TWI599601B - Optical film manufacturing method and manufacturing apparatus - Google Patents
Optical film manufacturing method and manufacturing apparatus Download PDFInfo
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- TWI599601B TWI599601B TW105137490A TW105137490A TWI599601B TW I599601 B TWI599601 B TW I599601B TW 105137490 A TW105137490 A TW 105137490A TW 105137490 A TW105137490 A TW 105137490A TW I599601 B TWI599601 B TW I599601B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
- B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
- B26D1/01—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work
- B26D1/12—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis
- B26D1/14—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a circular cutting member, e.g. disc cutter
- B26D1/24—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a circular cutting member, e.g. disc cutter coacting with another disc cutter
- B26D1/245—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a circular cutting member, e.g. disc cutter coacting with another disc cutter for thin material, e.g. for sheets, strips or the like
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
- B29D11/00432—Auxiliary operations, e.g. machines for filling the moulds
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
- G02B3/0006—Arrays
- G02B3/0012—Arrays characterised by the manufacturing method
- G02B3/0025—Machining, e.g. grinding, polishing, diamond turning, manufacturing of mould parts
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- 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
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Ophthalmology & Optometry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Forests & Forestry (AREA)
- Polarising Elements (AREA)
Description
本發明係關於將長條傾斜配向薄膜的寬度方向的兩端部切斷並取剩餘的部分作為光學薄膜的光學薄膜之製造方法及上述光學薄膜之製造裝置。 The present invention relates to a method for producing an optical film in which an end portion of a long obliquely oriented film in the width direction is cut and a remaining portion is taken as an optical film, and an apparatus for producing the optical film.
長條狀之光學薄膜係例如藉由溶液流延製膜法或熔融流延製膜法所製造。所製造出的光學薄膜之寬度方向的兩端部,係由於膜厚不均勻,或端面之形狀不均勻,因此藉由切斷裝置而被切落。例如,在專利文獻1中,係構成為使用圓形的上刀和圓形的下刀來將光學薄膜之兩端部切落。 The elongated optical film is produced, for example, by a solution casting film forming method or a melt casting film forming method. Both end portions in the width direction of the produced optical film are cut off by the cutting device because the film thickness is not uniform or the shape of the end face is not uniform. For example, in Patent Document 1, a circular upper blade and a circular lower blade are used to cut both end portions of the optical film.
[專利文獻1]日本特開2009-154252號公報(參照請求項1、第1圖、第2圖等) [Patent Document 1] Japanese Laid-Open Patent Publication No. 2009-154252 (refer to claim 1, first figure, second figure, etc.)
另外,近年來,如同亦被稱為OLED(Organic light-Emitting Diode)之有機EL(Electro-Luminescence)顯示裝置般的自發光型之顯示裝置係受到矚目。在OLED中,為了提高光的取出效率,係在顯示器的背面側設置有鋁板等之反射體,因此,因射入至顯示器中之外光被此反射體所反射,影像的對比會降低。 Further, in recent years, a self-luminous type display device such as an organic EL (Electro-Luminescence) display device which is also called an OLED (Organic Light-Emitting Diode) has been attracting attention. In the OLED, in order to improve the light extraction efficiency, a reflector such as an aluminum plate is provided on the back side of the display. Therefore, light incident on the display is reflected by the reflector, and contrast of the image is lowered.
因此,為了達成由防止外光之反射所致的明暗對比之提昇,係將延伸薄膜與偏光元件相貼合而構成圓偏光板,並將此圓偏光板配置在顯示器的表面側,此事係為已知。此時,上述的圓偏光板,係藉由以相對於偏光元件的透射軸而使延伸薄膜之面內遲相軸以所期望之角度來傾斜的方式而將偏光元件與延伸薄膜貼合來形成。 Therefore, in order to achieve an improvement in the contrast between the light and the dark caused by the reflection of the external light, the stretched film and the polarizing element are bonded to each other to form a circularly polarizing plate, and the circular polarizing plate is disposed on the surface side of the display. Is known. In this case, the circular polarizing plate is formed by bonding a polarizing element and a stretched film so that the in-plane slow axis of the stretched film is inclined at a desired angle with respect to the transmission axis of the polarizing element. .
此時,作為上述的延伸薄膜,藉由使用相對於長度方向及寬度方向而朝向傾斜方向作延伸的長條傾斜延伸薄膜(亦稱為長條傾斜配向薄膜),由於可將長條偏光薄膜和長條傾斜配向薄膜藉由卷對卷方式來貼合並製造圓偏光板,因此圓偏光板之生產性係大幅度提昇。因而,近年來,如此之長條傾斜配向薄膜的製造係被活躍地進行。 At this time, as the above-mentioned stretched film, by using an elongated obliquely extending film (also referred to as a long obliquely oriented film) extending in the oblique direction with respect to the longitudinal direction and the width direction, since the long polarizing film and the long polarizing film can be used The strip-shaped oblique alignment film is bonded and manufactured by a roll-to-roll method to produce a circular polarizing plate, so that the productivity of the circular polarizing plate is greatly improved. Therefore, in recent years, the manufacture of such a long oblique alignment film has been actively carried out.
在上述的長條傾斜配向薄膜中,亦同樣地,寬度方向的兩端部,係由於膜厚不均勻,因此在製造後藉由切斷裝置而被切落。但,得知若藉由以往之切斷裝置來將長條傾斜配向薄膜的兩端部切斷,則在將切斷後所剩餘 的光學薄膜作捲繞時,於卷端面會產生些許的卷芯方向之偏移,切斷後的光學薄膜係邊傾斜前進邊被捲繞。進而,得知在切斷後所剩餘的光學薄膜(製品部)之寬度方向的單側之端部,會出現有鬚狀的纖維狀異物(以下,單稱為鬚)或起毛。可推測其原因在於,由於長條傾斜配向薄膜之配向方向係相對於長度方向及寬度方向而傾斜之方向,因此在藉由切斷裝置來將長條傾斜配向薄膜沿著長度方向切斷時,長條傾斜配向薄膜之配向會成為阻抗,長條傾斜配向薄膜係成為相對於切斷裝置(上刀、下刀)而容易相對性地被朝向配向方向彈開,因此,長條傾斜配向薄膜之切斷狀態會變差。若長條傾斜配向薄膜的切斷狀態為差,則在切斷時也會有於光學薄膜產生破斷之虞。可推測,上述之切斷後的光學薄膜之傾斜前進,係起因於在切斷時長條傾斜配向薄膜會被朝向配向方向彈開之故。 Similarly, in the above-described elongated oblique alignment film, both end portions in the width direction are not evenly formed, and therefore are cut off by the cutting device after the production. However, it has been found that if the both ends of the long oblique alignment film are cut by the conventional cutting device, the remaining after the cutting is completed When the optical film is wound, a slight deviation of the core direction occurs in the end surface of the roll, and the cut optical film is wound while being inclined. Further, it is found that a fibrous foreign matter (hereinafter referred to as "sole") or fluffing is formed in the end portion on one side in the width direction of the optical film (product portion) remaining after the cutting. It is presumed that the reason why the alignment direction of the long oblique alignment film is inclined with respect to the longitudinal direction and the width direction is such that when the long oblique alignment film is cut along the longitudinal direction by the cutting device, The alignment of the elongated oblique alignment film becomes an impedance, and the elongated oblique alignment film is easily deflected toward the alignment direction with respect to the cutting device (upper blade, lower blade), and therefore, the elongated oblique alignment film The cutoff state will deteriorate. If the cut state of the long oblique alignment film is poor, the optical film may be broken at the time of cutting. It is presumed that the tilting of the optical film after the above-described cutting is caused by the fact that the elongated alignment film is ejected in the alignment direction at the time of cutting.
在上述之專利文獻1中,針對長條傾斜配向薄膜之切斷並未作任何探討,可以想見,當切斷對象為長條傾斜配向薄膜時,係無法對於在切斷後之作了傾斜配向的光學薄膜之端部的鬚或起毛之發生以及切斷時的光學薄膜之破斷作抑制。 In the above-mentioned Patent Document 1, the cutting of the elongated oblique alignment film is not discussed. It is conceivable that when the object to be cut is a long oblique alignment film, it is impossible to tilt the alignment after the cutting. The occurrence of whiskers or fuzzing at the ends of the optical film and the breaking of the optical film at the time of cutting are suppressed.
本發明係為了解決上述之問題所進行者,其目的在於,提供一種在將長條傾斜配向薄膜的兩端部切斷而取得光學薄膜的情況中,能夠對於在光學薄膜的兩端部的鬚或起毛之發生以及切斷時的光學薄膜之破斷作抑制的光學薄膜之製造方法及製造裝置。 The present invention has been made to solve the above problems, and an object of the invention is to provide a film for both ends of an optical film when the optical film is obtained by cutting both ends of the long oblique alignment film. Or a method for producing an optical film and a manufacturing apparatus for suppressing the occurrence of fuzzing and breaking of an optical film at the time of cutting.
本發明之上述目的,係藉由以下之光學薄膜之製造方法及製造裝置而達成。 The above object of the present invention is achieved by the following method and apparatus for producing an optical film.
亦即,本發明之其中一個側面的光學薄膜之製造方法,係具有將長條傾斜配向薄膜之寬度方向的兩端部分別藉由第1切斷部及第2切斷部進行切斷的切斷步驟,前述長條傾斜配向薄膜在薄膜面內相對於前述寬度方向的配向方向是傾斜的,取前述長條傾斜配向薄膜當中將前述兩端部切斷後剩餘的部分作為光學薄膜,其特徵在於,前述第1切斷部及前述第2切斷部分別含有第1刀及第2刀,前述第1刀,係配置於前述長條傾斜配向薄膜之薄膜面的一側,且將旋轉軸配置成沿著前述寬度方向;前述第2刀,係配置於前述薄膜面之另一側,在前述薄膜面內,以與相對於前述第1刀之束角對應的角度,使旋轉軸相對於前述寬度方向傾斜;在前述切斷步驟,在前述第1切斷部及前述第2切斷部各個,於前述第1刀之前述寬度方向的一側及另一側當中,隨著朝相對於前述第1刀的束角增大的方向將前述第2刀傾斜,在前述第2刀之形成前述束角的面和前述長條傾斜配向薄膜之前述配向方向所形成的角度變小的側配置前述第2刀,利用 前述第1刀和前述第2刀將前述長條傾斜配向薄膜夾住並切斷。 In other words, in the method of producing an optical film according to one aspect of the present invention, the end portions in the width direction of the long oblique alignment film are cut by the first cutting portion and the second cutting portion, respectively. In the breaking step, the strip-shaped oblique alignment film is inclined in the direction of the width direction of the film in the width direction, and the portion remaining in the strip-shaped oblique alignment film after cutting the both end portions is used as an optical film. The first cutting portion and the second cutting portion respectively include a first blade and a second blade, and the first blade is disposed on one side of the film surface of the long oblique alignment film, and the rotating shaft is disposed In the width direction, the second blade is disposed on the other side of the film surface, and the rotation axis is opposite to the aforementioned angle in the film surface at an angle corresponding to a beam angle of the first blade In the cutting step, each of the first cutting portion and the second cutting portion is in the side of the width direction of the first blade and the other side thereof Beam of the first knife The second blade is disposed in a direction in which the angle is increased, and the second blade is disposed on a side where the angle formed by the surface of the second blade forming the toe angle and the direction of the alignment of the long oblique alignment film is small. The first blade and the second blade sandwich and cut the long oblique alignment film.
本發明之另外一個側面的光學薄膜之製造裝置,係具備將長條傾斜配向薄膜之寬度方向的兩端部分別切斷之第1切斷部及第2切斷部,前述長條傾斜配向薄膜在薄膜面內相對於寬度方向的配向方向是傾斜的,取前述長條傾斜配向薄膜當中將前述兩端部切斷後剩餘的部分作為光學薄膜,其特徵在於,前述第1切斷部及前述第2切斷部分別含有第1刀及第2刀,前述第1刀,係配置於前述長條傾斜配向薄膜之薄膜面的一側,且將旋轉軸配置成沿著前述寬度方向;前述第2刀,係配置於前述薄膜面之另一側,在前述薄膜面內,以與相對於前述第1刀的束角對應的角度,使旋轉軸相對於前述寬度方向傾斜,在其和前述第1刀之間將前述長條傾斜配向薄膜夾住並切斷;在前述第1切斷部及前述第2切斷部各個,於前述第1刀之前述寬度方向的一側及另一側當中,隨著朝相對於前述第1刀的束角增大的方向將前述第2刀傾斜,在前述第2刀之形成前述束角的面和前述長條傾斜配向薄膜之前述配向方向所形成的角度變小的側配置前述第2刀。 The apparatus for producing an optical film according to another aspect of the present invention includes a first cutting portion and a second cutting portion that cut both end portions in the width direction of the long oblique alignment film, and the long oblique alignment film The alignment direction in the film surface is inclined with respect to the width direction, and the portion remaining in the long oblique alignment film after the both end portions are cut is an optical film, wherein the first cutting portion and the first portion Each of the cutting portions includes a first blade and a second blade, and the first blade is disposed on one side of the film surface of the long oblique alignment film, and the rotation axis is disposed along the width direction; a knife disposed on the other side of the film surface, wherein the rotation axis is inclined with respect to the width direction at an angle corresponding to a beam angle of the first blade in the film surface, and the first Each of the first cutting portion and the second cutting portion is formed between one side and the other side of the first blade in the width direction of the first cutting portion and the second cutting portion. With the opposite of the front The second blade is inclined in a direction in which the toe angle of the first blade is increased, and is disposed on a side where the angle formed by the surface of the second blade forming the toe angle and the alignment direction of the long oblique alignment film is small. The second knife mentioned above.
依據上述之製造方法及製造裝置,由於在寬 度方向上,第2刀係相對於第1刀而位置在更靠近長條傾斜配向薄膜的配向方向之側並切斷長條傾斜配向薄膜,因此相較於相對於第1刀而將第2刀配置在與上述相反之側並切斷的情況,係可對因長條傾斜配向薄膜之配向所導致的切斷時之阻抗作抑制。藉此,在切斷時,長條傾斜配向薄膜係成為相對於第1切斷部及第2切斷部而相對性地難以被朝向配向方向彈開,而可提昇長條傾斜配向薄膜之切斷狀態。其結果,即使在將長條傾斜配向薄膜的兩端部切斷而取得光學薄膜的情況,亦能夠對於在光學薄膜的端部的鬚或起毛之發生以及切斷時的光學薄膜之破斷作抑制。 According to the above manufacturing method and manufacturing apparatus, since it is wide In the direction of the first blade, the position of the second blade is closer to the direction of the alignment direction of the elongated oblique alignment film with respect to the first blade, and the long oblique alignment film is cut. Therefore, the second blade is second compared to the first blade. When the knives are disposed on the side opposite to the above and cut off, the impedance at the time of cutting due to the alignment of the elongated oblique alignment film can be suppressed. Therefore, at the time of cutting, the long oblique alignment film is relatively difficult to be bounced in the alignment direction with respect to the first cutting portion and the second cutting portion, and the slit oblique alignment film can be lifted. Broken state. As a result, even when the optical film is obtained by cutting both end portions of the long oblique alignment film, it is possible to cause breakage of the optical film at the end of the optical film at the end of the optical film or during the cutting. inhibition.
