (T 1
When −Tg) exceeds +20 (seconds / ° C.), the phase difference becomes large, and there is a risk of frequent scratches. There is no particular limitation on the amorphous thermoplastic resin for producing a sheet by applying the method of the present invention, for example, polyethylene, propylene-ethylene copolymer, polystyrene, terephthalic acid-ethylene glycol-cyclohexanedimethanol copolymer, Examples thereof include polycarbonate and resins having an alicyclic structure. Among these, the method of the present invention can be suitably applied to the production of a resin sheet having an alicyclic structure. The resin having an alicyclic structure is one containing an alicyclic structure in a polymer repeating unit, and examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure. Specific examples of the alicyclic structure-containing polymer resin include ring-opening polymers of monomers having a norbornene ring structure (hereinafter referred to as norbornene-based monomers) and hydrogenated products thereof, addition polymers of norbornene-based monomers and hydrogens thereof. Additives, norbornene-based polymers such as addition copolymers of norbornene-based monomers and vinyl compounds and hydrogenated products thereof; hydrogenated products including vinyl aromatic hydrocarbon compounds such as styrene up to the aromatic ring, vinyl And vinyl alicyclic hydrocarbon polymers such as polymers of alicyclic hydrocarbon compounds. The method of the present invention can be particularly suitably applied to the production of a hydrogenated product of a ring-opening polymer of the above norbornene-based monomer and a sheet of a vinyl alicyclic hydrocarbon polymer. FIG. 1 is an explanatory view of two modes as an example of a contact system between a sheet and a cooling drum in the method of the present invention. In the method A shown in FIG. 1A, the molten thermoplastic resin 2 extruded from the die 1 in a sheet shape is
Below the first cooling drum 3 and above the second cooling drum 4, they are brought into contact with the cooling drums to be cooled, respectively, and taken as a sheet 6. In one embodiment of FIG. 1 (a), the resin is in the first cooling drum, for example at a central angle 1
Contact at 40 degree circumference, in the second cooling drum,
The drum is in contact with, for example, a circumferential portion having a central angle of 50 degrees. In the method B shown in FIG. 1B, the molten thermoplastic resin 2 extruded in a sheet form from the die 1 is cooled below the first cooling drum 3 and below the second cooling drum 4, respectively. The sheet 6 is cooled by being brought into contact therewith, and is taken as the sheet 6. In one embodiment of FIG. 1 (b), the resin is in contact with the drum in the first cooling drum at a circumferential portion having a central angle of, for example, 90 degrees, and in the second cooling drum, the resin is in contact with the drum at a circumferential angle of, for example, a central angle of 50 degrees. Contact in parts. The method of the present invention is not limited by the arrangement of the drums and the resin passage. Other than FIG. 1, the present invention is also applicable to known drum arrangements such as L type and Z type.
