JPH106351A - Preparation of cellulose triacetate film and preparation of member for liquid crystal displaying - Google Patents
Preparation of cellulose triacetate film and preparation of member for liquid crystal displayingInfo
- Publication number
- JPH106351A JPH106351A JP8166041A JP16604196A JPH106351A JP H106351 A JPH106351 A JP H106351A JP 8166041 A JP8166041 A JP 8166041A JP 16604196 A JP16604196 A JP 16604196A JP H106351 A JPH106351 A JP H106351A
- Authority
- JP
- Japan
- Prior art keywords
- dope
- film
- cellulose triacetate
- weight
- substrate
- 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.)
- Pending
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
- Liquid Crystal (AREA)
Abstract
Description
【０００１】[0001]
（１）本発明はセルローストリアセテートフィルムの製
造方法に係り、詳しくは寸法安定性に優れたセルロース
トリアセテートフィルムの製造方法に関する。(1) The present invention relates to a method for producing a cellulose triacetate film, and more particularly, to a method for producing a cellulose triacetate film having excellent dimensional stability.
【０００２】（２）本発明は（１）に記載したセルロー
ストリアセテートフィルムの製造方法を含む液晶表示用
部材の製造方法に関する。(2) The present invention relates to a method for producing a liquid crystal display member including the method for producing a cellulose triacetate film described in (1).
【０００３】[0003]
【従来の技術】セルローストリアセテートフィルムは写
真用、光学用など種々の用途に利用されている。例えば
光学用としての液晶モジュール部材に用いる場合、様々
な環境（温度、湿度条件など）下での耐久性が要求され
るが、そのひとつとしてプラスチックフィルム自体の伸
縮が少ないことが挙げられる。セルローストリアセテー
トフィルムは、この寸法安定性という点において充分な
ものとはいいきれなかったが透明性など要求される他の
性能に優れるため従来広く実用されてきていた。2. Description of the Related Art Cellulose triacetate films are used for various purposes such as photographic and optical applications. For example, when it is used for a liquid crystal module member for optical use, durability under various environments (temperature, humidity conditions, etc.) is required. One of them is that the plastic film itself does not expand or contract. Cellulose triacetate films have not been sufficient in terms of dimensional stability, but have been widely used in the past because they are excellent in other required properties such as transparency.
【０００４】本発明者らは、この寸法安定性を達成する
手段として、製造過程における種々の条件を検討するこ
とに着目したものである。The present inventors have focused on examining various conditions in the manufacturing process as means for achieving the dimensional stability.
【０００５】セルローストリアセテートフィルムの製造
としては、一般にセルローストリアセテート樹脂をメチ
レンクロライド或いはエチレンクロライドと１０％程度
のアルコール類との混合溶媒溶に溶解し、得られたドー
プをドラム状或いはバンド状の無端状支持体上に流延
し、溶媒を蒸発させるか、或いは支持体を冷却すること
によりゲル化を行い、流延皮膜がある強度に達したとこ
ろで支持体から剥離し、残存する溶媒を除去乾燥して製
膜する方法が用いられてきている。In the production of a cellulose triacetate film, generally, a cellulose triacetate resin is dissolved in a mixed solvent of methylene chloride or a mixed solvent of ethylene chloride and about 10% of an alcohol, and the obtained dope is drum-shaped or band-shaped endless. It is cast on a support and gelled by evaporating the solvent or cooling the support. When the casting film reaches a certain strength, it is peeled off from the support and the remaining solvent is removed and dried. A film forming method has been used.
【０００６】生産性を向上する目的から、米国特許第
２，２２１，０１９号には流延したドープを冷却するこ
とによりゲル化を速める方法が、特開昭６２−３７１１
３号、同６２−６４５１４号には高濃度で特定の溶媒組
成を用いたドープを用い、表面温度１０℃以下の支持体
上に流延し、その後剥離乾燥して、製膜する方法が記載
されている。For the purpose of improving productivity, US Pat. No. 2,221,019 discloses a method of accelerating gelation by cooling a cast dope.
Nos. 3 and 62-64514 describe a method in which a dope containing a specific solvent composition at a high concentration is used, cast on a support having a surface temperature of 10 ° C. or lower, and then peeled and dried to form a film. Have been.
【０００７】しかしながら、これらの方法は生産性の向
上を図ることを主目的とするものであって、出来上がっ
たフィルムの物性、特に寸法安定性に関しては何ら言及
されていない。[0007] However, these methods are mainly intended to improve the productivity, and no mention is made of the physical properties of the resulting film, particularly the dimensional stability.
【０００８】後述の本発明者らの検討により、優れた寸
法安定性が得られる条件を見いだすことができたもので
あるが、従来は製造方法自体の改善によって寸法安定性
を改良したという報告は見られない。Although the inventors of the present invention described below have found conditions under which excellent dimensional stability can be obtained, it has been reported that dimensional stability was improved by improving the manufacturing method itself. can not see.
【０００９】[0009]
【発明が解決しようとする課題】光学用途に用いられる
セルローストリアセテートフィルムには需要の高まりと
ともに、要求品質も厳しくなり、従来の寸法安定性では
不足し、またより高度な耐久性も要求されている。The demand for cellulose triacetate films used for optical applications is increasing, and the required quality is becoming severer. Conventional dimensional stability is insufficient, and higher durability is also required. .
【００１０】本発明者はセルローストリアセテートフィ
ルムの更なる寸法安定性を実現するために鋭意検討し、
その製造過程において種々の工夫を重ねた結果本発明を
見いだすに至った。The present inventors have made intensive studies to realize further dimensional stability of the cellulose triacetate film,
As a result of various efforts in the manufacturing process, the present invention has been found.