1‧‧‧製造裝置 1‧‧‧ manufacturing equipment
8a‧‧‧第1切斷部 8a‧‧‧1st cut-off
8b‧‧‧第2切斷部 8b‧‧‧2nd cut-off
10a‧‧‧上刀(第2刀) 10a‧‧‧Upper knife (2nd knife)
10a1‧‧‧旋轉軸 10a 1 ‧‧‧Rotary axis
10b‧‧‧下刀(第1刀) 10b‧‧‧Blade (1st knife)
10b1‧‧‧旋轉軸 10b 1 ‧‧‧Rotary axis
F‧‧‧光學薄膜 F‧‧‧Optical film
F’‧‧‧長條傾斜配向薄膜 F’‧‧‧Long strip oblique alignment film
S‧‧‧面 S‧‧‧ face
Ta‧‧‧端部 Ta‧‧‧ end
Tb‧‧‧端部 Tb‧‧‧ end
θ‧‧‧角度 Θ‧‧‧ angle
θ 1‧‧‧束角 θ 1‧‧‧beam angle
[第1圖]係示意性顯示本發明之實施形態的光學薄膜之製造裝置的概略構成之平面圖。 [Fig. 1] is a plan view schematically showing a schematic configuration of an apparatus for manufacturing an optical film according to an embodiment of the present invention.
[第2圖]係示意性顯示上述製造裝置所具備的延伸部之軌形態的其中一例之平面圖。 [Fig. 2] is a plan view schematically showing an example of a rail form of an extension portion provided in the above-described manufacturing apparatus.
[第3圖]係顯示上述製造裝置所具備的薄膜切斷裝置之概略構成之立體圖。 [Fig. 3] A perspective view showing a schematic configuration of a film cutting device provided in the above-described manufacturing apparatus.
[第4圖]係上述薄膜切斷裝置之平面圖。 [Fig. 4] is a plan view of the above film cutting device.
[第5圖]係參考例之薄膜切斷裝置之平面圖。 [Fig. 5] is a plan view of a film cutting device of a reference example.
[第6圖]係顯示作為適用藉由上述製造裝置所製造的光學薄膜之其中一例之有機EL顯示裝置的概略構成之剖面圖。 [Fig. 6] Fig. 6 is a cross-sectional view showing a schematic configuration of an organic EL display device as an example of an optical film to be produced by the above-described manufacturing apparatus.
[第7圖]係顯示作為適用上述光學薄膜之其他例之液晶顯示裝置的概略構成之剖面圖。 [Fig. 7] Fig. 7 is a cross-sectional view showing a schematic configuration of a liquid crystal display device as another example in which the above optical film is applied.
若針對本發明之其中一實施形態,根據附圖來進行說明,則如以下所述。另外,在本說明書中,當將數值範圍標記為A~B的情況時,係視為在該數值範圍中包含下限A及上限B之值。又,本發明並不限定於以下的內容。 An embodiment of the present invention will be described below with reference to the drawings. Further, in the present specification, when the numerical range is marked as A to B, it is considered that the value of the lower limit A and the upper limit B is included in the numerical range. Further, the present invention is not limited to the following.
本實施形態之光學薄膜之製造方法,係具有將長條傾斜配向薄膜之寬度方向的兩端部分別藉由第1切斷部及第2切斷部來切斷的切斷步驟,前述長條傾斜配向薄膜在薄膜面內相對於寬度方向的配向方向是傾斜的,取前述長條傾斜配向薄膜當中將前述兩端部切斷後剩餘的部分作為光學薄膜。前述第1切斷部及前述第2切斷部分別含有第1刀及第2刀,前述第1刀,係配置於前述長條傾斜配向薄膜之薄膜面的一側,且將旋轉軸配置成沿著前述寬度方向;前述第2刀,係配置於前述薄膜面之另一側,在前述薄膜面內,以與相對於前述第1刀的束角對應的角度,使旋轉軸相對於前述寬度方向傾斜。在前述切斷步驟,在前述第1切斷部及前述第2切斷部各個,於前述第1刀之前述寬度方向的一側及另一側當中,隨著朝相對於前述第1刀的束角增大的方向將前述第2刀傾斜,在前述第2刀之形成前述束角的面和前述長條傾斜配向薄膜之前 述配向方向所形成的角度變小的側配置前述第2刀,利用前述第1刀和前述第2刀將前述長條傾斜配向薄膜夾住並切斷。 The method for producing an optical film according to the present embodiment includes a cutting step of cutting both end portions in the width direction of the long oblique alignment film by the first cutting portion and the second cutting portion, and the strip The oblique alignment film is inclined in the alignment direction with respect to the width direction in the film surface, and the remaining portion of the long oblique alignment film after the both end portions are cut is used as an optical film. Each of the first cutting portion and the second cutting portion includes a first blade and a second blade, and the first blade is disposed on one side of the film surface of the long oblique alignment film, and the rotating shaft is disposed so that In the width direction, the second blade is disposed on the other side of the film surface, and the rotation axis is opposite to the width in the film surface at an angle corresponding to a beam angle of the first blade. Tilt in direction. In the cutting step, each of the first cutting portion and the second cutting portion is in the one side and the other side in the width direction of the first blade, with respect to the first blade The second blade is inclined in a direction in which the toe angle is increased, before the surface of the second blade forming the toe angle and the long oblique alignment film The second blade is disposed on the side where the angle formed by the alignment direction is reduced, and the long oblique alignment film is sandwiched and cut by the first blade and the second blade.
又,本實施形態之光學薄膜之製造裝置,係具備將長條傾斜配向薄膜之寬度方向的兩端部分別切斷之第1切斷部及第2切斷部,前述長條傾斜配向薄膜在薄膜面內相對於寬度方向的配向方向是傾斜的,取前述長條傾斜配向薄膜當中將前述兩端部切斷後剩餘的部分作為光學薄膜。前述第1切斷部及前述第2切斷部分別含有第1刀及第2刀,前述第1刀,係配置於前述長條傾斜配向薄膜之薄膜面的一側,且將旋轉軸配置成沿著前述寬度方向,前述第2刀,係配置於前述薄膜面之另一側,在前述薄膜面內,以與相對於前述第1刀的束角對應的角度,使旋轉軸相對於前述寬度方向傾斜,在其和前述第1刀之間將前述長條傾斜配向薄膜夾住並切斷。在前述第1切斷部及前述第2切斷部各個,於前述第1刀之前述寬度方向的一側及另一側當中,隨著朝相對於前述第1刀的束角增大的方向將前述第2刀傾斜,在前述第2刀之形成前述束角的面和前述長條傾斜配向薄膜之前述配向方向所形成的角度變小的側配置前述第2刀。 Moreover, the apparatus for manufacturing an optical film according to the present embodiment includes a first cutting portion and a second cutting portion that cut both end portions in the width direction of the long oblique alignment film, and the long oblique alignment film is The alignment direction of the inside of the film in the width direction is inclined, and the remaining portion of the long oblique alignment film after the both end portions are cut is used as an optical film. Each of the first cutting portion and the second cutting portion includes a first blade and a second blade, and the first blade is disposed on one side of the film surface of the long oblique alignment film, and the rotating shaft is disposed so that The second blade is disposed on the other side of the film surface along the width direction, and the rotation axis is opposite to the width in the film surface at an angle corresponding to a beam angle of the first blade. The direction is inclined, and the long oblique alignment film is sandwiched and cut between the first blade and the first blade. Each of the first cutting portion and the second cutting portion increases in a direction toward a toe angle with respect to the first blade in one side and the other side in the width direction of the first blade. The second blade is disposed such that the second blade is inclined, and the angle formed by the surface of the second blade forming the toe angle and the direction of the alignment of the long oblique alignment film is reduced.
在此,長條傾斜配向薄膜的配向方向,亦即,遲相軸的方向,係在長條傾斜配向薄膜的薄膜面內(與厚度方向垂直的面內),相對於薄膜的寬度方向而成超過0°未達90°的角度之方向(自動性地相對於薄膜的長 度方向亦成為超過0°而未達90°的角度之方向)。遲相軸,由於通常係出現於延伸方向或者是與延伸方向成直角的方向,因此藉由以相對於薄膜的寬度方向而超過0°未達90°的角度來進行延伸,而能夠製造具有此種遲相軸的長條傾斜配向薄膜。長條傾斜配向薄膜的寬度方向與遲相軸間所成之角度,亦即配向角度,係可在超過0°未達90°的範圍內任意設定為所期望的角度。 Here, the alignment direction of the long oblique alignment film, that is, the direction of the slow axis is in the film surface of the long oblique alignment film (in the plane perpendicular to the thickness direction), and is formed with respect to the width direction of the film. The direction of the angle exceeding 0° below 90° (automatically relative to the length of the film) The direction of the dimension also becomes an angle of more than 0° and less than 90°). Since the retardation axis is usually present in the extending direction or in a direction perpendicular to the extending direction, it can be manufactured by extending at an angle of more than 0° with respect to the width direction of the film of less than 90°. A long obliquely oriented film of a slow phase axis. The angle formed between the width direction of the elongated oblique alignment film and the late phase axis, that is, the alignment angle, can be arbitrarily set to a desired angle within a range of more than 0° and less than 90°.
於本實施形態中,長條係指相對於薄膜的寬幅而至少具有5倍程度以上的長度者,較佳係具有10倍或者10倍以上的長度,具體而言,係可視為具有能夠捲繞成卷狀並作保管或搬運的程度之長度者(薄膜卷)。 In the present embodiment, the long strip refers to a length of at least 5 times or more with respect to the width of the film, and preferably has a length of 10 times or more, more specifically, it can be regarded as having a roll. The length (film roll) of the length that is wound into a roll and stored or transported.
在製造長條傾斜配向薄膜時,係藉由連續性地製造薄膜,而可將薄膜設為所期望的長度。另外,長條傾斜配向薄膜,係可構成為在將長條薄膜製膜之後,將其一度捲繞在卷芯上而作成捲繞體,並從此捲繞體將長條薄膜供給至傾斜延伸步驟中而進行製造,亦可不將製膜後之長條薄膜作捲繞而從製膜步驟連續地供給至傾斜延伸步驟中而進行製造。將製膜步驟和傾斜延伸步驟連續進行者,係由於可將延伸後之薄膜的膜厚或光學值之結果作反饋並變更製膜條件,以得到所期望的長條傾斜配向薄膜,因此為佳。 In the production of a long oblique alignment film, the film can be formed into a desired length by continuously producing a film. Further, the elongated oblique alignment film may be configured such that after the long film is formed into a film, it is once wound on a winding core to form a wound body, and the long film is supplied from the winding body to the oblique stretching step. In the case of manufacturing, the long film after the film formation may be wound and continuously supplied from the film forming step to the oblique stretching step to be produced. When the film forming step and the tilting step are continuously performed, it is preferable to feed back the film thickness or optical value of the stretched film and change the film forming conditions to obtain a desired long oblique alignment film. .
以下,適當參照附圖,來具體地說明本發明之實施樣態。另外,在以下的說明中,在記載為長條薄膜的情況,係指在傾斜延伸步驟中之成為延伸對象的長條狀 之薄膜者,以與傾斜延伸後之長條傾斜配向薄膜作區分。 Hereinafter, embodiments of the present invention will be specifically described with reference to the accompanying drawings. In addition, in the following description, when it is described as a long film, it is the strip shape which becomes an extension object in the inclination extension process. The film is distinguished from the obliquely oriented film which is obliquely extended.
作為在本實施形態之光學薄膜之製造裝置(詳細內容係後述)中成為延伸對象的長條薄膜並無特別限定,只要是由熱塑性樹脂所構成的薄膜即可,例如,在將延伸後之薄膜使用於光學用途的情況,係以由相對於所期望之波長而具有透明之性質的樹脂所成之薄膜為佳。作為如此之樹脂係可列舉:聚碳酸酯系樹脂、聚醚碸系樹脂、聚對苯二甲酸乙二酯系樹脂、聚醯亞胺系樹脂、聚甲基丙烯酸甲酯系樹脂、聚碸系樹脂、聚芳酯系樹脂、聚乙烯系樹脂、聚氯乙烯系樹脂、具有脂環構造之烯烴聚合物系樹脂(脂環式烯烴聚合物系樹脂、亦單稱為環狀烯烴系樹脂)、纖維素酯系樹脂等。 The long film to be stretched in the apparatus for producing an optical film of the present embodiment (details will be described later) is not particularly limited as long as it is a film made of a thermoplastic resin, for example, a film which is stretched. In the case of use for optical use, a film made of a resin having a property of being transparent with respect to a desired wavelength is preferred. Examples of such a resin include a polycarbonate resin, a polyether oxime resin, a polyethylene terephthalate resin, a polyamidene resin, a polymethyl methacrylate resin, and a polyfluorene system. Resin, polyarylate resin, polyethylene resin, polyvinyl chloride resin, olefin polymer resin having an alicyclic structure (alicyclic olefin polymer resin, also referred to simply as cyclic olefin resin), A cellulose ester resin or the like.
此等當中,就透明性或機械強度等的觀點而言,較佳為聚碳酸酯系樹脂、脂環式烯烴聚合物系樹脂、纖維素酯系樹脂。其中,又以在作為光學薄膜的情況時之對於相位差進行調整一事為容易的脂環式烯烴聚合物系樹脂、纖維素酯系樹脂為更佳。因此,以下,針對於本實施形態中所較佳使用的脂環式烯烴聚合物系樹脂、纖維素酯系樹脂、聚碳酸酯系樹脂進行說明。 Among these, from the viewpoints of transparency, mechanical strength, and the like, a polycarbonate resin, an alicyclic olefin polymer resin, or a cellulose ester resin is preferable. In addition, it is more preferable that the alicyclic olefin polymer-based resin or the cellulose ester-based resin is easy to adjust the phase difference in the case of the optical film. Therefore, the alicyclic olefin polymer resin, the cellulose ester resin, and the polycarbonate resin which are preferably used in the present embodiment will be described below.
作為脂環式烯烴聚合物系樹脂,係可採用於日本特開 平05-310845號公報中所記載的環狀烯烴無規多元共聚合物、於日本特開平05-97978號公報中所記載的氫化聚合物、於日本特開平11-124429號公報中所記載的熱塑性二環戊二烯系開環聚合物及其氫化物等。 As an alicyclic olefin polymer resin, it can be used in Japan. The cyclic olefin random multi-component copolymer described in Japanese Laid-Open Patent Publication No. Hei 05-97978, the entire disclosure of which is incorporated herein by reference. A thermoplastic dicyclopentadiene ring-opening polymer, a hydride thereof, or the like.