【０００６】本発明方法においては、樹脂が第一冷却ド
ラムを離れ、第二冷却ドラムに接触するまでの時間が
０.３〜５（秒）であることが好ましく、０.５〜３.５
（秒）であることがより好ましい。また、第二冷却ドラ
ム接触開始時の樹脂温度がＴg−８０〜Ｔg＋１０（℃）
であることが好ましく、Ｔg−６０〜Ｔg＋５（℃）であ
ることがより好ましい。樹脂が第一冷却ドラムを離れ、
第二冷却ドラムに接触するまでの時間を０.３（秒）未
満とすると、第一冷却ドラムと第二冷却ドラムの位置関
係に無理が生じて、設備的な困難を伴うおそれがあり、
あるいは、シートの引取速度が速くなりすぎて、安定し
たシートの製造が困難になるおそれがある。樹脂が第一
冷却ドラムを離れ、第二冷却ドラムに接触するまでの時
間が５（秒）を超えると、シートの引取速度が遅くなり
すぎてシートの生産性が低下するおそれがあり、シワな
どの外観欠陥が発生しやすくなる。第二冷却ドラム接触
開始時の樹脂温度がＴg−８０（℃）未満であると、シ
ワなどの外観欠陥が発生するおそれがある。第二冷却ド
ラム接触開始時の樹脂温度がＴg＋１０（℃）を超える
と、位相差が大きくなるおそれがある。本発明方法にお
いては、第二冷却ドラムの表面温度がＴg−９０〜Ｔg−
１０（℃）であることが好ましく、Ｔg−８０〜Ｔg−２
０（℃）であることがより好ましい。第二冷却ドラムの
表面温度がＴg−９０（℃）未満であると、外観欠陥が
発生するおそれがある。第二冷却ドラムの表面温度がＴ
g−１０(℃)を超えると、位相差が大きくなるおそれが
ある。さらに、本発明方法においては、第一冷却ドラム
の表面温度がＴg−６０〜Ｔg＋２０（℃）であることが
好ましい。また、第一冷却ドラムでの樹脂接触時間ｔは
０.５〜１０（秒）の範囲内で、第一冷却ドラムを離れ
るときの樹脂温度Ｔ1はＴg−５０〜Ｔg＋２０（℃）の
範囲内で、ｔ×（Ｔ1−Ｔg）が−５０〜＋２０（秒・
℃）となるように制御する。In the method of the present invention, the time until the resin leaves the first cooling drum and contacts the second cooling drum is preferably 0.3 to 5 (seconds), and 0.5 to 3.5.
(Seconds) is more preferable. The resin temperature at the start of contact with the second cooling drum is Tg-80 to Tg + 10 (° C).
Is preferable, and Tg−60 to Tg + 5 (° C.) is more preferable. The resin leaves the first cooling drum,
If the time to contact the second cooling drum is less than 0.3 (seconds), the positional relationship between the first cooling drum and the second cooling drum may be unreasonable, which may cause equipment difficulty.
Alternatively, the sheet take-up speed may become too fast, which may make it difficult to manufacture a stable sheet. If the time it takes for the resin to leave the first cooling drum and come into contact with the second cooling drum exceeds 5 (seconds), the sheet take-up speed may be too slow and the sheet productivity may be reduced. The appearance defect of is likely to occur. If the resin temperature at the start of contact with the second cooling drum is lower than Tg-80 (° C), appearance defects such as wrinkles may occur. If the resin temperature at the start of contact with the second cooling drum exceeds Tg + 10 (° C.), the phase difference may increase. In the method of the present invention, the surface temperature of the second cooling drum is Tg-90 to Tg-.
It is preferably 10 (° C.), and Tg-80 to Tg-2
It is more preferably 0 (° C.). If the surface temperature of the second cooling drum is lower than Tg-90 (° C), appearance defects may occur. The surface temperature of the second cooling drum is T
If it exceeds g-10 (° C), the phase difference may increase. Further, in the method of the present invention, the surface temperature of the first cooling drum is preferably Tg-60 to Tg + 20 (° C). Further, the resin contact time t in the first cooling drum is in the range of 0.5 to 10 (seconds), and the resin temperature T 1 when leaving the first cooling drum is in the range of Tg-50 to Tg + 20 (° C). And t × (T 1 −Tg) is −50 to +20 (seconds.
℃).