【００１１】[0011]
【課題を解決するための手段】本発明は、ドープを支持
体上に流延後、剥離までの間に、支持体温度が１０℃を
超え、かつ３０℃未満である状態を経由することを特徴
とする溶液流延法によるセルローストリアセテートフィ
ルムの製造方法であってこれにより寸法安定性に優れた
フィルムを提供することができるのである。According to the present invention, after casting a dope on a support, the temperature of the support must be higher than 10 ° C. and lower than 30 ° C. before peeling. This is a characteristic method for producing a cellulose triacetate film by a solution casting method, whereby a film having excellent dimensional stability can be provided.
【００１２】また本発明は、セルローストリアセテート
樹脂に対して可塑剤添加量が３重量％以上であり、かつ
１２重量％以下であるドープを支持体上に流延後、剥離
までの間に、支持体温度が１０℃を超え、かつ３０℃未
満である状態を経由することを特徴とする溶液流延法に
よるセルローストリアセテートフィルムの製造方法であ
って、これによりさらに寸法安定性に優れ、また欠陥の
少ないフィルムを提供することができるのである。Further, according to the present invention, a dope containing a plasticizer in an amount of 3% by weight or more and 12% by weight or less with respect to a cellulose triacetate resin is cast on a support and then separated from the dope. A method for producing a cellulose triacetate film by a solution casting method, which comprises passing through a state in which a body temperature is higher than 10 ° C. and lower than 30 ° C., whereby the dimensional stability is further improved and the defect It is possible to provide fewer films.
【００１３】また本発明は前記セルローストリアセテー
トフィルムの製造方法を含む液晶表示用部材の製造方法
であってこれにより耐久性に優れ、あるいは、さらに欠
陥の少ない液晶表示用部材を提供することができるので
ある。Further, the present invention is a method for producing a liquid crystal display member including the above-mentioned method for producing a cellulose triacetate film, which can provide a liquid crystal display member having excellent durability or less defects. is there.
【００１４】まず本発明に係る概要を述べる。First, an outline according to the present invention will be described.
【００１５】セルローストリアセテート樹脂の溶媒とし
ては、該樹脂を良く溶解する良溶媒と、溶解性の低い或
いは溶解性の殆ど溶解しない貧溶媒とに分けることがで
きる。このような良溶媒と貧溶媒との混合溶媒にセルロ
ーストリアセテート樹脂などを溶解させたドープを連続
的に回転するバンドやドラムのような無端支持体上にホ
ッパーから均一に流延し、支持体上にて溶媒を蒸発させ
ドープが固化した後に支持体から剥離し、更に残存する
溶媒を蒸発乾燥させてフィルムを得る。The solvent for the cellulose triacetate resin can be classified into a good solvent which dissolves the resin well and a poor solvent which has low or almost insoluble solubility. A dope obtained by dissolving a cellulose triacetate resin or the like in a mixed solvent of such a good solvent and a poor solvent is uniformly cast from a hopper onto an endless support such as a continuously rotating band or drum, and After the solvent is evaporated to solidify the dope, the film is separated from the support, and the remaining solvent is evaporated and dried to obtain a film.
【００１６】支持体上への流延後、剥離するまでの間と
は、前述の説明の中での、支持体上に流延した後溶媒を
蒸発させてドープを固化し支持体から剥離するまでの過
程をいう。The period from casting on the support to peeling off is the same as that described above, after casting on the support, the solvent is evaporated to solidify the dope and peel off from the support. The process up to.
【００１７】支持体温度が１０℃を超え、かつ３０℃未
満になるように調整するには、支持体のドープ接触面
の反対側に所望の温度の液体を接触させる方法が挙げら
れる。In order to adjust the temperature of the support to be higher than 10 ° C. and lower than 30 ° C., there is a method in which a liquid at a desired temperature is brought into contact with the opposite side of the dope contact surface of the support.
【００１８】ドラム式の製膜機には、流延後、剥離まで
の部分のドラムの内側に液体槽を設け、この液体槽をさ
らに内側から所望の温度に設定することにより支持体で
あるドラム温度を調整することができる。バンド式の製
膜機の場合は、外部から液体の給排を行うことによりバ
ンドに直接液体を接触させて調整する。In the drum type film forming machine, a liquid tank is provided inside the drum at a portion from the casting to the peeling, and the liquid tank is set at a desired temperature from the inside further to form a drum as a support. Temperature can be adjusted. In the case of a band-type film-forming machine, the liquid is supplied and discharged from the outside to make adjustment by bringing the liquid into direct contact with the band.
【００１９】また支持体のドープ接触面の反対側に所
望の温度の風を吹き付ける方法が挙げられる。また支
持体のドープ接触面に所望の風を吹き付ける方法も挙げ
られる。更にこれらからの方法を適宜組み合わせて
もよい。Another method is to blow air at a desired temperature to the opposite side of the dope contact surface of the support. Also, a method of blowing a desired wind to the dope contact surface of the support may be used. Further, these methods may be appropriately combined.
【００２０】流延後、剥離までの間での支持体温度とし
ては１０℃を超え、かつ３０℃未満であることが必要で
あるが、１０℃以下を経由すると、例えば製膜時に剥離
性が悪化し、保護フィルムとして使えないほどの剥離横
段を発生する等の品質の劣化を招いたり、フィルムが破
断し生産工程でのトラブルを発生するなどのため好まし
くない。３０℃以上を経由すると寸法変化率が悪化し良
くない。また偏光板にして耐久性評価すると、３０℃以
上では偏光板の直交状態で縁の部分が白く抜ける故障が
発生し、偏光板として問題が発生することが分かった。It is necessary that the temperature of the support after casting and before peeling is higher than 10 ° C. and lower than 30 ° C. It is not preferable because it causes deterioration of quality such as deterioration and generation of a peeling horizontal step that cannot be used as a protective film, or breakage of the film to cause troubles in the production process. If the temperature exceeds 30 ° C. or more, the dimensional change rate deteriorates, which is not good. When the durability of the polarizing plate was evaluated at 30 ° C. or higher, it was found that a failure occurred in which the edges of the polarizing plate became white in an orthogonal state, which caused a problem as a polarizing plate.