脂環式烯烴聚合物系樹脂,係具有如同飽和脂環烴(環烷烴)構造或不飽和脂環烴(環烯)構造一般的脂環式構造之聚合物。構成脂環式構造之碳原子數雖無特別限制,但在通常為4~30個、較佳為5~20個、更佳為5~15個之範圍時,在機械強度、耐熱性以及長條薄膜的成形性之特性上係能夠取得高度的平衡,而為適宜。 The alicyclic olefin polymer-based resin is a polymer having an alicyclic structure as a saturated alicyclic hydrocarbon (cycloalkane) structure or an unsaturated alicyclic hydrocarbon (cycloolefin) structure. Although the number of carbon atoms constituting the alicyclic structure is not particularly limited, it is mechanical strength, heat resistance, and long in the range of usually 4 to 30, preferably 5 to 20, more preferably 5 to 15. It is suitable that the film has a high degree of balance in the formability of the film.
脂環式烯烴聚合物中之含有脂環式構造所成之重複單位的比例,係只要適當選擇即可,但較佳為55重量%以上,更佳為70重量%以上,特佳為90重量%以上。若脂環式烯烴樹脂中之具有脂環式構造之重複單位的比例落在此範圍中,則由於藉由本實施形態之長條傾斜配向薄膜所得到的相位差薄膜等之光學材料的透明性及耐熱性會提昇,因此為佳。 The proportion of the repeating unit in which the alicyclic structure is contained in the alicyclic olefin polymer is preferably selected as appropriate, but is preferably 55% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight. %the above. When the ratio of the repeating unit having an alicyclic structure in the alicyclic olefin resin falls within this range, the transparency of the optical material such as the retardation film obtained by the long oblique alignment film of the present embodiment and Heat resistance will improve, so it is better.
作為具有脂環構造之烯烴聚合物系樹脂係可列舉:降莰烯系樹脂、單環之環狀烯烴系樹脂、環狀共軛二烯系樹脂、乙烯基脂環式烴系樹脂及此等之氫化物等。此等當中,降莰烯系樹脂,係由於其透明性與成形性為良好,因此可適宜使用。 Examples of the olefin polymer-based resin having an alicyclic structure include a norbornene-based resin, a monocyclic cyclic olefin-based resin, a cyclic conjugated diene-based resin, a vinyl alicyclic hydrocarbon-based resin, and the like. Hydride, etc. Among these, the norbornene-based resin is preferably used because it has good transparency and moldability.
作為降莰烯系樹脂係可列舉例如:具有降莰烯構造之單體的開環聚合物或具有降莰烯構造之單體與其 他單體之開環共聚物或者該等之氫化物、具有降莰烯構造之單體之加成聚合物或具有降莰烯構造之單體與其他單體之加成共聚物或者該等之氫化物等。此等當中,具有降莰烯構造之單體的開環(共)聚合物氫化物,就透明性、成形性、耐熱性、低吸濕性、尺寸安定性以及輕量性的觀點而言,係可特別適宜使用。 Examples of the norbornene-based resin include a ring-opening polymer having a monomer having a norbornene structure or a monomer having a norbornene structure and a monomeric ring-opening copolymer or such a hydride, an addition polymer of a monomer having a norbornene structure or an addition copolymer of a monomer having a norbornene structure and other monomers or the like Hydride, etc. Among these, a ring-opened (co)polymer hydride having a monomer having a norbornene structure, from the viewpoints of transparency, formability, heat resistance, low hygroscopicity, dimensional stability, and lightness, It is particularly suitable for use.
作為成形如上述般之使用有降莰烯系樹脂的長條薄膜之方法,係以後述之溶液流延法(溶液製膜法)或熔融流延法(例如熔融押出法)的製造方法為佳。作為熔融押出法,係可列舉使用有模之膨脹法等,在生產性與厚度精度優異的觀點,係以使用T模之方法為佳。 As a method of forming a long film using a norbornene-based resin as described above, a method of producing a solution casting method (solution film forming method) or a melt casting method (for example, melt-bending method) described later is preferable. . The melt extrusion method is exemplified by the use of a mold expansion method, and is preferably a method using a T mold from the viewpoint of excellent productivity and thickness precision.
作為使用有T模之押出成形法,係可藉由如於日本特開2004-233604號公報中所記載般之將密著於冷卻筒時的熔融狀態之熱塑性樹脂保持在安定的狀態的方法,來製造遲滯(Retardation)或配向角之類之光學特性的參差為小的長條薄膜。 As a method of using a T-die, the thermoplastic resin which is in a molten state when it is adhered to a cooling cylinder is kept in a stable state as described in Japanese Laid-Open Patent Publication No. 2004-233604. To produce a small strip of film with a staggered optical characteristic such as retardation or alignment angle.
具體而言係可列舉:1)在藉由熔融押出法而製造長條薄膜時,使從模被押出之薄片狀的熱塑性樹脂在50kPa以下之壓力下密著於冷卻筒上並作拉取的方法;2)在藉由熔融押出法而製造長條薄膜時,將從模開口部起直到最初所密著的冷卻筒為止的範圍藉由包圍構件來作覆蓋,並將從包圍構件起直到模開口部或者最初所密著的冷卻筒為止之距離設為100mm以下的方法;3)在藉由熔融押出法而製造長條薄膜時,將距離從模開口部被押出的 薄片狀之熱塑性樹脂10mm以內的環境之溫度加溫至特定之溫度的方法;4)以滿足關係的方式來使從模被押出的薄片狀之熱塑性樹脂在50kPa以下之壓力下密著於冷卻筒上並作拉取的方法;5)在藉由熔融押出法而製造長條薄膜時,對於從模開口部被押出之薄片狀的熱塑性樹脂吹附與最初所密著的冷卻筒之拉取速度之間的速度差為0.2m/s以下之風的方法。 Specifically, when a long film is produced by a melt extrusion method, the sheet-like thermoplastic resin extruded from the mold is adhered to the cooling cylinder under a pressure of 50 kPa or less and pulled. Method 2) When a long film is produced by a melt extrusion method, the range from the opening portion of the mold to the first cooling cylinder is covered by the surrounding member, and will be from the surrounding member to the mold. a method in which the distance from the opening or the first cooling cylinder is set to 100 mm or less; and 3) when the long film is produced by the melt extrusion method, the distance is pushed out from the opening of the mold. a method of heating the temperature of the sheet-like thermoplastic resin to a specific temperature within a temperature of 10 mm; 4) satisfying the relationship so that the sheet-like thermoplastic resin extruded from the mold is adhered to the cooling cylinder under a pressure of 50 kPa or less When the long film is produced by the melt extrusion method, the sheet-like thermoplastic resin extruded from the opening of the mold is blown with the drawing speed of the initially sealed cooling cylinder. A method in which the speed difference between the winds is less than 0.2 m/s.
此長條薄膜係可為單層,亦可為2層以上之層合薄膜。層合薄膜,係可藉由共押出成形法、共流延成形法、薄膜層壓法、塗佈法等之周知的方法來得到。此等當中,係以共押出成形法、共流延成形法為佳。 The long film may be a single layer or a laminated film of two or more layers. The laminated film can be obtained by a well-known method such as a co-extrusion molding method, a co-cast molding method, a film lamination method, or a coating method. Among these, a co-extrusion molding method and a co-cast molding method are preferred.
作為纖維素酯系樹脂薄膜係可列舉:含有滿足下述式(1)及(2)之纖維素醯化物,且含有以下述一般式(A)所表示之化合物者。 The cellulose ester-based resin film is a compound containing a cellulose halide satisfying the following formulas (1) and (2) and containing a compound represented by the following general formula (A).
式(1) 2.0≦Z1<3.0 Equation (1) 2.0≦Z1<3.0
式(2) 0≦X<3.0(於式(1)及(2)中,Z1係表示纖維素醯化物之總醯基取代度,X係表示纖維素醯化物之丙醯基取代度及丁醯基取代度之總和)。 Formula (2) 0≦X<3.0 (In the formulae (1) and (2), Z1 represents the total thiol substitution degree of the cellulose oxime, and X represents the propylene group substitution degree of the cellulose ruthenium and the butyl group The sum of the degrees of substitution).
以下,針對一般式(A)進行詳細說明。於一般式(A)中,L1及L2係各自獨立表示單鍵或2價之連結基。作為L1及L2,係可列舉例如下述構造。(下述R係表示氫原子或取代基)。 Hereinafter, the general formula (A) will be described in detail. In the general formula (A), each of L 1 and L 2 independently represents a single bond or a divalent linking group. Examples of L 1 and L 2 include the following structures. (The following R represents a hydrogen atom or a substituent).
作為L1及L2,較佳為-O-、-COO-、-OCO-。 As L 1 and L 2 , -O-, -COO-, -OCO- are preferable.
R1、R2及R3係各自獨立表示取代基。作為以R1、R2及R3所表示之取代基的具體例係可列舉:鹵素原子(氟原子、氯原子、溴原子、碘原子等)、烷基(甲基、乙基、n-丙基、異丙基、tert-丁基、n-辛基、2-乙基己基等)、環烷基(環己基、環戊基、4-n-十二烷基環己基等)、烯基(乙烯基、烯丙基等)、環烯基(2-環戊烯-1-基、2-環己烯-1-基等)、炔基(乙炔基、炔丙基 等)、芳基(苯基、p-甲苯基、萘基等)、雜環基(2-呋喃基、2-噻吩基、2-嘧啶基、2-苯并噻唑基等)、氰基、羥基、硝基、羧基、烷氧基(甲氧基、乙氧基、異丙氧基、tert-丁氧基、n-辛氧基、2-甲氧乙氧基等)、芳氧基(苯氧基、2-甲基苯氧基、4-tert-丁基苯氧基、3-硝苯氧基、2-十四醯基胺基苯氧基等)、醯氧基(甲醯氧基、乙醯氧基、新戊醯氧基(pivaloyloxy)、硬脂醯氧基、苯甲醯氧基、p-甲氧苯基羰氧基等)、胺基(胺基、甲基胺基、二甲基胺基、苯胺基、N-甲基-苯胺基、二苯基胺基等)、醯基胺基(甲醯基胺基、乙醯基胺基、新戊醯基胺基、月桂醯基胺基、苯甲醯基胺基等)、烷基及芳基磺醯基胺基(甲基磺醯基胺基、丁基磺醯基胺基、苯基磺醯基胺基、2,3,5-三氯苯基磺醯基胺基、p-甲基苯基磺醯基胺基等)、巰基、烷硫基(甲硫基、乙硫基、n-十六烷硫基等)、芳硫基(苯硫基、p-氯苯硫基、m-甲氧苯硫基等)、胺磺醯基(N-乙基胺磺醯基、N-(3-十二烷氧丙基)胺磺醯基、N,N-二甲基胺磺醯基、N-乙醯基胺磺醯基、N-苯甲醯基胺磺醯基、N-(N’苯基胺甲醯基)胺磺醯基等)、磺基、醯基(乙醯基、新戊醯基苯甲醯基等)、胺甲醯基(胺甲醯基、N-甲基胺甲醯基、N,N-二甲基胺甲醯基、N,N-二-n-辛基胺甲醯基、N-(甲基磺醯基)胺甲醯基等)。 R 1 , R 2 and R 3 each independently represent a substituent. Specific examples of the substituent represented by R 1 , R 2 and R 3 include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), and an alkyl group (methyl group, ethyl group, n- group). Propyl, isopropyl, tert-butyl, n-octyl, 2-ethylhexyl, etc.), cycloalkyl (cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl, etc.), alkene (vinyl, allyl, etc.), cycloalkenyl (2-cyclopenten-1-yl, 2-cyclohexen-1-yl, etc.), alkynyl (ethynyl, propargyl, etc.), aromatic (phenyl, p-tolyl, naphthyl, etc.), heterocyclic (2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, etc.), cyano, hydroxy, nitro , a carboxyl group, an alkoxy group (methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group, etc.), an aryloxy group (phenoxy group, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecylaminophenoxy, etc., decyloxy (methyloxyl, acetamidine) Oxyl, pivaloyloxy, stearyloxy, benzhydryloxy, p-methoxyphenylcarbonyloxy, etc., amine group (amine group, methylamino group, dimethyl group) Amine, anilino, N -Methyl-anilino, diphenylamino, etc.), mercaptoamine (carbomethylamino, ethionylamino, neopentylamino, laurylamine, benzhydrylamine Base, etc., alkyl and arylsulfonylamino (methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonate Mercaptoamine, p-methylphenylsulfonylamino, etc., mercapto, alkylthio (methylthio, ethylthio, n-hexadecanethio, etc.), arylthio (phenylthio) , p-chlorophenylthio, m-methoxyphenylthio, etc.), amidoxime (N-ethylaminesulfonyl, N-(3-dodecyloxypropyl)aminesulfonyl, N , N-dimethylamine sulfonyl, N-acetyl sulfonyl sulfonyl, N-benzhydryl sulfonyl sulfonyl, N-(N' phenyl carbamoyl) sulfonyl sulfhydryl, etc.) , sulfo, fluorenyl (ethylidene, neopentyl benzoyl thiol, etc.), amine methyl sulfhydryl (amine methyl sulfhydryl, N-methyl carbamoyl, N, N-dimethylamine Anthracenyl, N,N-di-n-octylaminecarbamyl, N-(methylsulfonyl)amine, mercapto, etc.).
作為R1及R2,較佳為取代或無取代之苯基、取代或無取代之環己基,更佳為具有取代基之苯基、具有 取代基之環己基,再更佳為於4位具有取代基之苯基、於4位具有取代基之環己基。 R 1 and R 2 are preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted cyclohexyl group, more preferably a substituted phenyl group, a substituted cyclohexyl group, and even more preferably a 4-position. A phenyl group having a substituent and a cyclohexyl group having a substituent at the 4-position.
作為R3,較佳為氫原子、鹵素原子、烷基、烯基、芳基、雜環基、羥基、羧基、烷氧基、芳氧基、醯氧基、氰基、胺基,更佳為氫原子、鹵素原子、烷基、氰基、烷氧基。 R 3 is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, a decyloxy group, a cyano group or an amine group, more preferably It is a hydrogen atom, a halogen atom, an alkyl group, a cyano group, or an alkoxy group.
Wa及Wb,係表示氫原子或取代基,但,(I)Wa及Wb亦可相互結合而形成環;(H)Wa及Wb之至少一個亦可具有環構造;或者(III)Wa及Wb之至少一個亦可為烯基或者炔基。 Wa and Wb are a hydrogen atom or a substituent, but (I) Wa and Wb may be bonded to each other to form a ring; (H) at least one of Wa and Wb may have a ring structure; or (III) Wa and Wb At least one of them may also be an alkenyl or alkynyl group.