【０００７】本発明の方法においては、第一冷却ドラム
と第二冷却ドラムとの相対的位置を変えることにより、
第一冷却ドラムでの樹脂接触時間、及び、第一冷却ドラ
ムを離れ第二冷却ドラムに接触するまでの時間を調整す
ることができる。第一冷却ドラムと第二冷却ドラムとの
相対的位置は、例えば、第一冷却ドラム及び／又は第二
冷却ドラムの位置を、上下・左右・斜め方向に移動させ
て変えることができる。図２は、本発明方法の実施の一
態様の説明図であり、図２(ａ)は、図１(ａ)のＡ法にお
いて第二冷却ドラムを上方向に移動させた状態（Ｃ法）
を、図２(ｂ)は、図１(ｂ)のＢ法において第二冷却ドラ
ムを下方向に移動させた状態（Ｄ法）を示す。本態様に
おいては、ダイス１からシート状に押し出された溶融状
態の熱可塑性樹脂２は、第一冷却ドラム３、第二冷却ド
ラム４、第三冷却ドラム５において、それぞれ冷却ドラ
ムと接触して冷却され、シート６として引き取られる。
図２(ａ)に示す第二冷却ドラムを上方向に移動させた状
態では、樹脂は、第一冷却ドラムにおいて、ドラムと中
心角約１６０度の円周部分で接触し、第二冷却ドラムに
おいて、ドラムと中心角約１４０度の円周部分で接触す
る。また、樹脂が第一冷却ドラムを離れて第二冷却ドラ
ムに接触する間の距離は、第一冷却ドラムの円周の長さ
の０.５５倍である。図２(ｂ)に示す第二冷却ドラムを
下方向に移動させた状態では、樹脂は、第一冷却ドラム
において、ドラムと中心角約６０度の円周部分で接触
し、第二冷却ドラムにおいて、ドラムと中心角約９０度
の円周部分で接触する。また、樹脂が第一冷却ドラムを
離れて第二冷却ドラムに接触する間の距離は、第一冷却
ドラムの円周の長さの０.４３倍である。このように第
二冷却ドラムを上下方向に移動させることにより、同一
の設備を用いて、第一冷却ドラムでの樹脂接触時間や、
第一冷却ドラムを離れ第二冷却ドラムに接触するまでの
距離、したがって、第一冷却ドラムを離れ第二冷却ドラ
ムに接触するまでの時間を連続的に可変として調整する
ことが可能となる。In the method of the present invention, by changing the relative positions of the first cooling drum and the second cooling drum,
The resin contact time in the first cooling drum and the time until the resin leaves the first cooling drum and contacts the second cooling drum can be adjusted. The relative position between the first cooling drum and the second cooling drum can be changed, for example, by moving the positions of the first cooling drum and / or the second cooling drum in the vertical, horizontal, and diagonal directions. FIG. 2 is an explanatory view of an embodiment of the method of the present invention, and FIG. 2 (a) shows a state in which the second cooling drum is moved upward in the method A of FIG. 1 (a) (method C).
2 (b) shows a state (method D) in which the second cooling drum is moved downward in method B of FIG. 1 (b). In the present embodiment, the molten thermoplastic resin 2 extruded from the die 1 in a sheet shape is cooled by coming into contact with the cooling drums in the first cooling drum 3, the second cooling drum 4, and the third cooling drum 5, respectively. Then, the sheet 6 is taken up.
In the state where the second cooling drum shown in FIG. 2 (a) is moved upward, the resin comes into contact with the drum at a circumferential portion having a central angle of about 160 degrees in the first cooling drum, and in the second cooling drum. , It contacts the drum at the circumference of the center angle of about 140 degrees. The distance during which the resin leaves the first cooling drum and contacts the second cooling drum is 0.55 times the length of the circumference of the first cooling drum. In the state in which the second cooling drum shown in FIG. 2 (b) is moved downward, the resin comes into contact with the drum in the circumferential portion having a central angle of about 60 degrees in the first cooling drum, and in the second cooling drum. , It contacts the drum at the circumference of the center angle of about 90 degrees. The distance during which the resin leaves the first cooling drum and contacts the second cooling drum is 0.43 times the circumferential length of the first cooling drum. By moving the second cooling drum up and down in this way, using the same equipment, the resin contact time in the first cooling drum,
It is possible to continuously adjust the distance until the second cooling drum is separated from the first cooling drum, that is, the time until the second cooling drum is separated from the first cooling drum.