【００２１】支持体温度が１５℃以上２４℃以下が剥離
性と寸法変化率、耐久性のバランスがとれていて特に好
ましい。A support temperature of 15 ° C. or more and 24 ° C. or less is particularly preferred because the balance between the releasability, the dimensional change and the durability is maintained.
【００２２】支持体温度が１０℃を超え、かつ３０℃未
満になるように調整する場所は、溶解させたドープをホ
ッパーから支持体に均一に流延した後であって、剥離す
るまでの間の少なくとも一部分であればどこであっても
良いが、前半部分の支持体温度が１０℃を超え、かつ３
０℃未満になるように調整することが、寸法安定性に対
する効果が大きく好ましい。The place where the temperature of the support is adjusted so as to be higher than 10 ° C. and lower than 30 ° C. is after the melted dope is uniformly cast from the hopper onto the support and before the peeling. The temperature of the support in the first half may exceed 10 ° C.
Adjusting the temperature to be lower than 0 ° C. is preferable because the effect on dimensional stability is large.
【００２３】前半と後半部分の両方の支持体温度が１０
℃を超え、かつ３０℃未満になるように調整すること
が、寸法安定性に対する効果がさらに大きくもっとも好
ましい。When the temperature of the support in both the first half and the second half is 10
It is most preferable to adjust the temperature to be higher than 0 ° C. and lower than 30 ° C. because the effect on dimensional stability is further increased.
【００２４】支持体の前半部分、後半部分とは、ドープ
流延後から剥離するまでの間の支持体の長さを半分に分
け、ドープ流延直後からの半分を前半部分、前半部分の
終わりから剥離部分までの半分を後半部分と本発明では
定義する。The first half and the second half of the support are divided into halves of the length of the support from the time after the casting of the dope to the time of separation, and the half immediately after the casting of the dope is divided into the first half and the end of the first half. In the present invention, the half from the part to the peeled part is defined as the latter part.
【００２５】支持体温度が１０℃を超え、かつ３０℃未
満である状態を１０秒以上経由することが好ましい。こ
の温度を経由する時間は寸法安定性の観点からはできる
だけ長い方が好ましいが、乾燥効率、生産性の観点か
ら、１０分以内とすることが好ましい。特に好ましくは
３０秒以上５分以内であることが好ましい。It is preferable that the state in which the temperature of the support is higher than 10 ° C. and lower than 30 ° C. is passed for 10 seconds or more. The time through this temperature is preferably as long as possible from the viewpoint of dimensional stability, but is preferably within 10 minutes from the viewpoint of drying efficiency and productivity. It is particularly preferable that the time is 30 seconds or more and 5 minutes or less.
【００２６】本発明に係るセルローストリアセテートは
酢化度６０〜６２％のものを用いるのが好ましい。The cellulose triacetate of the present invention preferably has a degree of acetylation of 60 to 62%.
【００２７】このようなセルローストリアセテート及び
可塑剤を溶媒に溶解してドープを得る。Such a cellulose triacetate and a plasticizer are dissolved in a solvent to obtain a dope.
【００２８】本発明で用いることのできる可塑剤として
は特に限定はないが、リン酸エステル系では、トリフェ
ニルホスフェート、トリクレジルホスフェート、クレジ
ルジフェニルホスフェート、オクチルジフェニルホスフ
ェート、ジフェニルビフェニルホスフェート、トリオク
チルホスフェート、トリブチルホスフェート等、フタル
酸エステル系では、ジエチルフタレート、ジメトキシエ
チルフタレート、ジメチルフタレート、ジオクチルフタ
レート等、グリコール酸エステル系では、トリアセチ
ン、トリブチリン、ブチルフタリルブチルグリコレー
ト、エチルフタリルエチルグリコレート、メチルフタリ
ルエチルグリコレート、ブチルフタリルブチルグリコレ
ート等を単独あるいは併用するのが好ましい。The plasticizer that can be used in the present invention is not particularly limited, but in the case of a phosphate ester type, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl Phosphates, tributyl phosphate, etc., phthalate esters, diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, etc., glycolate esters, triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, It is preferable to use methylphthalylethyl glycolate, butylphthalylbutyl glycolate or the like alone or in combination.
【００２９】可塑剤は寸法安定性、加工性の点を考慮す
ると、セルローストリアセテートに対して、３〜１２重
量％の範囲で使用するのが好ましく、４〜８重量％がさ
らに好ましい。In consideration of dimensional stability and processability, the plasticizer is preferably used in an amount of 3 to 12% by weight, more preferably 4 to 8% by weight, based on cellulose triacetate.
【００３０】可塑剤量は寸法安定性及び加工性を考慮す
ると、セルローストリアセテート樹脂に対して３重量％
以上であり、１２重量％以下であるドープを用いるのが
好ましく、特にこれが４重量％以上であり、８重量％以
下であるドープを用いるのが更に好ましい。Considering dimensional stability and processability, the amount of the plasticizer is 3% by weight based on the cellulose triacetate resin.
Thus, it is preferable to use a dope having a content of 12% by weight or less, and particularly preferably a dope having a content of 4% by weight or more and 8% by weight or less.
【００３１】可塑剤が１２重量％以下であれば寸法安定
性の点でより良好となり好ましく、また３重量％以上で
あればスリット加工や打ち抜き加工した際、滑らかな切
断面を得ることができる結果、切り屑の発生が少なく、
製品欠陥を引き起こすことも無い。If the plasticizer is 12% by weight or less, it is preferable in terms of dimensional stability, and if it is 3% by weight or more, a smooth cut surface can be obtained when slitting or punching. , Less generation of chips,
It does not cause product defects.