作為以Wa及Wb所表示之取代基的具體例係可列舉:鹵素原子(氟原子、氯原子、溴原子、碘原子等)、烷基(甲基、乙基、n-丙基、異丙基、tert-丁基、n-辛基、2-乙基己基等)、環烷基(環己基、環戊基、4-n-十二烷基環己基等)、烯基(乙烯基、烯丙基等)、環烯基(2-環戊烯-1-基、2-環己烯-1-基等)、炔基(乙炔基、炔丙基等)、芳基(苯基、p-甲苯基、萘基等)、雜環基(2-呋喃基、2-噻吩基、2-嘧啶基、2-苯并噻唑基等)、氰基、羥基、硝基、羧基、烷氧基(甲氧基、乙氧基、異丙氧基、tert-丁氧基、n-辛氧基、2-甲氧乙氧基等)、芳氧基(苯氧基、2-甲基苯氧基、4-tert-丁基苯氧基、3-硝苯氧基、2-十四醯基胺基苯氧基等)、醯氧基(甲醯氧基、乙醯氧基、新戊醯氧基、硬脂醯氧基、苯甲醯氧基、p-甲氧苯基羰氧基等)、胺基(胺基、甲基胺 基、二甲基胺基、苯胺基、N-甲基-苯胺基、二苯基胺基等)、醯基胺基(甲醯基胺基、乙醯基胺基、新戊醯基胺基、月桂醯基胺基、苯甲醯基胺基等)、烷基及芳基磺醯基胺基(甲基磺醯基胺基、丁基磺醯基胺基、苯基磺醯基胺基、2,3,5-三氯苯基磺醯基胺基、p-甲基苯基磺醯基胺基等)、巰基、烷硫基(甲硫基、乙硫基、n-十六烷硫基等)、芳硫基(苯硫基、p-氯苯硫基、m-甲氧苯硫基等)、胺磺醯基(N-乙基胺磺醯基、N-(3-十二烷氧丙基)胺醯基、N,N-二甲基胺磺醯基、N-乙醯基胺磺醯基、N-苯甲醯基胺磺醯基、N-(N’苯基胺甲醯基)胺磺醯基等)、磺基、醯基(乙醯基、新戊醯基苯甲醯基等)、胺甲醯基(胺甲醯基、N-甲基胺甲醯基、N,N-二甲基胺甲醯基、N,N-二-n-辛基胺甲醯基、N-(甲基磺醯基)胺甲醯基等)。 Specific examples of the substituent represented by Wa and Wb include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), and an alkyl group (methyl group, ethyl group, n-propyl group, and isopropyl group). Base, tert-butyl, n-octyl, 2-ethylhexyl, etc.), cycloalkyl (cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl, etc.), alkenyl (vinyl, Allyl group, etc., cycloalkenyl (2-cyclopenten-1-yl, 2-cyclohexen-1-yl, etc.), alkynyl (ethynyl, propargyl, etc.), aryl (phenyl, P-tolyl, naphthyl, etc.), heterocyclic group (2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, etc.), cyano, hydroxy, nitro, carboxyl, alkoxy (methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy, etc.), aryloxy (phenoxy, 2-methylbenzene) Oxyl, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecylaminophenoxy, etc., decyloxy (methyloxy, ethoxylated, neopentyl) Alkoxy, stearyloxy, benzhydryloxy, p-methoxyphenylcarbonyloxy, etc.), amine group (amine group, methylamine) Base, dimethylamino, anilino, N-methyl-anilino, diphenylamino, etc.), mercaptoamino (carbomethylamino, ethionylamino, neopentylamino) , lauryl mercapto, benzhydrylamino, etc., alkyl and arylsulfonylamino (methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino) , 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino, etc., mercapto, alkylthio (methylthio, ethylthio, n-hexadecane) Sulfur-based, etc., arylthio (phenylthio, p-chlorophenylthio, m-methoxyphenylthio, etc.), aminesulfonyl (N-ethylaminesulfonyl, N-(3-ten) Dialkyloxypropyl)amine fluorenyl, N,N-dimethylamine sulfonyl, N-acetyl sulfonyl sulfonyl, N-benzamide sulfonyl, N-(N'phenyl Aminomethyl) sulfonyl, etc., sulfo, fluorenyl (ethyl fluorenyl, neopentyl benzoyl thiol, etc.), amine carbaryl (amine carbaryl, N-methylamine formazan) Base, N,N-dimethylaminecarbamyl, N,N-di-n-octylaminecarbamyl, N-(methylsulfonyl)amine, mercapto, etc.).
上述之取代基亦可進一步以上述之基來取代。 The above substituent may be further substituted with the above groups.
(I)在Wa及Wb相互鍵結而形成環的情況,該環較佳為含氮5員環或者含硫5員環。又,一般式(A),特佳係以下述一般式(1)或一般式(2)所表示之化合物。 (I) In the case where Wa and Wb are bonded to each other to form a ring, the ring is preferably a nitrogen-containing 5-membered ring or a sulfur-containing 5-membered ring. Further, the general formula (A) is particularly preferably a compound represented by the following general formula (1) or general formula (2).
於一般式(1)中,A1及A2係各自獨立表示-O-、-S-、-NRx-(Rx係表示氫原子或取代基)或者-CO-。以Rx所表示之取代基的例子係與以上述Wa及Wb所表示之取代基的具體例同義。作為Rx,較佳為氫原子、烷基、芳基、雜環基。 In the general formula (1), A 1 and A 2 each independently represent -O-, -S-, -NRx- (Rx represents a hydrogen atom or a substituent) or -CO-. Examples of the substituent represented by Rx are the same as the specific examples of the substituent represented by the above Wa and Wb. Rx is preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
於一般式(1)中,X係表示第14~16族之非金屬原子。作為X,較佳為=O、=S、=NRc、=C(Rd)Re。在此,Rc、Rd、Re係表示取代基,作為例子係與以上述Wa及Wb所表示之取代基的具體例同義。L1、L2、R1、R2、R3、n,係與一般式(A)中之L1、L2、R1、R2、R3、n同義。 In the general formula (1), the X system represents a non-metal atom of Groups 14 to 16. As X, it is preferably =O, =S, =NRc, and =C(Rd)Re. Here, Rc, Rd, and Re represent a substituent, and the examples are the same as the specific examples of the substituent represented by the above Wa and Wb. L 1, L 2, R 1 , R 2, R 3, n, and line (A) of the general formula L 1, L 2, R 1, R 2, R 3, n synonymous.
於一般式(2)中,Q1係表示-O-、-S-、-NRy-(Ry係表示氫原子或取代基)、-CRaRb-(Ra及Rb係表示氫原子或取代基)或者-CO-。在此,Ry、Ra、Rb係表示取代基,作為例子,係與以上述Wa及Wb所表示的取代基之具體例為同義。 In the general formula (2), Q 1 represents -O-, -S-, -NRy- (Ry represents a hydrogen atom or a substituent), -CRaRb- (Ra and Rb represent a hydrogen atom or a substituent) or -CO-. Here, Ry, Ra, and Rb represent a substituent, and as an example, they are synonymous with a specific example of the substituent represented by the above-mentioned Wa and Wb.
Y係表示取代基。作為以Y所表示之取代基的例子,係與以上述Wa以及Wb所表示之取代基的具體例同義。作為Y,較佳為芳基、雜環基、烯基、炔基。 The Y system represents a substituent. The example of the substituent represented by Y is synonymous with the specific example of the substituent represented by the above-mentioned Wa and Wb. Y is preferably an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group.
作為以Y所表示之芳基係可列舉:苯基、萘基、蒽基、菲基、聯苯基等,較佳為苯基、萘基,更佳為苯基。 The aryl group represented by Y may, for example, be a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group or a biphenyl group, and is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
作為雜環基係可列舉:呋喃基、吡咯基、噻吩基、吡啶基、噻唑基、苯并噻唑基等之至少包含一個氮原子、氧原子、硫原子等之雜原子的雜環基,較佳為呋喃基、吡咯基、噻吩基、吡啶基、噻唑基。 Examples of the heterocyclic group include a heterocyclic group containing at least one hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom, such as a furyl group, a pyrrolyl group, a thienyl group, a pyridyl group, a thiazolyl group or a benzothiazolyl group. Preferably, it is a furyl group, a pyrrolyl group, a thienyl group, a pyridyl group or a thiazolyl group.
此等之芳基或雜環基亦可具有至少一個取代 基。作為此取代基係可列舉:鹵素原子、碳數1~6之烷基、氰基、硝基、碳數1~6之烷基亞磺醯基、碳數1~6之烷基磺醯基、羧基、碳數1~6之氟烷基、碳數1~6之烷氧基、碳數1~6之烷硫基、碳數1~6之N-烷基胺基、碳數2~12之N,N-二烷基胺基、碳數1~6之N-烷基胺磺醯基、碳數2~12之N,N-二烷基胺磺醯基等。 These aryl or heterocyclic groups may also have at least one substitution base. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, and an alkylsulfonyl group having 1 to 6 carbon atoms. , carboxyl group, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, N-alkylamino group having 1 to 6 carbon atoms, carbon number 2~ 12 N,N-dialkylamino group, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, N,N-dialkylamine sulfonyl group having 2 to 12 carbon atoms, and the like.
L1、L2、R1、R2、R3、n,係與一般式(A)中之L1、L2、R1、R2、R3、n同義。 L 1, L 2, R 1 , R 2, R 3, n, and line (A) of the general formula L 1, L 2, R 1, R 2, R 3, n synonymous.
(II)於一般式(A)中,作為Wa及Wb之至少一個為具有環構造的情況時之具體例,較佳為下述一般式(3)。 (II) In the general formula (A), as a specific example in the case where at least one of Wa and Wb has a ring structure, the following general formula (3) is preferable.
於一般式(3)中,Q3係表示=N-或=CRz-(Rz係氫原子或取代基)、Q4係表示第14~16族之非金屬原子。Z係表示與Q3及Q4一起形成環之非金屬原子群。 In the general formula (3), Q 3 represents =N- or =CRz- (Rz-based hydrogen atom or a substituent), and Q 4 represents a non-metal atom of Groups 14 to 16. The Z system represents a non-metal atom group which forms a ring together with Q 3 and Q 4 .
由Q3、Q4及Z所形成之環,亦可進一步以另一環進行縮環。由Q3、Q4及Z所形成之環,較佳為以苯環縮環之含氮5員環或者6員環。 The ring formed by Q 3 , Q 4 and Z may be further condensed with another ring. The ring formed by Q 3 , Q 4 and Z is preferably a nitrogen-containing 5-membered ring or a 6-membered ring which is a benzene ring condensed ring.
L1、L2、R1、R2、R3、n,係與一般式(A)中之L1、L2、R1、R2、R3、n同義。 L 1, L 2, R 1 , R 2, R 3, n, and line (A) of the general formula L 1, L 2, R 1, R 2, R 3, n synonymous.
(III)在Wa及Wb之至少一個為烯基或炔基的情況,該等較佳係具有取代基之乙烯基或乙炔基。 (III) In the case where at least one of Wa and Wb is an alkenyl group or an alkynyl group, these are preferably a vinyl group or an ethynyl group having a substituent.
以上述一般式(1)、一般式(2)以及一般式(3)所表示之化合物當中,特佳係以一般式(3)所表示之化合物。 Among the compounds represented by the above general formula (1), general formula (2) and general formula (3), a compound represented by the general formula (3) is particularly preferred.
以一般式(3)所表示之化合物,相較於以一般式(1)所表示之化合物,其耐熱性及耐光性優異,相較於以一般式(2)所表示之化合物,其對於有機溶劑之溶解性或與聚合物之相溶性為良好。 The compound represented by the general formula (3) is superior in heat resistance and light resistance to the compound represented by the general formula (1), and is organic to the compound represented by the general formula (2). The solubility of the solvent or the compatibility with the polymer is good.
以一般式(A)所表示之化合物,係可為了賦予所期望之波長分散性以及防滲出性,而適當調整量來含有,但作為添加量,較佳係相對於纖維素衍生物,包含1~15質量%,尤其是以包含2~10質量%為佳。若為此範圍內,則可對上述纖維素衍生物賦予充分的波長分散性以及防滲出性。 The compound represented by the general formula (A) may be appropriately adjusted in order to impart desired wavelength dispersibility and anti-bleed property, but the amount of addition is preferably 1 with respect to the cellulose derivative. ~15% by mass, especially including 2 to 10% by mass. Within this range, sufficient cellulose dispersibility and anti-bleed property can be imparted to the above cellulose derivative.
另外,以一般式(A)、一般式(1)、一般式(2)及一般式(3)所表示的化合物,係可參照既知之方法來得到。具體而言係可參照Journal of Chemical Crystallography(1997);27(9);512-526)、日本特開2010- 31223號公報、日本特開2008-107767號公報等來進行合成。 Further, the compounds represented by the general formula (A), the general formula (1), the general formula (2), and the general formula (3) can be obtained by referring to a known method. Specifically, reference can be made to Journal of Chemical Crystallography (1997); 27 (9); 512-526), and Japanese Special Open 2010- The synthesis is carried out in the publication No. 31223 and JP-A-2008-107767.
本實施形態之纖維素醯化物薄膜係含有纖維素醯化物作為主成分。例如,本實施形態之纖維素醯化物薄膜,係相對於薄膜之全質量(100質量%),包含較佳為60~100質量%之範圍的纖維素醯化物。又,纖維素醯化物之總醯基取代度係2.0以上未達3.0,更佳為2.2~2.7。 The cellulose halide film of the present embodiment contains cellulose halide as a main component. For example, the cellulose halide film of the present embodiment contains a cellulose halide which is preferably in the range of 60 to 100% by mass based on the total mass (100% by mass) of the film. Further, the total thiol substitution degree of the cellulose oxime is less than 3.0, more preferably from 2.2 to 2.7.
作為纖維素醯化物係可列舉:纖維素與碳數2~22程度之脂肪族羧酸及/或芳香族羧酸的酯,尤其是以纖維素與碳數為6以下之低級脂肪酸的酯為佳。 Examples of the cellulose oxime compound include an ester of cellulose and an aliphatic carboxylic acid and/or an aromatic carboxylic acid having a carbon number of 2 to 22, and particularly an ester of cellulose and a lower fatty acid having a carbon number of 6 or less. good.
鍵結於纖維素之羥基的醯基係可為直鏈,亦可為分支,又,亦可形成環。進而,亦可以另一取代基進行取代。在相同取代度的情況,由於若上述之碳數為多,則雙折射性會降低,因此作為碳數較佳係在碳數2~6之醯基當中進行選擇,丙醯基取代度及丁醯基取代度之總和為0以上未達3.0。較佳係作為前述纖維素醯化物之碳數為2~4,更佳係碳數為2~3。 The thiol group bonded to the hydroxyl group of the cellulose may be a straight chain, a branch, or a ring. Further, it may be substituted with another substituent. In the case of the same degree of substitution, since the birefringence is lowered if the number of carbon atoms is large, the carbon number is preferably selected among the fluorenyl groups having 2 to 6 carbon atoms, and the degree of substitution of the fluorenyl group and the butyl group. The sum of the degrees of substitution is 0 or more and less than 3.0. Preferably, the cellulose halide has a carbon number of 2 to 4, more preferably 2 to 3.
具體而言,作為纖維素醯化物係如纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯、纖維素乙酸酯丙酸酯丁酸酯或纖維素乙酸酯鄰苯二甲酸酯般之乙醯基,此外可使用鍵結有丙酸酯基、丁酸酯基或鄰苯二甲醯基之纖維素的混合脂肪酸酯。另外,形成丁酸酯之丁醯基係可為直 鏈,亦可為分支。 Specifically, as a cellulose halide such as cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate or cellulose acetate phthalate An acid ester-like ethyl group, in addition, a mixed fatty acid ester in which a cellulose ester of a propionate group, a butyrate group or a phthalic acid group is bonded can be used. In addition, the butyrate group forming butyrate can be straight Chains can also be branches.