【０００８】本発明方法に用いる押出機に特に制限はな
く、例えば、単軸押出機、同方向回転二軸押出機、異方
向回転二軸押出機などを挙げることができる。押出機の
ホッパーに特に制限はないが、樹脂の吸湿防止のために
ホッパードライヤーを用いることが好ましい。スクリュ
ーに特に制限はなく、窒化鋼やクロム−モリブデン鋼に
硬質クロムメッキをしたスクリューなどを用いることが
できる。シートの耳部を粉砕した再生品を原料に混入す
る場合は、押出安定性を向上させるために副フライトを
有するバリヤー型スクリューを用いることが好ましい。
必要に応じて、ベント付き押出機を用いることができ
る。シリンダーの終端部には、異物除去のためにフィル
ターを設けることが好ましい。本発明方法に用いるダイ
スは、Ｔダイであることが好ましい。Ｔダイとしては、
ストレートマニホールド形、コートハンガー形のいずれ
をも用いることができるが、膜厚精度を向上するために
は、コートハンガー形を用いることが好ましい。本発明
方法に用いる冷却ドラムは、特に制限はないが金属製で
あって、表面が鏡面加工され、内部に例えば熱媒や冷媒
による冷却手段を有することが好ましい。鏡面加工は、
表面粗さがＲaで５μｍ以下であることが好ましく、２
μｍ以下であることがより好ましい。冷却ドラムの径に
特に制限はなく、生産速度に応じて適宜選択することが
できる。第一冷却ドラムには、エアナイフ又はエアチャ
ンバーを設けて、押し出された溶融状態の熱可塑性樹脂
をドラムに密着させることが好ましい。冷却されて固化
した熱可塑性樹脂シートは、必要に応じて両耳をトリミ
ングし、巻き取ることができる。The extruder used in the method of the present invention is not particularly limited, and examples thereof include a single-screw extruder, a co-rotating twin-screw extruder, and a different-direction rotating twin-screw extruder. The hopper of the extruder is not particularly limited, but it is preferable to use a hopper dryer to prevent the resin from absorbing moisture. The screw is not particularly limited, and a screw in which hard chrome plating is applied to nitride steel or chrome-molybdenum steel can be used. When a recycled product obtained by crushing the ears of the sheet is mixed in the raw material, it is preferable to use a barrier type screw having a sub flight in order to improve extrusion stability.
If necessary, a vented extruder can be used. A filter is preferably provided at the end of the cylinder to remove foreign matter. The die used in the method of the present invention is preferably a T die. As a T-die,
Although either a straight manifold type or a coat hanger type can be used, it is preferable to use the coat hanger type in order to improve the film thickness accuracy. The cooling drum used in the method of the present invention is not particularly limited, but it is preferably made of metal, the surface of which is mirror-finished, and the inside of which has a cooling means such as a heating medium or a cooling medium. Mirror finishing is
The surface roughness Ra is preferably 5 μm or less, and 2
More preferably, it is less than or equal to μm. The diameter of the cooling drum is not particularly limited and can be appropriately selected according to the production rate. It is preferable that an air knife or an air chamber be provided in the first cooling drum so that the extruded molten thermoplastic resin is brought into close contact with the drum. The thermoplastic resin sheet that has been cooled and solidified can be trimmed on both ears as necessary and wound up.
【０００９】[0009]
【実施例】以下に、実施例を挙げて本発明をさらに詳細
に説明するが、本発明はこれらの実施例によりなんら限
定されるものではない。なお、実施例及び比較例におい
ては、非晶性熱可塑性樹脂として、ノルボルネン系開環
重合体水素添加物［日本ゼオン(株)、ゼオノア１４２０
Ｒ、ガラス転移温度１３６℃］を用いた。シリンダー内
径５０mm、スクリューＬ／Ｄ＝３０の単軸押出機［(株)
日本製鋼所］に、吐出口の幅３５０mm、リップ間隔０.