【００３２】本発明でドープを作製する際に使用される
溶媒としては、セルローストリアセテートを溶解できる
溶媒であれば何でも良く、また単独で溶解できない溶媒
であっても他の溶媒と混合することにより、溶解できる
ものであれば使用することができる。The solvent used in preparing the dope in the present invention may be any solvent as long as it can dissolve cellulose triacetate. Even if the solvent cannot be dissolved alone, it can be mixed with another solvent. Any substance that can be dissolved can be used.
【００３３】一般的には良溶媒であるメチレンクロライ
ドとセルローストリアセテートの貧溶媒からなる混合溶
媒を用い、かつ混合溶媒中には貧溶媒を７〜３０重量％
含有するものである。In general, a mixed solvent of methylene chloride, which is a good solvent, and a poor solvent of cellulose triacetate is used, and the mixed solvent contains 7 to 30% by weight of the poor solvent.
It contains.
【００３４】セルローストリアセテートの貧溶媒として
は、例えばメタノール、エタノール等の炭素原子数１〜
８のアルコール、メチルエチルケトン、メチルイソブチ
ルケトン、酢酸エチル、酢酸プロピル、モノクロルベン
ゼン、ベンゼン、シクロヘクサン、テトラヒドロフラ
ン、メチルセルソルブ、エチレングリコールモノメチル
エーテル等をあげることができ、これらの貧溶媒は単独
もしくは２種以上を適宜組み合わせて用いることができ
る。The poor solvent for cellulose triacetate is, for example, one having 1 to carbon atoms such as methanol and ethanol.
8 alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, monochlorobenzene, benzene, cyclohexane, tetrahydrofuran, methylcellosolve, ethylene glycol monomethyl ether, etc., and these poor solvents may be used alone or in combination of two or more. Can be used in appropriate combination.
【００３５】流延支持体から剥ぎ取られた後のフィルム
を乾燥させる手段は特に制限なく、一般的に熱風、赤外
線、加熱ロール等で行う。簡便さの点で熱風で行うのが
好ましい。乾燥温度は４０℃〜１４０℃の範囲で３〜４
段階の温度に分けて、段々高くしていくことが好まし
く、８０℃〜１４０℃の範囲で行うことが寸法安定性を
良くするためさらに好ましい。The means for drying the film after being peeled off from the casting support is not particularly limited, and is generally performed using hot air, infrared rays, a heating roll, or the like. It is preferable to use hot air in terms of simplicity. Drying temperature is 3-4 in the range of 40-140 ° C.
It is preferable that the temperature is gradually increased in stages, and it is more preferable that the temperature is increased in the range of 80 to 140 ° C. in order to improve dimensional stability.
【００３６】本発明に係る偏光板の作製方法は特に限定
されず、一般的な方法で作製することができる。例え
ば、セルローストリアセテートフィルムをアルカリ処理
し、沃素溶液中に浸漬延伸して作製した偏光膜の両面
に、完全ケン化型ポリビニルアルコール水溶液を用いて
貼り合わせる方法がある。アルカリ処理の代わりに特開
平６−９４９１５号、特開平６−１１８２３２号に記載
されているような易接着加工を使用しても良い。The method for producing the polarizing plate according to the present invention is not particularly limited, and it can be produced by a general method. For example, there is a method in which a cellulose triacetate film is subjected to alkali treatment and immersed and stretched in an iodine solution, and bonded to both surfaces of the polarizing film using a completely saponified polyvinyl alcohol aqueous solution. Instead of the alkali treatment, an easy bonding process as described in JP-A-6-94915 and JP-A-6-118232 may be used.
【００３７】液晶表示用部材とは液晶表示装置に使用さ
れる部材のことで、例えば、偏光板、偏光板用保護フィ
ルム、位相差板、反射板、視野角向上フィルム、防眩フ
ィルム、無反射フィルム、帯電防止フィルムなどがあげ
られる。The liquid crystal display member is a member used in a liquid crystal display device, and includes, for example, a polarizing plate, a protective film for a polarizing plate, a retardation plate, a reflector, a viewing angle improving film, an antiglare film, and a non-reflective film. Films, antistatic films and the like.
【００３８】その中でも寸法安定性に対して厳しい要求
のある偏光板、偏光板用保護フィルム、位相差板、視野
角向上フィルムの製造方法において、本発明を適用する
ことがより好ましい。Among them, the present invention is more preferably applied to a method for producing a polarizing plate, a protective film for a polarizing plate, a retardation plate, and a viewing angle improving film, which have strict requirements for dimensional stability.
【００３９】[0039]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明はこれらに限定されるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
【００４０】実施例１ 〈本発明試料１〉 （ドープ組成物Ａ） 三酢酸セルロース（酢化度６１．０％） １００重量部 トリフェニルホスフェート １３重量部 ２−（２′−ヒドロキシ−３′，５′−ジ−ｔ −ブチルフェニル）ベンゾトリアゾール ８重量部 メチレンクロライド ４７５重量部 エタノール ５０重量部 以上を密閉容器に投入し、４１℃で撹拌しながら完全に
溶解した。ドープ組成物Ａを濾過し、ベルト流延装置を
用い、ドープ温度３３℃でステンレスバンド支持体上に
均一に流延した。ステンレスバンド支持体の前半部分を
１２℃、後半部分を４０℃になるようにコントロールし
ながら溶媒を蒸発させ、ステンレスバンド支持体上から
剥離した。その後、乾燥ゾーンを多数のロールで搬送さ
せながら乾燥を終了させ、膜厚８０μｍの三酢酸セルロ
ースフィルムの本発明試料１を得た。Example 1 <Sample 1 of the present invention> (Dope composition A) 100 parts by weight of cellulose triacetate (degree of acetylation: 61.0%) 13 parts by weight of triphenyl phosphate 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole 8 parts by weight Methylene chloride 475 parts by weight Ethanol 50 parts by weight The above was charged into a closed vessel and completely dissolved with stirring at 41 ° C. The dope composition A was filtered and uniformly cast on a stainless steel band support at a dope temperature of 33 ° C. using a belt casting apparatus. The solvent was evaporated while controlling the first half of the stainless steel band support to 12 ° C. and the second half thereof to 40 ° C., and peeled off from the stainless steel band support. Thereafter, the drying was completed while being conveyed by a number of rolls in the drying zone, to obtain a sample 1 of the present invention of a cellulose triacetate film having a thickness of 80 μm.