於本實施形態中,作為纖維素醯化物,特佳使用纖維素乙酸酯、纖維素乙酸酯丁酸酯、或纖維素乙酸酯丙酸酯。 In the present embodiment, cellulose acetate, cellulose acetate butyrate or cellulose acetate propionate is particularly preferably used as the cellulose halide.
又,上述之纖維素醯化物,較佳係同時滿足下述之數式(i)及數式(ii)者。 Further, the cellulose halide described above preferably satisfies the following formula (i) and formula (ii).
式(i) 2.0≦X+Y<3.0 Equation (i) 2.0≦X+Y<3.0
式(ii) 0≦X<3.0 Formula (ii) 0≦X<3.0
式中,Y係表示乙醯基之取代度,X係表示丙醯基或丁醯基或者其混合物之取代度。 In the formula, Y represents the degree of substitution of an ethyl group, and X represents the degree of substitution of a propyl group or a butyl group or a mixture thereof.
又,為了得到可達成目的之光學特性,亦可將取代度相異之樹脂進行混合使用。作為此時之混合比,較佳為1:99~99:1(質量比)。 Further, in order to obtain an optical property that can achieve the object, a resin having a different degree of substitution may be used in combination. The mixing ratio at this time is preferably 1:99 to 99:1 (mass ratio).
上述當中,尤其是較佳使用纖維素乙酸酯丙酸酯作為纖維素醯化物。於纖維素乙酸酯丙酸酯中,較佳為0≦Y≦2.5,且0.5≦X≦3.0(但,2.0≦X+Y<3.0),更佳為0.5≦Y≦2.0,且1.0≦X≦2.0(但,2.0≦X+Y<3.0)。另外,醯基之取代度係可依據ASTM(American Society for Testing and Materials;美國試驗材料協會)所策定/發行的規格之一的ASTM-D817-96進行測定。 Among the above, cellulose acetate propionate is particularly preferably used as the cellulose halide. In the cellulose acetate propionate, it is preferably 0≦Y≦2.5, and 0.5≦X≦3.0 (but, 2.0≦X+Y<3.0), more preferably 0.5≦Y≦2.0, and 1.0≦. X≦2.0 (but, 2.0≦X+Y<3.0). Further, the degree of substitution of the thiol group can be measured in accordance with ASTM-D817-96, one of the specifications specified/issued by ASTM (American Society for Testing and Materials).
若纖維素醯化物之數量平均分子量為60000~300000之範圍,則所得之薄膜的機械強度會增強,故為佳。更佳係使用數量平均分子量為70000~200000之纖維 素醯化物。 If the number average molecular weight of the cellulose halide is in the range of 60,000 to 300,000, the mechanical strength of the resulting film is enhanced, so that it is preferable. More preferably, the fiber having a number average molecular weight of 70,000 to 200,000 is used. Sputum.
纖維素醯化物之重量平均分子量(Mw)及數量平均分子量(Mn)係使用凝膠滲透層析法(GPC)所測定。測定條件係如以下所述。另外,本測定方法亦可作為於本實施形態中之其他的聚合物之測定方法來使用。 The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose halide are determined by gel permeation chromatography (GPC). The measurement conditions are as follows. Further, the measurement method can also be used as a method for measuring other polymers in the present embodiment.
溶劑:二氯甲烷;管柱:將Shodex K806、K805、K803G(昭和電工股份有限公司製)作3根連接來使用;管柱溫度:25℃;試料濃度:0.1質量%;檢測器:RI Model 504(GL SCIENCE公司製);泵:L6000(日立製作所股份有限公司製);流量:1.0ml/min Solvent: dichloromethane; column: Shodex K806, K805, K803G (manufactured by Showa Denko Co., Ltd.) was used as three connections; column temperature: 25 ° C; sample concentration: 0.1% by mass; detector: RI Model 504 (manufactured by GL SCIENCE); pump: L6000 (manufactured by Hitachi, Ltd.); flow rate: 1.0 ml/min
校正曲線:使用標準聚苯乙烯STK standard聚苯乙烯(TOSOH股份有限公司製)Mw=1000000~500之13個樣本所得之校正曲線。13個樣本係以略等間隔來使用。 Calibration curve: A calibration curve obtained using 13 samples of standard polystyrene STK standard polystyrene (manufactured by TOSOH Co., Ltd.) Mw = 1000000 to 500. Thirteen samples were used at slightly equal intervals.
纖維素醯化物中之殘留硫酸含量,較佳係以硫元素換算,為0.1~45質量ppm之範圍。可以推測到,此等係以鹽的形態而含有。若殘留硫酸含量超過45質量ppm,則在熱延伸時或熱延伸後之剪切(slitting)時會有變得容易破斷的傾向。另外,殘留硫酸含量,更佳係1~30質量ppm之範圍。殘留硫酸含量,係可藉由ASTM-D817-96所規定之方法來測定。 The residual sulfuric acid content in the cellulose halide is preferably in the range of 0.1 to 45 ppm by mass in terms of sulfur element. It is presumed that these are contained in the form of a salt. When the residual sulfuric acid content exceeds 45 ppm by mass, it tends to be easily broken during hot stretching or slapping after heat stretching. Further, the residual sulfuric acid content is more preferably in the range of 1 to 30 ppm by mass. The residual sulfuric acid content can be determined by the method specified in ASTM-D817-96.
又,纖維素醯化物中之游離酸含量較佳為1~ 500質量ppm。若為上述之範圍,則由於與上述相同地難以破斷,因此為佳。另外,游離酸含量,較佳係1~100質量ppm之範圍,而變得更難以破斷。尤其是以1~70質量ppm之範圍為佳。游離酸含量係可藉由ASTM-D817-96所規定之方法來測定。 Moreover, the free acid content in the cellulose halide is preferably 1~ 500 mass ppm. If it is the said range, since it is hard to break like the above, it is preferable. Further, the free acid content is preferably in the range of 1 to 100 ppm by mass, and becomes more difficult to break. In particular, it is preferably in the range of 1 to 70 ppm by mass. The free acid content can be determined by the method specified in ASTM-D817-96.
藉由充分進行合成後之纖維素醯化物的洗淨,而可將殘留硫酸含量及游離酸含量設為上述範圍,而為佳。 It is preferred that the residual sulfuric acid content and the free acid content are in the above range by sufficiently washing the cellulose halide after the synthesis.
作為纖維素醯化物之原料的纖維素雖無特別限定,但可列舉:棉短絨、木材紙漿、洋麻等。又,由該等所得之纖維素醯化物係可分別以任意之比例進行混合使用。 The cellulose which is a raw material of the cellulose oxime is not particularly limited, and examples thereof include cotton linters, wood pulp, and kenaf. Further, the cellulose halide obtained by the above may be used in combination at any ratio.
纖維素醯化物係可藉由周知之方法進行製造。具體而言,例如係可參照於日本特開平10-45804號公報所記載之方法來進行合成。 Cellulose telluride can be produced by a known method. Specifically, for example, the synthesis can be carried out by referring to the method described in JP-A-10-45804.
又,纖維素醯化物亦會因纖維素醯化物中之微量金屬成分而受到影響。此等之微量金屬成分,雖可推測到與在製造步驟中所使用的水有關連,但,可能成為不溶性之核的成分係越少越好。尤其,鐵、鈣、鎂等之金屬離子係有會藉由與具有包含有機之酸性基的可能性之聚合物分解物等進行鹽形成而形成不溶物的情況,故較少為佳。又,鈣(Ca)成分係與羧酸或磺酸等之酸性成分,又與大部分配位子容易形成配位化合物(亦即,錯合物),而有形成較多來自不溶的鈣之浮渣(不溶性之沉澱、混 濁)之虞,故較少為佳。 Moreover, cellulose halides are also affected by trace amounts of metal components in the cellulose halide. Although such a trace amount of a metal component is presumably related to the water used in the manufacturing process, the component which may become an insoluble core is as small as possible. In particular, metal ions such as iron, calcium, magnesium, and the like may be formed by salt formation with a polymer decomposition product or the like having an organic acid group, and it is less preferable. Further, the calcium (Ca) component is an acidic component such as a carboxylic acid or a sulfonic acid, and a complex compound (i.e., a complex compound) is easily formed with most of the ligands, and a large amount of calcium derived from insoluble calcium is formed. Slag (insoluble precipitation, mixing Less turbid, so less is better.
具體而言,關於鐵(Fe)成分,較佳係纖維素醯化物中之含量為1質量ppm以下。又,關於鈣(Ca)成分,纖維素醯化物中之含量較佳為60質量ppm以下,更佳為0~30質量ppm。再者,關於鎂(Mg)成分,由於若過多則會產生不溶物質,因此較佳係纖維素醯化物中之含量為0~70質量ppm,尤其是以0~20質量ppm為佳。 Specifically, the content of the iron (Fe) component is preferably 1 ppm by mass or less in the cellulose halide. Further, the content of the calcium (Ca) component in the cellulose halide is preferably 60 ppm by mass or less, more preferably 0 to 30 ppm by mass. Further, as for the magnesium (Mg) component, if it is too large, an insoluble matter is generated. Therefore, the content of the cellulose halide is preferably from 0 to 70 ppm by mass, particularly preferably from 0 to 20 ppm by mass.
另外,鐵(Fe)成分之含量、鈣(Ca)成分之含量、鎂(Mg)成分之含量等的金屬成分之含量,係可將絕乾之纖維素醯化物利用微波消化濕式分解裝置以硫硝酸進行分解,並以鹼熔融進行前處理,之後,使用ICP-AES(電感式耦合電漿發光分光分析裝置)來進行分析。 Further, the content of the metal component such as the content of the iron (Fe) component, the content of the calcium (Ca) component, and the content of the magnesium (Mg) component can be obtained by using a microwave digestion wet decomposition apparatus for the dried cellulose halide. Sulfuric acid was decomposed and pretreated by alkali fusion, and then analyzed by ICP-AES (inductively coupled plasma luminescence spectroscopic analyzer).
作為聚碳酸酯系樹脂係可無特別限定地使用各種類,就化學性質及物性的觀點而言,較佳為芳香族聚碳酸酯樹脂,尤其是以雙酚A系聚碳酸酯樹脂為佳。其中,更佳係使用於雙酚A導入有苯環、環己烷環、及脂肪族烴基等的雙酚A衍生物者。進而,特佳係使用對於雙酚A之中央的碳,非對稱地導入上述官能基的衍生物所得之使單位分子內之異向性減少的構造之聚碳酸酯樹脂。作為如此之聚碳酸酯樹脂,特佳係例如使用將雙酚A之中央的碳之2個甲基於苯環上作取代者、將雙酚A之各苯環的一個氫以甲 基或苯基等對於中央碳作非對稱地取代者所得之聚碳酸酯樹脂。 Various types of polycarbonate resin are used without particular limitation, and from the viewpoint of chemical properties and physical properties, an aromatic polycarbonate resin is preferable, and a bisphenol A-based polycarbonate resin is particularly preferable. Among them, those obtained by introducing a bisphenol A derivative such as a benzene ring, a cyclohexane ring, or an aliphatic hydrocarbon group into bisphenol A are more preferable. Further, a polycarbonate resin having a structure in which the anisotropy in a unit molecule is obtained by introducing a derivative of the above functional group asymmetrically into the carbon of the center of bisphenol A is particularly preferable. As such a polycarbonate resin, for example, two methyl groups of carbon in the center of bisphenol A are used as a substituent on the benzene ring, and one hydrogen of each benzene ring of bisphenol A is used as a A polycarbonate resin obtained by asymmetrically replacing a central carbon with a phenyl group or the like.
具體而言,由4,4’-二羥二苯基烷烴或者此等之鹵素取代體藉由光氣法或者酯交換法所得者,可列舉例如:4,4’-二羥二苯基甲烷、4,4’-二羥二苯基乙烷、4,4’-二羥二苯基丁烷等。又,除此之外,例如亦可列舉:於日本特開2006-215465號公報、日本特開2006-91836號公報、日本特開2005-121813號公報、日本特開2003-167121號公報、日本特開2009-126128號公報、日本特開2012-31369號公報、日本特開2012-67300號公報、國際公開第00/26705號等中所記載的聚碳酸酯系樹脂。 Specifically, those obtained by a phosgene method or a transesterification method from a 4,4'-dihydroxydiphenyl alkane or a halogen substituent thereof may, for example, be 4,4'-dihydroxydiphenylmethane. 4,4'-dihydroxydiphenylethane, 4,4'-dihydroxydiphenylbutane, and the like. In addition, Japanese Laid-Open Patent Publication No. 2006-215465, JP-A-2006-91836, JP-A-2005-121813, JP-A-2003-167121, and Japan A polycarbonate-based resin described in, for example, Japanese Laid-Open Patent Publication No. 2012-67300, No. 00-26705, and the like.
聚碳酸酯樹脂係可與聚苯乙烯系樹脂、甲基丙烯酸甲酯系樹脂、及纖維素乙酸酯系樹脂等之透明性樹脂進行混合來使用。又,亦可於使用纖維素乙酸酯系樹脂所形成之樹脂薄膜的至少其中一面,層合含有聚碳酸酯系樹脂之樹脂層。 The polycarbonate resin can be used by mixing with a transparent resin such as a polystyrene resin, a methyl methacrylate resin, or a cellulose acetate resin. Further, a resin layer containing a polycarbonate resin may be laminated on at least one of the resin films formed of the cellulose acetate resin.
聚碳酸酯系樹脂,較佳係玻璃轉移點(Tg)為110℃以上,且吸水率(在23℃水中,以24小時的條件所測定之值)為0.3%以下者。又,更佳係Tg為120℃以上,且吸水率為0.2%以下者。 The polycarbonate resin preferably has a glass transition point (Tg) of 110 ° C or higher and a water absorption ratio (a value measured under conditions of 24 hours in 23 ° C water) of 0.3% or less. Further, it is more preferable that the Tg is 120 ° C or more and the water absorption rate is 0.2% or less.
可在本實施形態使用的聚碳酸酯系樹脂薄膜,係可藉由周知之方法來製膜,其中,又以溶液流延法或熔融流延法為佳。 The polycarbonate resin film which can be used in the present embodiment can be formed into a film by a known method. Among them, a solution casting method or a melt casting method is preferred.
本實施形態之長條薄膜亦可包含添加劑。作為添加劑,係存在有可塑劑、紫外線吸收劑、遲滯調整劑、抗氧化劑、抗劣化劑、剝離助劑、界面活性劑、染料、微粒子等。於本實施形態中,關於微粒子以外的添加劑,係可在摻雜液之調製時作添加,亦可在微粒子分散液之調製時作添加。 The long film of this embodiment may also contain an additive. As the additive, there are a plasticizer, an ultraviolet absorber, a hysteresis adjuster, an antioxidant, an anti-deterioration agent, a peeling aid, a surfactant, a dye, a fine particle, and the like. In the present embodiment, the additives other than the fine particles may be added during the preparation of the doping liquid, or may be added during the preparation of the fine particle dispersion.