５mmのコートハンガーダイを取り付けた。第一冷却ドラ
ムは、直径１５０mm、幅５００mm、第二冷却ドラムは、
直径２００mm、幅５００mm、第三冷却ドラムは、直径２
００mm、幅５００mmであり、図１(ａ)に示されるＡ法又
は図１(ｂ)に示されるＢ法のように、樹脂を冷却ドラム
に接触させ、厚み５０μｍのシートを製造した。また、
得られたシートについて、長さ方向２０mmごとに１０か
所について、シート中央部と両端部の厚みを測定し、最
大厚みと最小厚みの差を厚み精度とした。シートから３
００mm×２００mmの試験片３枚を切り出し、長さ５０μ
ｍ以上のスジ又は欠陥を目視により観察し、傷の数とし
た。複屈折測定装置［王子計測機器(株)、ＫＯＢＲＡ−
２１ＡＤＨ］を用い、シートの長さ方向１ｍごとに５か
所について、シート中央部と端部の位相差を測定し、中
央部及び端部それぞれの平均値を求めた。
実施例１
冷却ドラムとの接触方式はＡ法、シート引取速度が１０
ｍ／分となるように第三冷却ドラムの後ろに設置された
巻取りロール速度を設定し、ダイス温度２６０℃、第一
冷却ドラム温度１４０℃、第二冷却ドラム温度１００
℃、第一冷却ドラムでの樹脂接触時間３.２秒、第一冷
却ドラムを離れるときの樹脂温度１３１℃、ｔ×（Ｔ1
−Ｔg）＝−１６（秒・℃）、第一冷却ドラム〜第二冷
却ドラムの移動時間０.８秒、第二冷却ドラム接触開始
時の樹脂温度１２１℃の条件でシートを製膜した。得ら
れたシートの膜厚精度は４.８μｍ、傷個数は０個、位
相差は中央部３.２ｎｍ、端部３.６ｎｍであった。
実施例２〜５
第１表に示す条件で、シートの製造を行った。
比較例１
冷却ドラムへの接触方式はＢ法、シート引取速度は１０
ｍ／分となるように設定、ダイス温度２６０℃、第一冷
却ドラム温度１１０℃、第二冷却ドラム温度１００℃、
第一冷却ドラムでの樹脂接触時間３.２秒、第一冷却ド
ラムを離れるときの樹脂温度１１９℃、ｔ×（Ｔ1−Ｔ
g）＝−５４（秒・℃）、第一冷却ドラム〜第二冷却ド
ラムの移動時間０.８秒、第二冷却ドラム接触開始時の
樹脂温度１０３℃の条件でシートを製膜した。得られた
シートの膜厚精度は１５.４μｍ、傷個数は３０個以
上、位相差は中央部３.１ｎｍ、端部３.３ｎｍであっ
た。
比較例２
第１表に示す条件で、シートの製造を行った。実施例１
〜５及び比較例１〜２の結果を、第１表に示す。The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, a hydrogenated norbornene ring-opening polymer [Nippon Zeon Co., Ltd., ZEONORE 1420] was used as the amorphous thermoplastic resin.
R, glass transition temperature 136 ° C.] was used. Single screw extruder with cylinder inner diameter 50mm and screw L / D = 30
[Japan Steel Works]], discharge port width 350 mm, lip spacing 0.
A 5 mm coat hanger die was attached. The first cooling drum has a diameter of 150 mm and a width of 500 mm, and the second cooling drum is
Diameter 200mm, width 500mm, 3rd cooling drum has diameter 2
A sheet having a thickness of 50 μm was produced by bringing the resin into contact with a cooling drum as in the method A shown in FIG. 1A or the method B shown in FIG. Also,
With respect to the obtained sheet, the thickness of the central portion and both end portions of the sheet was measured at 10 locations every 20 mm in the length direction, and the difference between the maximum thickness and the minimum thickness was defined as the thickness accuracy. 3 from the sheet
Cut out three 00mm x 200mm test pieces, length 50μ
Streaks or defects of m or more were visually observed and taken as the number of scratches. Birefringence measuring device [Oji Scientific Instruments Co., Ltd., KOBRA-
21 ADH], the phase difference between the central portion and the end portion of the sheet was measured at 5 positions per 1 m in the length direction of the sheet, and the average value of each of the central portion and the end portion was obtained. Example 1 The method of contact with the cooling drum is method A, and the sheet take-up speed is 10
The take-up roll speed installed behind the third cooling drum was set to be m / min, and the die temperature was 260 ° C, the first cooling drum temperature was 140 ° C, and the second cooling drum temperature was 100 ° C.