【００４１】〈本発明試料２〜９，比較試料１〜６〉本
発明試料１のステンレスバンド支持体の温度を表１記載
の温度に変更した以外は本発明試料１の作成方法と同様
にして本発明試料２〜９、比較試料１〜６を得た。<Samples 2 to 9 of the Present Invention, Comparative Samples 1 to 6> The method of preparing Sample 1 of the present invention was performed in the same manner as in Sample 1 of the present invention except that the temperature of the stainless steel band support of Sample 1 of the present invention was changed to the temperature shown in Table 1. Inventive samples 2 to 9 and comparative samples 1 to 6 were obtained.
【００４２】〈本発明試料１０〉本発明試料２のドープ
組成物Ａをドープ組成物Ｂに変更した以外は同じにして
本発明試料１０を得た。<Sample 10 of the Present Invention> Sample 10 of the present invention was obtained in the same manner as Sample 2 of the present invention except that Dope composition A was changed to Dope composition B.
【００４３】 （ドープ組成物Ｂ） 三酢酸セルロース（酢化度６１．０％） １００重量部 トリフェニルホスフェート ２重量部 エチルフタリルエチルグリコレート １１重量部 ２−（２′−ヒドロキシ−３′，５′−ジ−ｔ −ブチルフェニル）ベンゾトリアゾール ８重量部 メチレンクロライド ４７５重量部 エタノール ５０重量部 〈本発明試料１１〉本発明試料２のドープ組成物Ａをド
ープ組成物Ｃに変更した以外は同じにして本発明試料１
１を得た。(Dope composition B) Cellulose triacetate (degree of acetylation: 61.0%) 100 parts by weight Triphenyl phosphate 2 parts by weight Ethylphthalylethyl glycolate 11 parts by weight 2- (2′-hydroxy-3 ′, 5'-di-t-butylphenyl) benzotriazole 8 parts by weight Methylene chloride 475 parts by weight Ethanol 50 parts by weight <Sample 11 of the present invention> Same except that dope composition A of sample 2 of the present invention was changed to dope composition C. Inventive sample 1
1 was obtained.
【００４４】 （ドープ組成物Ｃ） 三酢酸セルロース（酢化度６１．０％） １００重量部 エチルフタリルエチルグリコレート ６．５重量部 ２−（２′−ヒドロキシ−３′，５′−ジ−ｔ −ブチルフェニル）ベンゾトリアゾール ８重量部 メチレンクロライド ４７５重量部 エタノール ５０重量部 〈本発明試料１２〉本発明試料２のドープ組成物Ａをド
ープ組成物Ｄに変更した以外は同じにして本発明試料１
２を得た。(Dope Composition C) Cellulose triacetate (degree of acetylation: 61.0%) 100 parts by weight Ethylphthalylethyl glycolate 6.5 parts by weight 2- (2′-hydroxy-3 ′, 5′-di) -T-Butylphenyl) benzotriazole 8 parts by weight Methylene chloride 475 parts by weight Ethanol 50 parts by weight <Sample 12 of the present invention> The present invention was carried out in the same manner except that dope composition A of sample 2 of the present invention was changed to dope composition D. Sample 1
2 was obtained.
【００４５】 （ドープ組成物Ｄ） 三酢酸セルロース（酢化度６１．０％） １００重量部 トリフェニルホスフェート ７重量部 ビフェニルジフェニルホスフェート ３．６重量部 ２−（２′−ヒドロキシ−３′，５′−ジ−ｔ −ブチルフェニル）ベンゾトリアゾール ８重量部 メチレンクロライド ４７５重量部 エタノール ５０重量部 〈本発明試料１３〉本発明試料２のドープ組成物Ａをド
ープ組成物Ｅに変更した以外は同じにして本発明試料１
３を得た。(Dope Composition D) Cellulose triacetate (degree of acetylation: 61.0%) 100 parts by weight Triphenyl phosphate 7 parts by weight Biphenyl diphenyl phosphate 3.6 parts by weight 2- (2′-hydroxy-3 ′, 5) '-Di-t-butylphenyl) benzotriazole 8 parts by weight Methylene chloride 475 parts by weight Ethanol 50 parts by weight <Sample 13 of the present invention> The same procedure was carried out except that dope composition A of sample 2 of the present invention was changed to dope composition E. Sample 1 of the present invention
3 was obtained.
【００４６】 （ドープ組成物Ｅ） 三酢酸セルロース（酢化度６１．０％） １００重量部 エチルフタリルエチルグリコレート ８．０重量部 ２−（２′−ヒドロキシ−３′，５′−ジ−ｔ −ブチルフェニル）ベンゾトリアゾール ８重量部 メチレンクロライド ４７５重量部 エタノール ５０重量部 〈本発明試料１４〉本発明試料２のドープ組成物Ａをド
ープ組成物Ｆに変更した以外は同じにして本発明試料１
４を得た。(Dope Composition E) Cellulose triacetate (degree of acetylation: 61.0%) 100 parts by weight Ethylphthalylethyl glycolate 8.0 parts by weight 2- (2′-hydroxy-3 ′, 5′-di) -T-butylphenyl) benzotriazole 8 parts by weight Methylene chloride 475 parts by weight Ethanol 50 parts by weight <Sample 14 of the present invention> The present invention was carried out in the same manner as in Sample 2 of the present invention except that dope composition A was changed to dope composition F. Sample 1
4 was obtained.