作為被添加於長條薄膜的可塑劑係可列舉:鄰苯二甲酸酯系、脂肪酸酯系、偏苯三甲酸酯系、磷酸酯系、聚酯系、糖酯系、丙烯酸系聚合物等。其中,就透濕性的觀點而言,可較佳使用聚酯系、及糖酯系聚合物之可塑劑。 Examples of the plasticizer to be added to the long film include a phthalate type, a fatty acid ester type, a trimellitate type, a phosphate type, a polyester type, a sugar ester type, and an acrylic polymer. Wait. Among them, from the viewpoint of moisture permeability, a plasticizer of a polyester-based or sugar-ester-based polymer can be preferably used.
聚酯系可塑劑,相較於鄰苯二甲酸二辛酯等之鄰苯二甲酸酯系之可塑劑,其非轉移性或耐萃取性更優異。藉由因應於用途來選擇或併用此等之可塑劑,而可適用於廣範圍之用途中。作為丙烯酸系聚合物,較佳為丙烯酸或甲基丙烯酸烷基酯之均聚物或者共聚物。作為丙烯酸酯之單體,係可列舉例如:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯(i-、n-)、丙烯酸丁酯(n-、i-、s-、t-)、丙烯酸戊酯(n-、i-、s-)、丙烯酸己酯(n-、i-)、丙烯酸庚酯(n-、i-)、丙烯酸辛酯(n-、i-)、丙烯酸壬酯(n-、i-)、丙烯酸十四酯(n-、i-)、丙烯酸(2-乙基己酯)、丙烯酸(ε-己內酯)、丙烯酸(2-羥乙酯)、丙烯 酸(2-羥丙酯)、丙烯酸(3-羥丙酯)、丙烯酸(4-羥丁酯)、丙烯酸(2-羥丁酯)、丙烯酸(2-甲氧乙酯)、丙烯酸(2-乙氧乙酯)等,或者將上述丙烯酸酯變更成甲基丙烯酸酯者。丙烯酸系聚合物雖為上述單體之均聚物或者共聚物,但較佳係具有丙烯酸甲基酯單體單位為30質量%以上,又,較佳係具有甲基丙烯酸甲酯單體單位為40質量%以上。尤其是以丙烯酸甲酯或者甲基丙烯酸甲酯之均聚物為佳。 The polyester-based plasticizer is superior in non-transferability or extraction resistance to a phthalate-based plasticizer such as dioctyl phthalate. It can be applied to a wide range of applications by selecting or using these plasticizers in accordance with the use. As the acrylic polymer, a homopolymer or a copolymer of acrylic acid or alkyl methacrylate is preferred. Examples of the acrylate monomer include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), and butyl acrylate. Ester (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), decyl acrylate (n -, i-), tetradecyl acrylate (n-, i-), acrylic acid (2-ethylhexyl ester), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl ester), propylene Acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), acrylic acid (2-methoxyethyl), acrylic acid (2- Ethyl ethoxylate or the like, or the above acrylate is changed to methacrylate. The acrylic polymer is a homopolymer or a copolymer of the above monomers, but preferably has a methyl acrylate monomer unit of 30% by mass or more, and more preferably has a methyl methacrylate monomer unit. 40% by mass or more. In particular, a homopolymer of methyl acrylate or methyl methacrylate is preferred.
聚酯系可塑劑雖為一價至四價之羧酸酸與一價至六價之醇的反應物,但主要使用使二價羧酸與二醇進行反應所得者。作為代表性的二價羧酸係可列舉:戊二酸、衣康酸、己二酸、鄰苯二甲酸、壬二酸、癸二酸等。又,聚酯系可塑劑較佳者係芳香族末端酯系可塑劑。作為芳香族末端酯系可塑劑,較佳係具有使鄰苯二甲酸、己二酸、至少一種的苯單羧酸及至少一種的碳數2~12之烷二醇進行反應的構造之酯化合物。只要具有己二酸殘基及鄰苯二甲酸殘基作為最終的化合物之構造即可,於製造酯化合物時,係可作為二羧酸之酸酐或酯化物進行反應。 The polyester-based plasticizer is a reactant of a monovalent to tetravalent carboxylic acid and a monovalent to hexavalent alcohol, but mainly obtained by reacting a divalent carboxylic acid with a diol. Typical examples of the divalent carboxylic acid include glutaric acid, itaconic acid, adipic acid, phthalic acid, sebacic acid, and sebacic acid. Further, the polyester-based plasticizer is preferably an aromatic terminal ester-based plasticizer. The aromatic terminal ester-based plasticizer preferably has an ester compound having a structure in which phthalic acid, adipic acid, at least one benzene monocarboxylic acid, and at least one carbon number 2 to 12 alkanediol are reacted. . As long as it has a structure in which an adipic acid residue and a phthalic acid residue are used as a final compound, when an ester compound is produced, it can be reacted as an acid anhydride or an esterified product of a dicarboxylic acid.
作為苯單羧酸成分,例如,存在有苯甲酸、對第三丁基苯甲酸、鄰甲苯甲酸、間甲苯甲酸、對甲苯甲酸、二甲基苯甲酸、乙基苯甲酸、正丙基苯甲酸、胺基苯甲酸、乙醯氧基苯甲酸等,最佳為苯甲酸。又,此等係可分別一種或者作為二種以上之混合物來使用。 As the benzene monocarboxylic acid component, for example, benzoic acid, p-tert-butylbenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid are present. Aminobenzoic acid, ethoxylated benzoic acid, etc., preferably benzoic acid. Further, these may be used alone or as a mixture of two or more.
作為碳數2~12之烷二醇成分係可列舉:乙 二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,2-丙二醇、2-甲基-1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、2,2-二甲基-1,3-丙二醇(新戊二醇)、2,2-二乙基-1,3-丙二醇(3,3-三羥甲基戊烷)、2-n-丁基-2-乙基-1,3-丙二醇(3,3-三羥甲基庚烷)、3-甲基-1,5-戊二醇、1,6-己二醇、2,2,4-三甲基-1,3-戊二醇、2-乙基-1,3-己二醇、2-甲基-1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,12-十八烷二醇等。此等當中,尤其是以1,2-丙二醇為佳。此等之二醇係可一種或者作為二種以上之混合物來使用。 Examples of the alkanediol component having 2 to 12 carbon atoms include: Glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1, 4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentylene glycol), 2,2-diethyl-1,3-propanediol (3, 3-trimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-trimethylolpheptane), 3-methyl-1,5-pentyl Glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8 - octanediol, 1,9-nonanediol, 1,10-nonanediol, 1,12-octadecanediol, and the like. Among these, especially 1,2-propanediol is preferred. These diols may be used singly or as a mixture of two or more.
芳香族末端酯系可塑劑係低聚酯(oligoester)、聚酯之形式中任一者皆可,分子量係以100~10000之範圍為佳,但較佳為350~3000之範圍。又,酸價為1.5mgKOH/g以下,羥(羥基)價為25mgKOH/g以下,較佳係酸價為0.5mgKOH/g以下、羥(羥基)價為15mgKOH/g以下者。 The aromatic terminal ester-based plasticizer may be in the form of an oligoester or a polyester, and the molecular weight is preferably in the range of 100 to 10,000, but preferably in the range of 350 to 3,000. Further, the acid value is 1.5 mgKOH/g or less, and the hydroxy (hydroxyl) value is 25 mgKOH/g or less, preferably the acid value is 0.5 mgKOH/g or less, and the hydroxy (hydroxyl) value is 15 mgKOH/g or less.
具體而言係可列舉以下所示之化合物等,但並不限定於此等。 Specific examples thereof include the compounds shown below, but are not limited thereto.
作為糖酯系化合物係纖維素酯以外之酯,將下述單糖、二糖、三糖或低聚糖等之糖的OH基之全部或一部分進行酯化後的化合物,作為更具體的例示係可列舉 以一般式(4)所表示之化合物等。 As an ester other than the cellulose ester of the sugar ester-based compound, a compound obtained by esterifying all or a part of the OH group of a sugar such as a monosaccharide, a disaccharide, a trisaccharide or an oligosaccharide is more specifically exemplified. Can be enumerated A compound represented by the general formula (4) or the like.
式中,R1~R8係表示氫原子、取代或無取代之碳數2~22之烷基羰基、或者取代或無取代之碳數2~22之芳基羰基。R1~R8係可為相同,亦可為相異。 In the formula, R 1 to R 8 represent a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group having 2 to 22 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 2 to 22 carbon atoms. The R 1 to R 8 systems may be the same or different.
以下,雖針對藉由一般式(4)所表示的化合物作具體性展示(化合物1-1~化合物1-23),但,並不限定於此等。另外,當在下表中而平均取代度為未達8.0的情況時,R1~R8中之其中一者係表示氫原子。 In the following, the compound represented by the general formula (4) is specifically shown (compound 1-1 to compound 1-23), but it is not limited thereto. Further, when the average degree of substitution in the following table is less than 8.0, one of R 1 to R 8 represents a hydrogen atom.
此等之可塑劑,較佳係相對於纖維素酯薄膜100質量份,添加0.5~30質量份者。 The plasticizer is preferably added in an amount of from 0.5 to 30 parts by mass based on 100 parts by mass of the cellulose ester film.
作為為了調整遲滯所添加的化合物,係可使用如歐洲專利911,656A2號說明書中所記載般之具有二個以上的芳香族環之芳香族化合物。 As the compound to be added to adjust the hysteresis, an aromatic compound having two or more aromatic rings as described in the specification of European Patent No. 911,656A2 can be used.
又,亦可併用二種以上的芳香族化合物。於該芳香族化合物之芳香族環,除了芳香族烴環以外,特佳係包含芳香族性雜環。芳香族性雜環一般為不飽和雜環。其中,特佳為1,3,5-三嗪環。 Further, two or more kinds of aromatic compounds may be used in combination. The aromatic ring of the aromatic compound preferably contains an aromatic hetero ring in addition to the aromatic hydrocarbon ring. The aromatic heterocyclic ring is generally an unsaturated heterocyclic ring. Among them, a 1,3,5-triazine ring is particularly preferred.
本實施形態之長條薄膜,較佳係含有纖維素酯、與具有由羧基、羥基、胺基、醯胺基、及磺酸基中選出的取代基,且重量平均分子量為500~200,000之範圍內的乙烯基系化合物之聚合物或者寡聚物。較佳係該纖維素酯與該聚合物或者寡聚物之含量的質量比為95:5~50:50之範圍內。 The long film of the present embodiment preferably contains a cellulose ester, and has a substituent selected from a carboxyl group, a hydroxyl group, an amine group, a guanamine group, and a sulfonic acid group, and has a weight average molecular weight of 500 to 200,000. A polymer or oligomer of a vinyl compound within. Preferably, the mass ratio of the cellulose ester to the polymer or oligomer is in the range of 95:5 to 50:50.
於本實施形態中,係可作為消光劑而於長條薄膜中含有微粒子,藉此,可使長條薄膜以及使用其所製造的長條傾斜配向薄膜之搬送或捲取變得容易進行。 In the present embodiment, fine particles can be contained in the long film as a matting agent, whereby the transport and winding of the long film and the long oblique alignment film produced using the long film can be easily performed.
消光劑之粒徑,較佳係10nm~0.1μm之1次粒子或2次粒子。1次粒子之針狀比為1.1以下的略球狀之消光劑係可較佳使用。 The particle size of the matting agent is preferably a primary particle or a secondary particle of 10 nm to 0.1 μm. A slightly spherical matting agent having a needle-like ratio of primary particles of 1.1 or less can be preferably used.
作為微粒子係以包含矽者為佳,特其是以二氧化矽為佳。作為於本實施形態中較佳之二氧化矽的微粒子,例如,可列舉:日本AEROSIL(股)製之以AEROSIL R972、R972V、R974、R812、200、200V、300、R202、OX50、TT600(以上為日本AEROSIL(股)製)的商品名稱作市售者,可較佳使用AEROSIL 200V、R972、R972V、R974、R202、R812。作為聚合物之微粒子的例子係可列舉:矽酮樹脂、氟樹脂及丙烯酸樹脂。較 佳為矽酮樹脂,尤其是以具有三維之網狀構造者為佳。作為如此之樹脂,例如,可列舉:TOSPEARL 103、同105、同108、同120、同145、同3120及同240(TOSHIBA SILICON(股)製)。 It is preferable that the fine particle system is contained, and it is preferably cerium oxide. Examples of the fine particles of ceria which are preferred in the present embodiment include AEROSIL R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 manufactured by Japan AEROSIL Co., Ltd. (the above is The trade name of Japan AEROSIL Co., Ltd. is commercially available, and AEROSIL 200V, R972, R972V, R974, R202, and R812 can be preferably used. Examples of the fine particles of the polymer include an anthrone resin, a fluororesin, and an acrylic resin. More Preferably, the fluorenone resin is preferably a three-dimensional network structure. Examples of such a resin include TOSPEARL 103, 105, 108, 120, 145, 3120, and 240 (TOSHIBA SILICON).
二氧化矽之微粒子,較佳係1次平均粒徑為20nm以下且表觀比重(apparent specific gravity)為70g/L以上者。更佳係1次粒子之平均直徑為5~16nm,再更佳係5~12nm。若1次粒子的平均直徑越小,則霧度越低,而為佳。表觀比重,較佳係90~200g/L以上,更佳係100~200g/L以上。若表觀比重越大,則成為能夠作出高濃度之微粒子分散液,並且不會產生霧狀物、凝聚物,而為佳。 The fine particles of cerium oxide are preferably those having a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g/L or more. More preferably, the average diameter of the primary particles is 5 to 16 nm, and more preferably 5 to 12 nm. If the average diameter of the primary particles is smaller, the haze is preferably lower. The apparent specific gravity is preferably 90 to 200 g/L or more, more preferably 100 to 200 g/L or more. When the apparent specific gravity is larger, it is preferable that a fine particle dispersion liquid having a high concentration can be produced without generating a mist or agglomerates.
於本實施形態中之消光劑的添加量,較佳係每1m2之長條薄膜中為0.01~1.0g,更佳係0.03~0.3g,再更佳係0.08~0.16g。 The amount of the matting agent to be added in the present embodiment is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, and still more preferably 0.08 to 0.16 g per 1 m 2 of the long film.
除此之外,亦可添加高嶺土、滑石、矽藻土、石英、碳酸鈣、硫酸鋇、氧化鈦、氧化鋁等之無機微粒子、鈣、鎂等之鹼土類金屬之鹽等的熱安定劑。進而,亦可添加界面活性劑、剝離促進劑、抗靜電劑、難燃劑、潤滑劑、油劑等。 In addition to this, a thermal stabilizer such as inorganic fine particles such as kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, or aluminum oxide, or a salt of an alkaline earth metal such as calcium or magnesium may be added. Further, a surfactant, a peeling accelerator, an antistatic agent, a flame retardant, a lubricant, an oil agent, or the like may be added.