℃, the resin contact time in the first cooling drum 3.2 seconds, the resin temperature when leaving the first cooling drum 131 ℃, t × (T 1
A sheet was formed under the conditions of −Tg) = − 16 (sec · ° C.), a moving time of the first cooling drum to the second cooling drum of 0.8 seconds, and a resin temperature of 121 ° C. at the start of contact with the second cooling drum. The thickness of the obtained sheet was 4.8 μm, the number of scratches was 0, and the phase difference was 3.2 nm in the central part and 3.6 nm in the end part. Examples 2 to 5 Sheets were manufactured under the conditions shown in Table 1. Comparative Example 1 Method of contacting the cooling drum is method B, and sheet take-up speed is 10
m / min, die temperature 260 ° C., first cooling drum temperature 110 ° C., second cooling drum temperature 100 ° C.,
Resin contact time with the first cooling drum is 3.2 seconds, resin temperature when leaving the first cooling drum is 119 ° C., t × (T 1 −T
g) =-54 (sec. ° C.), the moving time of the first cooling drum to the second cooling drum was 0.8 seconds, and the resin temperature was 103 ° C. at the start of contact with the second cooling drum to form a film. The thickness accuracy of the obtained sheet was 15.4 μm, the number of scratches was 30 or more, and the phase difference was 3.1 nm in the central part and 3.3 nm in the edge part. Comparative Example 2 A sheet was manufactured under the conditions shown in Table 1. Example 1
Table 1 shows the results of Comparative Examples 5 to 5 and Comparative Examples 1 to 2.
【００１０】[0010]
【表１】 [Table 1]
【００１１】第１表に見られるように、本発明方法によ
り製造された実施例１〜５のシートは、膜厚精度が１０
μｍ以下と小さく、シートのスジ又は欠陥は皆無又は５
個以下と極めて少なく、位相差はシートの中央部、端部
ともに１０ｎｍ以下と小さい。これに対して、比較例１
のシートは、位相差は小さいが、膜厚精度に劣り、傷が
多発しており、比較例２のシートは、膜厚精度は良好だ
が、傷が多発し、位相差が大きい。As can be seen from Table 1, the sheets of Examples 1 to 5 produced by the method of the present invention have a film thickness accuracy of 10
It is as small as less than μm, and there are no stripes or defects on the sheet or
The number is less than or equal to 10 and extremely small, and the phase difference is as small as 10 nm or less at both the central portion and the edge portion of the sheet. On the other hand, Comparative Example 1
The sheet of No. 2 has a small phase difference, but is inferior in film thickness accuracy and has many scratches. The sheet of Comparative Example 2 has good film thickness accuracy, but has many scratches and a large phase difference.
【００１２】[0012]
【発明の効果】本発明方法によれば、非晶性熱可塑性樹
脂から、厚みムラが小さく、スジ、欠陥などがなく、位
相差の小さいシートを安定して製造することができる。
本発明方法は、脂環式構造を有する樹脂のシートの製造
に特に好適に適用することができる。EFFECTS OF THE INVENTION According to the method of the present invention, a sheet having a small thickness unevenness, no streaks and no defects, and a small retardation can be stably produced from an amorphous thermoplastic resin.
The method of the present invention can be particularly suitably applied to the production of a resin sheet having an alicyclic structure.
【図１】図１は、本発明方法におけるシートと冷却ドラ
ムとの接触方式の２態様の説明図である。FIG. 1 is an explanatory diagram of two modes of a contact system between a sheet and a cooling drum in the method of the present invention.
【図２】図２は、本発明方法の実施の一態様の説明図で
ある。FIG. 2 is an explanatory diagram of an embodiment of the method of the present invention.