【００４７】 （ドープ組成物Ｆ） 三酢酸セルロース（酢化度６１．０％） １００重量部 トリフェニルホスフェート １４重量部 ２−（２′−ヒドロキシ−３′，５′−ジ−ｔ −ブチルフェニル）ベンゾトリアゾール ８重量部 メチレンクロライド ４７５重量部 エタノール ５０重量部 以上のようにして作成した本発明試料１〜１４及び比較
試料１〜６について以下の性能評価を行った。(Dope composition F) Cellulose triacetate (degree of acetylation: 61.0%) 100 parts by weight Triphenyl phosphate 14 parts by weight 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) ) Benzotriazole 8 parts by weight Methylene chloride 475 parts by weight Ethanol 50 parts by weight The following performance evaluation was performed on the inventive samples 1 to 14 and comparative samples 1 to 6 prepared as described above.
【００４８】〔剥離性〕試料の表面を目視で下記の３段
階に分けて剥離性を評価した。[Releasability] The surface of the sample was visually evaluated in three stages as follows.
【００４９】◎：横段ムラが全くない ○：かすかな横段ムラがある ×：横段ムラがあるか又は剥離が困難で剥離時もしくは
搬送時に破断してしまう ○以上であれば液晶用保護フィルムとして使用可能であ
る。◎: No horizontal unevenness at all ：: Slight horizontal unevenness ×: Horizontal unevenness or difficulty in peeling and breaking during peeling or transport It can be used as a film.
【００５０】〔寸法安定性〕試料の表面２ケ所に十文字
型の印を付し、熱処理（条件：９０℃、５０時間）を施
し、工場顕微鏡で印間の距離を測定した。[Dimensional stability] A cross-shaped mark was formed at two places on the surface of the sample, heat-treated (condition: 90 ° C, 50 hours), and the distance between the marks was measured with a factory microscope.
【００５１】熱処理前の距離をａ1とし、熱処理後の距
離をａ2として、下記式で寸法変化率を算出した。Assuming that the distance before the heat treatment was a 1 and the distance after the heat treatment was a 2 , the dimensional change was calculated by the following equation.
【００５２】寸法変化率（％）＝〔（ａ1−ａ2）／
ａ1〕×１００ 尚、寸法安定性としては、比較試料２の寸法変化率を１
００％とした時の各々の寸法変化率を相対値で算出し
た。Dimensional change rate (%) = [(a 1 -a 2 ) /
a 1 ] × 100 The dimensional stability is as follows.
Each dimensional change rate when it was set to 00% was calculated as a relative value.
【００５３】〔偏光板耐久性〕以下に示す方法により偏
光板を作成し、その耐久性を評価した。[Durability of Polarizing Plate] A polarizing plate was prepared by the following method, and its durability was evaluated.
【００５４】（偏光板の作成）試料フィルムを４０℃の
２．５Ｎ−水酸化ナトリウム水溶液で６０秒間アルカリ
処理し、３分間水洗して鹸化処理層を形成し、アルカリ
処理フィルムを得た。(Preparation of Polarizing Plate) A sample film was alkali-treated with a 2.5 N aqueous solution of sodium hydroxide at 40 ° C. for 60 seconds, and washed with water for 3 minutes to form a saponified layer to obtain an alkali-treated film.
【００５５】次に厚さ１２０μｍのポリビニルアルコー
ルフィルムを沃素１重量部、ホウ酸４重量部を含む水溶
液１００重量部に浸漬し、５０℃で４倍に延伸して偏光
膜を作った。この偏光膜の両面に前記アルカリ処理試料
フィルムを完全鹸化型ポリビニルアルコール５％水溶液
を粘着剤として各々貼り合わせ偏光板試料を作成した。Next, a polyvinyl alcohol film having a thickness of 120 μm was immersed in 100 parts by weight of an aqueous solution containing 1 part by weight of iodine and 4 parts by weight of boric acid, and stretched 4 times at 50 ° C. to form a polarizing film. The alkali-treated sample film was bonded to both surfaces of the polarizing film using a completely saponified polyvinyl alcohol 5% aqueous solution as an adhesive to prepare a polarizing plate sample.
【００５６】（偏光板耐久性テスト）１０ｃｍ×１０ｃ
ｍの偏光板試料２枚を熱処理（条件：９０℃、５０時
間）し、直行状態にした時の縦又は横の中心線部分のど
ちらか大きいほうの縁の白抜け部分の長さを測定し、下
記のレベルに判定した。縁の白抜けとは直行状態で光を
通さない偏光板の縁の部分が光を通す常態になること
で、目視で判定できる。偏光板の状態では縁の部分の表
示が見えなくなる故障となる。(Polarizing plate durability test) 10 cm × 10 c
The heat treatment (conditions: 90 ° C., 50 hours) of the two polarizing plate samples having a length of m was performed, and the length of the blank portion at the larger edge of the vertical or horizontal center line portion when the sample was placed in a perpendicular state was measured. And the following levels were determined. The white spot on the edge can be visually determined when the edge portion of the polarizing plate that does not transmit light in a straight state is in a normal state where light passes. In the state of the polarizing plate, a failure occurs in which the display of the edge part cannot be seen.
【００５７】◎：縁の白抜けが５％未満（偏光板として
問題ないレベル） ○：縁の白抜けが５％以上１０％未満（偏光板として問
題ないレベル） △：縁の白抜けが１０％以上２０％未満（偏光板として
何とか使えるレベル） ×：縁の白抜けが２０％以上（偏光板として問題のある
レベル） 評価結果を表１に示す。：: White spots on the edge are less than 5% (a level that does not cause a problem as a polarizing plate) ：: White spots on the edge are 5% to less than 10% (a level that does not cause a problem as a polarizing plate) Δ: White spots on the edge are 10 % Or more and less than 20% (a level that can be used as a polarizing plate) C: White spots on the edge are 20% or more (a problematic level as a polarizing plate) The evaluation results are shown in Table 1.