對於本實施形態之長條薄膜,係要求能夠耐住在更高溫之環境下的使用。因此,長條薄膜之張力軟化點,由於若為105℃~145℃則展現充分的耐熱性,而為佳,尤其是以110℃~130℃為佳。 The long film of the present embodiment is required to be able to withstand use in a higher temperature environment. Therefore, the tensile softening point of the long film is preferably from 105 ° C to 145 ° C, and is preferably from 110 ° C to 130 ° C.
作為張力軟化點之具體的測定方法,例如,係可使用TENSILON試驗機(ORIENTEC公司製、RTC-1225A),並將試料薄膜切出120mm(縱)×10mm(寬幅),而一面以10N之張力作拉伸一面以30℃/min之昇溫速度來持續昇溫,而對於在成為9N之時點的溫度進行3次測定,再根據其之平均值來求出。 As a specific measurement method of the tension softening point, for example, a TENSILON tester (RTC-1225A, manufactured by ORIENTEC Co., Ltd.) can be used, and the sample film can be cut out to 120 mm (vertical) × 10 mm (wide), and one side can be 10 N. While the tension was stretched, the temperature was continuously raised at a temperature increase rate of 30 ° C/min, and the temperature at the time point of 9 N was measured three times, and the average value was obtained from the average value.
在將本實施形態之長條薄膜作傾斜延伸後的薄膜使用於有機EL畫像顯示裝置中的情況,為了避免起因於由吸濕導致的尺寸變化而發生像是厚度不均或相位差值之變化、及對比之降低或顏色不均之類的問題,傾斜延伸薄膜之尺寸變化率(%),較佳係未達0.5%,進而,更佳係未達0.3%。 In the case where the film in which the long film of the present embodiment is obliquely stretched is used in an organic EL image display device, changes in thickness or phase difference occur in order to avoid a change in size due to moisture absorption. And the problem of reduction in contrast or color unevenness, the dimensional change rate (%) of the obliquely stretched film is preferably less than 0.5%, and more preferably less than 0.3%.
本實施形態之長條薄膜,較佳係薄膜中之缺陷為少。在此,缺陷係指在溶液製膜之乾燥步驟中起因於溶劑之急遽的蒸發所發生的薄膜中之空洞(發泡缺陷),或起因於 製膜原液中之異物或在製膜中所混入之異物導致的薄膜中之異物(異物缺陷)。 In the long film of the present embodiment, it is preferred that the film has few defects. Here, the defect refers to a void (foaming defect) in the film which occurs due to rapid evaporation of the solvent in the drying step of the solution film formation, or is caused by Foreign matter (foreign matter defect) in the film caused by foreign matter in the film forming solution or foreign matter mixed in the film forming.
具體而言,較佳係薄膜面內之直徑5μm以上的缺陷為1個/10cm平方以下。更佳為0.5個/10cm平方以下,再更佳為0.1個/10cm平方以下。 Specifically, it is preferable that the defect having a diameter of 5 μm or more in the plane of the film is one/10 cm square or less. More preferably, it is 0.5 /10 cm square or less, and even more preferably 0.1 /10 cm square or less.
上述缺陷之直徑,當缺陷為圓形的情況係表示其之直徑,當非為圓形的情況係藉由下述方法來以顯微鏡作觀察而決定缺陷之範圍,並設為其之最大直徑(外接圓之直徑)。 The diameter of the above defect, when the defect is circular, indicates the diameter thereof. When it is not circular, the range of the defect is determined by the microscope as follows, and the maximum diameter is set ( The diameter of the circumscribed circle).
缺陷之範圍,當缺陷為氣泡或異物的情況係在對於缺陷藉由微分干涉顯微鏡之透射光來進行觀察時之陰影的大小。在缺陷為輥傷痕之轉印或擦傷等之表面形狀的變化之情況,係對於缺陷藉由微分干涉顯微鏡之反射光來進行觀察並確認大小。 The range of defects, when the defect is a bubble or foreign matter, is the size of the shadow when the defect is observed by the transmitted light of the differential interference microscope. In the case where the defect is a change in the surface shape such as transfer or scratch of the roller flaw, the defect is observed by the reflected light of the differential interference microscope and the size is confirmed.
另外,在藉由反射光來進行觀察的情況,若缺陷之大小不明瞭,則在表面上蒸鍍鋁或鉑來進行觀察。為了生產性佳地得到以該缺陷頻率所表示的品質為優良之薄膜,在即將流延之前對聚合物溶液進行高精確度之過濾、或將流延機周邊之清淨度提高、或者是對流延後之乾燥條件進行階段性設定而有效率且將發泡加以抑制地進行乾燥等的手段係為有效。 Further, in the case of observation by reflected light, if the size of the defect is unknown, aluminum or platinum is vapor-deposited on the surface for observation. In order to obtain a film excellent in quality represented by the frequency of the defect, the polymer solution is subjected to high-precision filtration immediately before casting, or the degree of cleanness of the periphery of the casting machine is increased, or casting is performed. The subsequent drying conditions are preferably set in a stepwise manner, and it is effective to dry and suppress the foaming.
若缺陷之個數比1個/10cm平方以下更多,則如果是例如在後續步驟中之加工時等對薄膜施加張力,便會有以缺陷作為基點而導致薄膜破斷,生產性降低的情 況。又,若缺陷之直徑成為5μm以上,則可藉由偏光板觀察等而以目視確認,在作為光學構件使用時,會有產生亮點的情況。 If the number of defects is more than one/10 cm square or less, if the tension is applied to the film, for example, during processing in a subsequent step, the film may be broken due to the defect, and the productivity may be lowered. condition. In addition, when the diameter of the defect is 5 μm or more, it can be visually confirmed by observation of a polarizing plate or the like, and when it is used as an optical member, a bright spot may be generated.
本實施形態之長條薄膜,較佳係其之全光線透射率為90%以上,更佳為93%以上。又,作為全光線透射率之現實性的上限係為99%左右。為了達成以該全光線透射率所表示之優異的透明性,構成為不導入會吸收可見光之添加劑或共聚合成分、或將聚合物中之異物藉由高精度過濾來去除,使薄膜內部之光的擴散或吸收減低等的手段係為有效。又,藉由將製膜時之薄膜接觸部(冷卻輥、壓光輥、滾筒、皮帶、於溶液製膜中之塗佈基材、搬送輥等)的表面粗度縮小而使薄膜表面之表面粗度變小以使薄膜表面之光的擴散或反射減低之手段亦為有效。 The long film of the present embodiment preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, the upper limit of the practicality of the total light transmittance is about 99%. In order to achieve excellent transparency represented by the total light transmittance, it is configured not to introduce an additive or a copolymerization component that absorbs visible light, or to remove foreign matter in the polymer by high-precision filtration to cause light inside the film. The means of diffusion or absorption reduction is effective. Further, the surface of the film surface is reduced by reducing the surface roughness of the film contact portion (the cooling roll, the calender roll, the roll, the belt, the coated substrate in the solution film formation, the transfer roll, etc.) at the time of film formation. A means for reducing the thickness to reduce the diffusion or reflection of light on the surface of the film is also effective.
包含上述之樹脂的本實施形態之長條薄膜,係可藉由以下所示之溶液流延製膜法或熔融流延製膜法之其中一者來製膜。另外,在此,雖針對長條薄膜為包含有纖維素酯系樹脂的情況來進行說明,但在包含其他之樹脂的情況亦相同。 The long film of the present embodiment containing the above resin can be formed by one of the solution casting film forming method or the melt casting film forming method described below. In addition, although the case where the long film is a cellulose ester type resin is demonstrated here, it is the same also in the case of containing other resin.
在藉由溶液流延製膜法來製造長條薄膜的情況,係將作為纖維素酯系樹脂的長條薄膜之原料溶液的摻 雜劑,藉由流延模來流延於由旋轉金屬製無端皮帶所成的支持體上。藉由流延而形成於支持體上之摻雜劑膜亦即帶(web),係於在支持體上作了約一周的循環時,藉由剝離輥而被剝離。被剝離的帶(薄膜),係被導入至由拉幅機所成的延伸裝置。 In the case of producing a long film by a solution casting film forming method, it is a blending of a raw material solution of a long film as a cellulose ester resin. The dopant is cast by a casting die on a support made of a rotating metal endless belt. The dopant film formed on the support by casting is a web which is peeled off by a peeling roll when it is cycled on the support for about one week. The strip (film) to be peeled off is introduced into an extension device formed by a tenter.
在藉由熔融流延製膜法來製造長條薄膜的情況,於使用有T模之押出方法中,係以能夠將聚合物熔融之溫度來進行熔融,並從T模來以薄膜狀(薄片狀)押出至冷卻筒上,並使其冷卻固化,再從冷卻筒將薄膜剝離。被剝離的薄膜,係被導入至由拉幅機所成的延伸裝置。 In the case of producing a long film by a melt casting film forming method, in the method of extruding a T-die, it is melted at a temperature at which the polymer can be melted, and is formed into a film shape from the T-die. The film is extruded onto a cooling cylinder and allowed to cool and solidify, and the film is peeled off from the cooling cylinder. The peeled film is introduced into an extension device formed by a tenter.
以下,針對各製膜法之詳細內容進行說明。 Hereinafter, the details of each film forming method will be described.
在由溶液流延製膜法所致之長條薄膜的製造方法中,作為纖維素酯溶液之摻雜劑的固體成分濃度,通常為10~40質量%左右,於流延步驟中之流延時的摻雜劑黏度,係被調製為1~200泊(poise)之範圍。 In the method for producing a long film by a solution casting film forming method, the solid content concentration of the dopant as the cellulose ester solution is usually about 10 to 40% by mass, and the flow delay in the casting step The dopant viscosity is modulated to a range of 1 to 200 poise.
在此,首先,纖維素酯之溶解,通常係使用在溶解釜中之攪拌溶解方法、加熱溶解方法、超音波溶解方法等的手段,又,為了防止被稱作凝膠或團塊(lump)之塊狀未溶解物的產生,更佳係採用在加壓下,加熱至溶劑之常壓時的沸點以上且不會使溶劑沸騰的範圍內之溫度並一面攪拌一面使其溶解之方法。又,亦可使用於日本特開平9-95538號公報中所記載之冷卻溶解方法,或者於日 本特開平11-21379號公報中所記載的於高壓下進行溶解之方法等。 Here, first, the dissolution of the cellulose ester is usually carried out by means of a stirring and dissolving method in a dissolution vessel, a heating and dissolving method, an ultrasonic dissolving method, and the like, and further, in order to prevent being called a gel or a lump. The production of the bulk undissolved material is more preferably a method in which the temperature is increased to a temperature within a range of a normal pressure of the solvent at a pressure lower than the boiling point of the solvent, and the mixture is stirred while being stirred. Further, it is also possible to use the cooling and dissolving method described in Japanese Laid-Open Patent Publication No. Hei 9-95538, or A method of dissolving at a high pressure as described in Japanese Laid-Open Patent Publication No. Hei 11-21379.
在將纖維素酯與不良溶劑進行混合而使其濕潤或者膨潤之後,進一步與良溶劑進行混合並使其溶解之方法亦可較佳使用。此時,亦可使將纖維素酯與不良溶劑進行混合並濕潤或者膨潤的裝置和與良溶劑進行混合並使其溶解之裝置相互獨立。 After the cellulose ester is mixed with a poor solvent to wet or swell, a method of further mixing with a good solvent and dissolving it is also preferably used. In this case, a device for mixing and wetting or swelling the cellulose ester with a poor solvent may be used independently of the device which is mixed with the good solvent and dissolved.
在纖維素酯之溶解中所使用的加壓容器之種類並無特別限定,只要是可耐住既定之壓力並可在加壓下進行加熱、攪拌即可。除此之外,在加壓容器中,係適當配設壓力計、溫度計等之計器類。加壓,亦可藉由將氮氣等之惰性氣體作壓入的方法,或藉由以加熱所致的溶劑之蒸氣壓的上升來進行。加熱,較佳係從外部來進行,例如夾套(jacket)型者,係由於溫度控制為容易,因此為佳。 The type of the pressurized container to be used for the dissolution of the cellulose ester is not particularly limited as long as it can withstand a predetermined pressure and can be heated and stirred under pressure. In addition, in the pressurized container, a gauge such as a pressure gauge or a thermometer is appropriately disposed. The pressurization may be carried out by a method of pressurizing an inert gas such as nitrogen or by raising the vapor pressure of the solvent by heating. The heating is preferably performed from the outside, and for example, a jacket type is preferable because temperature control is easy.
添加溶劑之加熱溫度,係所使用之溶劑的沸點以上,在2種以上之混合溶劑的情況,較佳係加溫至沸點為較低的溶劑之沸點以上的溫度且為不會使該溶劑沸騰的範圍之溫度。若加熱溫度過高,則所需要的壓力會變大,生產性係變差。較佳之加熱溫度的範圍為20~120℃,更佳為30~100℃,再更佳為40~80℃之範圍。又,壓力,係以在設定溫度下而不會使溶劑沸騰的方式來作調整。 The heating temperature of the solvent to be added is not less than the boiling point of the solvent to be used. In the case of two or more kinds of mixed solvents, it is preferred to heat the temperature to a temperature higher than the boiling point of the solvent having a lower boiling point and not to boil the solvent. The temperature of the range. If the heating temperature is too high, the required pressure will become large, and the productivity will be deteriorated. The preferred heating temperature ranges from 20 to 120 ° C, more preferably from 30 to 100 ° C, and even more preferably from 40 to 80 ° C. Further, the pressure is adjusted so as not to boil the solvent at a set temperature.
除了纖維素酯與溶劑之外,亦可將必要之可 塑劑、紫外線吸收劑等之添加劑預先與溶劑相混合而使其溶解或分散,之後投入至纖維素酯溶解前之溶劑中,或者是亦可投入至纖維素酯溶解後之摻雜劑中。 In addition to cellulose esters and solvents, it is also necessary The additive such as a plasticizer or an ultraviolet absorber is previously mixed with a solvent to be dissolved or dispersed, and then introduced into a solvent before dissolution of the cellulose ester, or may be added to a dopant after dissolution of the cellulose ester.
在纖維素酯之溶解後,係一面冷卻一面從容器中取出,或者是藉由泵等來從容器中抽出並藉由熱交換器等來進行冷卻,而供以進行所得到的纖維素酯之摻雜劑之製膜,但此時之冷卻,亦可進行直至常溫為止。 After the cellulose ester is dissolved, it is taken out from the container while being cooled, or is taken out from the container by a pump or the like and cooled by a heat exchanger or the like to supply the obtained cellulose ester. The film is formed by a dopant, but cooling at this time can also be carried out until normal temperature.
在將纖維素酯原料和溶劑之混合物藉由具有攪拌機之溶解裝置來溶解時,較佳係將攪拌翼之周速設為至少0.5m/秒以上,並且進行30分鐘以上的攪拌來溶解。 When the mixture of the cellulose ester raw material and the solvent is dissolved by a dissolving device having a stirrer, it is preferred to set the peripheral speed of the stirring blade to at least 0.5 m/sec or more, and to dissolve by stirring for 30 minutes or longer.