１ ダイス ２ 溶融状態の熱可塑性樹脂 ３ 第一冷却ドラム ４ 第二冷却ドラム ５ 第三冷却ドラム ６ シート 1 die 2 Thermoplastic resin in molten state 3 first cooling drum 4 Second cooling drum 5 Third cooling drum 6 sheets
───────────────────────────────────────────────────── フロントページの続き (72)発明者 黒崎 勝尋 神奈川県川崎市川崎区夜光１丁目２番１号 日本ゼオン株式会社総合開発センター内 Ｆターム(参考） 4F207 AA12 AG01 AR06 AR11 KA01 KA17 KK64 KM16 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Katsuhiro Kurosaki 1-2-1, Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Zeon Corporation, General Development Center F-term (reference) 4F207 AA12 AG01 AR06 AR11 KA01 KA17 KK64 KM16
Claims (6)
塑性樹脂を、第一冷却ドラム、第二冷却ドラムの２本の
ドラムの周に沿って順に通過させる非晶性熱可塑性樹脂
シートの製造方法において、第一冷却ドラムでの樹脂接
触時間をｔ（秒）、第一冷却ドラムを離れるときの樹脂
温度をＴ1（℃）、樹脂のガラス転移温度をＴg（℃）と
したとき、ｔ×（Ｔ1−Ｔg）を、−５０〜＋２０（秒・
℃）とすることを特徴とする非晶性熱可塑性樹脂シート
の製造方法。1. Production of an amorphous thermoplastic resin sheet in which a sheet-shaped molten thermoplastic resin extruded from an extruder is sequentially passed along the circumference of two drums of a first cooling drum and a second cooling drum. In the method, when the resin contact time on the first cooling drum is t (seconds), the resin temperature when leaving the first cooling drum is T 1 (° C), and the glass transition temperature of the resin is Tg (° C), t is X (T 1 -Tg) is -50 to +20 (seconds
C.) The method for producing an amorphous thermoplastic resin sheet.
ラムに接触するまでの時間が０.３〜５（秒）であり、
かつ第二冷却ドラム接触開始時の樹脂温度がＴg−８０
〜Ｔg＋１０（℃）である請求項１記載の非晶性熱可塑
性樹脂シートの製造方法。2. The time until the resin leaves the first cooling drum and contacts the second cooling drum is 0.3 to 5 (seconds),
Moreover, the resin temperature at the start of contact with the second cooling drum is Tg-80.
To Tg + 10 (° C).
〜Ｔg−１０（℃）である請求項１又は請求項２記載の
非晶性熱可塑性樹脂シートの製造方法。3. The surface temperature of the second cooling drum is Tg-90.
-Tg-10 (degreeC), The manufacturing method of the amorphous thermoplastic resin sheet of Claim 1 or Claim 2.
的位置を変えることにより、第一冷却ドラムでの樹脂接
触時間、及び、第一冷却ドラムを離れ第二冷却ドラムに
接触するまでの時間を調整する請求項１又は請求項２記
載の非晶性熱可塑性樹脂シートの製造方法。4. By changing the relative position of the first cooling drum and the second cooling drum, the resin contact time on the first cooling drum and until the first cooling drum leaves the second cooling drum. The method for producing an amorphous thermoplastic resin sheet according to claim 1 or 2, wherein the time is adjusted.
である請求項１、請求項２又は請求項３記載の非晶性熱
可塑性樹脂シートの製造方法。5. The method for producing an amorphous thermoplastic resin sheet according to claim 1, 2 or 3, wherein the thermoplastic resin is a resin having an alicyclic structure.
系開環重合体水素添加物又はビニル脂環式炭化水素重合
体である請求項５記載の非晶性熱可塑性樹脂シートの製
造方法。6. The method for producing an amorphous thermoplastic resin sheet according to claim 5, wherein the resin having an alicyclic structure is a hydrogenated norbornene ring-opening polymer or a vinyl alicyclic hydrocarbon polymer.
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| JP2006327161A (en) * | 2005-05-30 | 2006-12-07 | Fujifilm Holdings Corp | Manufacturing method of thermoplastic film |
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| WO2006068221A1 (en) * | 2004-12-24 | 2006-06-29 | Fujifilm Corporation | Cellulose acylate film and method for producing same |
| CN101090929B (en) * | 2004-12-24 | 2010-11-10 | 富士胶片株式会社 | Cellulose acylate film and method for producing same |
| US8197726B2 (en) | 2004-12-24 | 2012-06-12 | Fujifilm Corporation | Cellulose acylate film and method for producing same |
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| JP2006327107A (en) * | 2005-05-27 | 2006-12-07 | Fujifilm Holdings Corp | Manufacturing method of thermoplastic film |
| JP2006327161A (en) * | 2005-05-30 | 2006-12-07 | Fujifilm Holdings Corp | Manufacturing method of thermoplastic film |
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| CN112549475A (en) * | 2020-11-24 | 2021-03-26 | 中国科学技术大学 | Method and device for preparing liquid crystal polymer film |
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