【００５８】[0058]
【表１】 [Table 1]
【００５９】実施例２ 〈本発明試料２１〉 （ドープ組成物Ｇ） 三酢酸セルロース（酢化度６１．０％） １００重量部 トリフェニルホスフェート １１重量部 ２−（２′−ヒドロキシ−３′，５′−ジ−ｔ −ブチルフェニル）ベンゾトリアゾール ８重量部 メチレンクロライド ３４０重量部 エタノール ３０重量部 以上を密閉容器に投入し、加圧下８０℃で撹拌しながら
完全に溶解した。ドープ組成物Ｇを濾過し、ドラム流延
装置を用い、ドープ温度３３℃で流延ドラム支持体上に
均一に流延し、流延ドラム支持体の前半部分を１２℃、
後半部分を４０℃になるようにコントロールしながら溶
媒を蒸発させ、流延ドラム支持体上から剥離した。その
後、乾燥ゾーンを多数のロールで搬送させながら乾燥を
終了させ、膜厚８０μｍの三酢酸セルロースフィルム本
発明試料２１を得た。Example 2 <Sample 21 of the Invention> (Dope Composition G) Cellulose triacetate (acetation degree: 61.0%) 100 parts by weight Triphenyl phosphate 11 parts by weight 2- (2'-hydroxy-3 ', 5'-Di-t-butylphenyl) benzotriazole 8 parts by weight Methylene chloride 340 parts by weight Ethanol 30 parts by weight The above was charged into a closed container, and completely dissolved with stirring at 80 ° C under pressure. The dope composition G was filtered, and uniformly cast on a casting drum support at a dope temperature of 33 ° C. using a drum casting apparatus. The first half of the casting drum support was heated at 12 ° C.
The solvent was evaporated while controlling the latter half part at 40 ° C., and peeled off from the casting drum support. Thereafter, the drying was terminated while being conveyed by a number of rolls in a drying zone, to obtain a cellulose triacetate film inventive sample 21 having a film thickness of 80 μm.
【００６０】〈本発明試料２２〜２５、比較試料２１、
２２〉本発明試料２１のドラム支持体の温度を表２記載
の温度に変更した以外は本発明試料２１の作成方法と同
様にして本発明試料２２〜２５、比較試料２１、２２を
得た。評価は実施例１に記載した方法と同様にして行っ
た。尚寸法安定性は比較試料２２を１００とした時の相
対値で示した。<Samples 22 to 25 of the present invention, Comparative Sample 21,
22> Samples 22 to 25 of the present invention and Comparative Samples 21 and 22 were obtained in the same manner as in the method of preparing Sample 21 of the present invention except that the temperature of the drum support of Sample 21 of the present invention was changed to the temperature shown in Table 2. The evaluation was performed in the same manner as in the method described in Example 1. In addition, the dimensional stability was shown as a relative value when the comparative sample 22 was 100.
【００６１】評価結果を表２に示す。Table 2 shows the evaluation results.
【００６２】[0062]
【表２】 [Table 2]
【００６３】以上の評価結果から次のことが言える。The following can be said from the above evaluation results.
【００６４】支持体温度が３０℃未満であれば寸法安定
性に優れ、耐久性にも優れていることが本発明試料１〜
７と比較試料２、４を比べることでわかる。When the temperature of the support is less than 30 ° C., the samples of the present invention 1 have excellent dimensional stability and excellent durability.
7 and Comparative Samples 2 and 4.
【００６５】支持体温度が２４℃以下であれば寸法安定
性と耐久性がさらに優れていることが本発明試料１〜３
と本発明試料４、本発明試料５〜６と本発明試料７を比
べることでわかる。When the temperature of the support was 24 ° C. or lower, it was found that the dimensional stability and durability were further excellent.
This can be seen by comparing Sample 4 of the present invention and Samples 5 and 6 of the present invention with Sample 7 of the present invention.
【００６６】支持体温度が１０℃以下だと剥離性が悪化
することが本発明試料１〜７と比較試料１、３を比べる
ことでわかる。It can be seen from the comparison between Samples 1 to 7 of the present invention and Comparative Samples 1 and 3 that the peelability deteriorates when the temperature of the support is 10 ° C. or lower.
【００６７】支持体後半よりも支持体前半の温度を１０
℃を超え３０℃未満にすることで、より寸法安定性、耐
久性に優れていることが本発明試料１〜４と本発明試料
５，６を比べることでわかる。The temperature of the first half of the support is set to 10 rather than the second half of the support.
It can be seen by comparing Samples 1 to 4 of the present invention and Samples 5 and 6 of the present invention that the dimensional stability and the durability are more excellent when the temperature is higher than 0 ° C and lower than 30 ° C.
【００６８】前半と後半両方の支持体温度が１０℃を超
え３０℃未満にすると、もっとも寸法安定性、耐久性に
優れていることが本発明試料８，９と本発明試料１〜７
を比べることでわかる。When the temperature of the support in both the first half and the second half is higher than 10 ° C. and lower than 30 ° C., the samples 8 and 9 of the present invention and the samples 1 to 7 of the present invention exhibit the most excellent dimensional stability and durability.
Can be understood by comparing.
【００６９】支持体の温度が１０℃を超え３０℃未満に
し、ドープに含有する可塑剤の量を減らすことで、さら
に寸法安定性が優れていることが本発明試料２、本発明
試料１０〜１４を比較することでわかる。The samples of the present invention 2 and 10 to 10 show that the dimensional stability is further improved by setting the temperature of the support to more than 10 ° C. and less than 30 ° C. and reducing the amount of the plasticizer contained in the dope. 14 can be seen by comparison.
【００７０】実施例１と実施例２を比較すると、支持体
がドラムであってもベルトと同様の効果が得られること
がわかる。Comparing Example 1 with Example 2, it can be seen that the same effect as the belt can be obtained even when the support is a drum.
【００７１】[0071]
【発明の効果】セルローストリアセテートフィルムの製
造過程において、流延後、剥離までの間に、支持体温度
を１０〜３０℃に保持した工程を経由することにより高
い寸法安定性を実現することができた。In the process of producing a cellulose triacetate film, high dimensional stability can be realized by passing through a process in which the temperature of the support is maintained at 10 to 30 ° C. after casting and before peeling. Was.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｂ２９Ｋ 1:00 Ｃ０８Ｌ 1:00 (72)発明者 小林 徹 東京都日野市さくら町１番地コニカ株式会 社内 (72)発明者 奈良 仁司 東京都日野市さくら町１番地コニカ株式会 社内──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical indication // B29K 1:00 C08L 1:00 (72) Inventor Toru Kobayashi 1 Sakuracho, Hino City, Tokyo Konica Stock Company In-house (72) Inventor Hitoshi Nara 1 Sakuracho, Hino-shi, Tokyo Konica Stock Company In-house
Claims (2)
間に、支持体温度が１０℃を超え、かつ３０℃未満であ
る状態を経由することを特徴とする溶液流延法によるセ
ルローストリアセテートフィルムの製造方法。1. A solution casting method, wherein a temperature of a support exceeds 10 ° C. and is lower than 30 ° C. after casting a dope on a support and before peeling. A method for producing a cellulose triacetate film.
テートフィルムの製造方法を含む液晶表示用部材の製造
方法。2. A method for producing a liquid crystal display member, comprising the method for producing a cellulose triacetate film according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8166041A JPH106351A (en) | 1996-06-26 | 1996-06-26 | Preparation of cellulose triacetate film and preparation of member for liquid crystal displaying |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8166041A JPH106351A (en) | 1996-06-26 | 1996-06-26 | Preparation of cellulose triacetate film and preparation of member for liquid crystal displaying |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH106351A true JPH106351A (en) | 1998-01-13 |
Family
ID=15823862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8166041A Pending JPH106351A (en) | 1996-06-26 | 1996-06-26 | Preparation of cellulose triacetate film and preparation of member for liquid crystal displaying |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH106351A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002225054A (en) * | 2001-01-30 | 2002-08-14 | Konica Corp | Cellulose ester film, production method thereof, polarizing plate and liquid crystal display device |
| JP2003071863A (en) * | 2001-09-05 | 2003-03-12 | Konica Corp | Method for manufacturing cellulose ester film |
| JP2006110881A (en) * | 2004-10-15 | 2006-04-27 | Konica Minolta Opto Inc | Method for cleaning metal support surface in cellulose ester film production apparatus |
| US7046944B2 (en) | 2001-05-18 | 2006-05-16 | Brother Kogyo Kabushiki Kaisha | Color image forming devices for use in color printers |
| US7351365B2 (en) | 2002-02-20 | 2008-04-01 | Fujifilm Corporation | Solution film-forming method, protective film of polarizing plate, optical functional film, polarizing plate, and liquid crystal display device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5514201A (en) * | 1977-12-28 | 1980-01-31 | Konishiroku Photo Ind Co Ltd | Method of manufacturing cellulose triacetate film |
| JPS61100421A (en) * | 1984-10-23 | 1986-05-19 | Fuji Photo Film Co Ltd | Manufacture of cellulose triacetate film |
| JPH02111511A (en) * | 1988-10-20 | 1990-04-24 | Konica Corp | Method for making film by casting |
| JPH05185443A (en) * | 1992-01-09 | 1993-07-27 | Fuji Photo Film Co Ltd | Method for making film from solution |
| JPH0857879A (en) * | 1994-08-19 | 1996-03-05 | Fuji Photo Film Co Ltd | Treating method and manufacture of cellulose ester film and manufacture of phootographic material or optical material |
-
1996
- 1996-06-26 JP JP8166041A patent/JPH106351A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5514201A (en) * | 1977-12-28 | 1980-01-31 | Konishiroku Photo Ind Co Ltd | Method of manufacturing cellulose triacetate film |
| JPS61100421A (en) * | 1984-10-23 | 1986-05-19 | Fuji Photo Film Co Ltd | Manufacture of cellulose triacetate film |
| JPH02111511A (en) * | 1988-10-20 | 1990-04-24 | Konica Corp | Method for making film by casting |
| JPH05185443A (en) * | 1992-01-09 | 1993-07-27 | Fuji Photo Film Co Ltd | Method for making film from solution |
| JPH0857879A (en) * | 1994-08-19 | 1996-03-05 | Fuji Photo Film Co Ltd | Treating method and manufacture of cellulose ester film and manufacture of phootographic material or optical material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002225054A (en) * | 2001-01-30 | 2002-08-14 | Konica Corp | Cellulose ester film, production method thereof, polarizing plate and liquid crystal display device |
| US7046944B2 (en) | 2001-05-18 | 2006-05-16 | Brother Kogyo Kabushiki Kaisha | Color image forming devices for use in color printers |
| JP2003071863A (en) * | 2001-09-05 | 2003-03-12 | Konica Corp | Method for manufacturing cellulose ester film |
| US7351365B2 (en) | 2002-02-20 | 2008-04-01 | Fujifilm Corporation | Solution film-forming method, protective film of polarizing plate, optical functional film, polarizing plate, and liquid crystal display device |
| JP2006110881A (en) * | 2004-10-15 | 2006-04-27 | Konica Minolta Opto Inc | Method for cleaning metal support surface in cellulose ester film production apparatus |
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