在纖維素酯摻雜劑中所包含的異物(特別是在液晶顯示裝置中會被誤認為畫像之異物),係必須要藉由對此摻雜劑進行過濾來去除。可以說作為光學薄膜之品質乃取決於此過濾。 The foreign matter contained in the cellulose ester dopant (especially a foreign matter which is mistaken for an image in a liquid crystal display device) must be removed by filtering the dopant. It can be said that the quality as an optical film depends on this filtration.
在過濾中所使用的濾材,係以絕對過濾精度為小者為佳,但若絕對過濾精度過小,則容易發生濾材的堵塞,而必須要頻繁地進行濾材的交換,故有著會使生產性降低的問題。因此,對於纖維素酯摻雜劑所使用的濾材,較佳係絕對過濾精度為0.008mm以下者,更佳係0.001~0.008mm之範圍,再更佳係0.003~0.006mm之範圍的濾材。 The filter medium used for the filtration is preferably one having a small absolute filtration accuracy. However, if the absolute filtration accuracy is too small, the filter material is likely to be clogged, and the filter material must be exchanged frequently, so that the productivity is lowered. The problem. Therefore, the filter medium used for the cellulose ester dopant is preferably a filter having an absolute filtration accuracy of 0.008 mm or less, more preferably 0.001 to 0.008 mm, and more preferably a range of 0.003 to 0.006 mm.
對於濾材之材質並無特別限制,可使用通常的濾材,但聚丙烯、TEFLON(註冊商標)等之塑膠纖維製的濾材或不鏽鋼纖維等金屬製的濾材係無纖維之脫落 等,而為佳。 The material of the filter material is not particularly limited, and a normal filter medium can be used. However, a filter material made of a plastic fiber such as polypropylene or TEFLON (registered trademark) or a metal filter material such as stainless steel fiber is free from fibers. Wait, and it is better.
纖維素酯摻雜劑之過濾係可使用通常的方法來進行,但以溶劑之常壓時的沸點以上且溶劑不會沸騰的範圍之溫度一面在加壓下進行加熱一面過濾的方法,係濾材前後之差壓(以下,有時記載為濾壓)的上昇為小,而為佳。 The filtration method of the cellulose ester dopant can be carried out by a usual method, but the method of filtering while heating under pressure at a temperature equal to or higher than the boiling point of the solvent at normal pressure and not boiling the solvent is a filter medium. The increase in the differential pressure (hereinafter, referred to as the filtration pressure) before and after is small, and is preferable.
較佳之過濾溫度的範圍為45~120℃,更佳為45~70℃,再更佳為45~55℃之範圍。 The preferred filtration temperature ranges from 45 to 120 ° C, more preferably from 45 to 70 ° C, and even more preferably from 45 to 55 ° C.
濾壓,較佳為3500kPa以下,更佳為3000kPa以下,再更佳為2500kPa以下。另外,濾壓係可藉由適當選擇過濾流量與過濾面積來進行控制。 The filtration pressure is preferably 3,500 kPa or less, more preferably 3,000 kPa or less, and still more preferably 2,500 kPa or less. In addition, the filtration system can be controlled by appropriately selecting the filtration flow rate and the filtration area.
為了製造纖維素酯系樹脂之長條薄膜,首先,將纖維素酯溶解在良溶劑以及不良溶劑之混合溶劑中,並於其中添加上述之可塑劑或紫外線吸收劑,而調製纖維素酯溶液(摻雜劑)。 In order to produce a long film of a cellulose ester resin, first, a cellulose ester solution is prepared by dissolving a cellulose ester in a mixed solvent of a good solvent and a poor solvent, and adding the above-mentioned plasticizer or ultraviolet absorber thereto. Doping).
摻雜劑,係能夠以支持體之溫度為一般的0℃~未達溶劑之沸點的範圍來流延於支持體上,進而,亦可以5℃~溶劑沸點-5℃之溫度範圍來流延於支持體上,但更佳係以5~30℃之溫度範圍來流延於支持體上。此時,周圍之環境溫度係有必要控制在露點以上。 The dopant can be cast on the support in a range of from 0 ° C to the boiling point of the solvent, and can also be cast in a temperature range of from 5 ° C to the boiling point of the solvent of -5 ° C. On the support, it is better to cast on the support at a temperature range of 5 to 30 °C. At this time, it is necessary to control the ambient temperature above the dew point.
又,將以使摻雜劑黏度成為1~200泊的方式調整後的摻雜劑,從流延模以在支持體上成為大致均一之膜厚的方式進行流延,並以使當流延膜中之殘留溶劑量相對於固體成分重量為200%以上時流延膜溫度會成為溶劑 沸點以下、並且當殘留溶劑量為200%以下~剝離為止時流延膜溫度會成為溶劑沸點+20℃以下之範圍的方式,來藉由乾燥風使流延膜(帶)進行乾燥。 Further, the dopant adjusted so that the dopant viscosity is 1 to 200 poise is cast from the casting die so as to have a substantially uniform film thickness on the support, so that the casting is performed. When the amount of residual solvent in the film is 200% or more based on the weight of the solid component, the cast film temperature becomes a solvent. The cast film (belt) is dried by a dry air when the amount of the residual solvent is 200% or less and the cast film temperature is in the range of the boiling point of the solvent + 20 ° C or less.
在此,殘留溶劑量係以下述之式來表示。 Here, the amount of residual solvent is expressed by the following formula.
殘留溶劑量(質量%)={(M-N)/N}×100 Residual solvent amount (% by mass) = {(M - N) / N} × 100
但,式中,M係帶之任意時點的重量,N係將重量M者以110℃來進行3小時乾燥後的重量。 However, in the formula, the weight of the M-belt at any time point, N is the weight of the weight M after drying at 110 ° C for 3 hours.
在支持體上,為了使帶被乾燥固化直至成為能夠從支持體剝離的膜強度為止,較佳係進行乾燥直至帶中之殘留溶劑量為150質量%以下,更佳係乾燥至50~120%。 In the support, in order to allow the tape to be dried and solidified until it is capable of being peeled off from the support, it is preferred to dry until the amount of residual solvent in the tape is 150% by mass or less, more preferably 50 to 120%. .
從支持體將帶剝離時的帶溫度較佳為0~30℃。又,由於帶係會在剛被從支持體剝離之後,起因於從支持體密著面側所發生之溶劑蒸發而導致溫度暫時急遽降低,環境中之水蒸氣或溶劑蒸氣等之揮發性成分係容易凝結,因此,剝離時之帶溫度為5~30℃係更佳。 The tape temperature at which the tape is peeled off from the support is preferably 0 to 30 °C. Further, since the tape is immediately peeled off from the support, the temperature is temporarily lowered rapidly due to evaporation of the solvent generated from the side of the support surface, and the volatile components such as water vapor or solvent vapor in the environment are It is easy to coagulate, so the strip temperature at the time of peeling is preferably 5 to 30 ° C.
在帶(或者薄膜)之乾燥步驟中,一般係採用輥懸吊方式、或一面藉由針梳拉幅方式或者鋏帶拉幅方式來搬送帶一面進行乾燥的方式。 In the drying step of the belt (or film), the belt is usually suspended by a roll suspension method or by a needle comb drawing method or a belt tenter method.
剝離後之帶,例如係被導入至一次乾燥裝置中。在一次乾燥裝置內,係藉由在從側面作觀察時被配置為交錯狀的複數之搬送輥來使帶被蛇行搬送,於此期間中,帶係藉由從乾燥裝置之頂板所吹入並從乾燥裝置之底部所排出的溫風而進行乾燥。 The strip after peeling is, for example, introduced into a primary drying device. In a primary drying apparatus, the belt is serpentinely conveyed by a plurality of conveying rollers arranged in a staggered manner when viewed from the side, during which the belt is blown from the top plate of the drying device. The air is dried by the warm air discharged from the bottom of the drying device.
接著,將所得到的薄膜(薄片)朝向單軸方向作延伸。藉由延伸,分子係被配向。進行延伸之方法並無特別限制,但係可較佳使用周知之針梳拉幅機或鋏帶式之拉幅機等。延伸方向,係可為長度方向,亦可為寬度方向,亦可為任意之方向(傾斜方向),但藉由將延伸方向設為寬度方向,而容易調整長條薄膜之破斷伸度(Breaking elongation),而為佳。 Next, the obtained film (sheet) is extended in a uniaxial direction. By extension, the molecular system is aligned. The method of performing the stretching is not particularly limited, but a well-known needle comber or a tenter type tenter or the like can be preferably used. The extending direction may be the length direction, the width direction, or any direction (inclination direction), but it is easy to adjust the breaking elongation of the long film by setting the extending direction to the width direction (Breaking) Elongation), and better.
尤其,在被從支持體剝離後之乾燥步驟中,起因於溶劑之蒸發,帶係會有在寬度方向上收縮的傾向。若以越高的溫度來進行乾燥,則收縮會變得越大。在使完成的薄膜之平面性成為良好的觀點上,較佳係一面盡可能地對此收縮作抑制一面進行乾燥。基於此觀點,例如,較佳係如於日本特開昭62-46625號公報中所揭示般之於全部之乾燥步驟或者一部分的乾燥步驟中一面在寬度方向上藉由夾鉗來將帶之寬幅兩端作寬幅保持一面使其乾燥之方法(拉幅方式)。 In particular, in the drying step after being peeled off from the support, the belt tends to shrink in the width direction due to evaporation of the solvent. If the drying is performed at a higher temperature, the shrinkage becomes larger. From the viewpoint of improving the planarity of the completed film, it is preferred to perform drying while suppressing the shrinkage as much as possible. Based on this point of view, for example, it is preferable to use a clamp to widen the width in the width direction of all the drying steps or a part of the drying step as disclosed in Japanese Laid-Open Patent Publication No. 62-46625 A method of maintaining the width at both ends of the web to make it dry (triangular manner).
作為長條薄膜之延伸條件,係能夠以可得到所期望之破斷伸度特性的方式來選擇溫度、倍率。通常,延伸倍率為1.1~2.0倍,較佳為1.2~1.5倍,延伸溫度,通常係被設定在構成薄片之樹脂的玻璃轉移溫度(Tg)-40℃~Tg+50℃,較佳係設定在Tg-40℃~Tg+40℃之溫度範圍內。若延伸倍率過小,則會有無法得到所期望之破斷伸度特性的情況,相反地若過大,則會有發生破斷的情況。若延伸溫度過低,則會有發生破斷的情況, 又,若過高,則會有無法得到所期望之破斷伸度特性的情況。 As a condition for extending the long film, the temperature and the magnification can be selected in such a manner that the desired breaking elongation characteristics can be obtained. Usually, the stretching ratio is 1.1 to 2.0 times, preferably 1.2 to 1.5 times, and the stretching temperature is usually set at a glass transition temperature (Tg) of -40 ° C to Tg + 50 ° C of the resin constituting the sheet, preferably set. In the temperature range of Tg-40 ° C ~ Tg + 40 ° C. If the stretching ratio is too small, the desired breaking elongation characteristics may not be obtained. Conversely, if the stretching ratio is too large, the breaking may occur. If the extension temperature is too low, there will be a breakage. Moreover, if it is too high, the desired breaking elongation characteristic may not be obtained.
在將藉由上述之方法所製作的熱塑性樹脂薄膜之破斷伸度特性修正為配合目的之所期望的特性的情況,亦可使薄膜在長度方向或寬度方向上作延伸或收縮。為了在長度方向上使其收縮,例如,存在有藉由將寬幅延伸作暫時性的鬆鋏而使其於長度方向上鬆弛之方法,或者是將橫延伸裝置之相鄰的鋏之間隔逐漸縮窄來使薄膜收縮之方法。後者之方法,係可藉由使用一般之同時雙軸延伸裝置,將縱方向之相鄰的鋏之間隔例如藉由縮放(pantograph)方式或者是線性驅動方式來驅動鋏部分並使其順暢地逐漸縮窄的方法而進行。 When the breaking elongation characteristic of the thermoplastic resin film produced by the above method is corrected to a desired property for the purpose of blending, the film may be stretched or shrunk in the longitudinal direction or the width direction. In order to shrink it in the longitudinal direction, for example, there is a method of relaxing the lengthwise direction by extending the wide width as a temporary looseness, or gradually spacing the adjacent turns of the lateral stretching device. A method of narrowing to shrink the film. In the latter method, the 铗 portion can be driven and gradually smoothed, for example, by a pantograph method or a linear driving method by using a general simultaneous biaxial stretching device. The method of narrowing is carried out.
拉幅機之把持、延伸係可在剛被剝離後之膜的殘留溶劑量為50~150質量%正要被捲取前之實質的殘留溶劑量為0質量%之範圍內的任意處來進行,但以在殘留溶劑量為5~10%之範圍內來進行為佳。 The holding and stretching of the tenter can be carried out at any position within a range of 50 to 150% by mass of the film immediately after being peeled off, and the amount of residual solvent before being wound up is 0% by mass. However, it is preferably carried out in the range of 5 to 10% of the residual solvent.
亦一般性地進行將拉幅機在基材的前進方向上區分成數個溫度區域。進行延伸時之溫度,係選擇能夠得到所期望之物性或平面性的溫度,但拉幅機前後之乾燥區域的溫度也因各種之理由而選擇與進行延伸時之溫度不同的溫度。例如,當拉幅機前之乾燥區域的環境溫度與拉幅機內之溫度不同的情況,一般係進行將拉幅機入口附近之區域的溫度設定為拉幅機前之乾燥區域之溫度與拉幅機中央部之溫度的中間性之溫度。針對拉幅機後與拉幅機內 之溫度為不同的情況,亦同樣地將拉幅機出口附近之區域的溫度設定為拉幅機後與拉幅機內之溫度的中間性之溫度。拉幅機前後之乾燥區域的溫度,一般為30~120℃,較佳為50~100℃,拉幅機內延伸部之溫度為50~180℃,較佳為80~170℃,拉幅機入口部或出口部之溫度係由該等溫度的中間性之溫度適當選擇。 The tenter is also generally divided into a plurality of temperature zones in the advancing direction of the substrate. The temperature at the time of stretching is selected to obtain a desired physical property or planarity. However, the temperature of the drying zone before and after the tenter is selected to have a temperature different from the temperature at which the stretching is performed for various reasons. For example, when the ambient temperature in the drying zone before the tenter is different from the temperature in the tenter, the temperature of the region near the entrance of the tenter is generally set to the temperature and the temperature of the drying zone before the tenter. The temperature of the intermediate temperature of the central part of the web. For the tenter and the inside of the tenter The temperature is different, and the temperature in the region near the exit of the tenter is similarly set to the temperature between the tenter and the temperature in the tenter. The temperature of the drying zone before and after the tenter is generally 30~120 °C, preferably 50~100 °C, and the temperature of the extension part of the tenter is 50~180 °C, preferably 80~170 °C, tenter The temperature at the inlet or outlet is suitably selected by the intermediate temperature of the temperatures.
延伸之形態,亦即把持鋏之軌跡,係與溫度相同地,基於膜之光學物性或平面性來作選擇,而有各種形態,但多使用在把持之開始後暫時維持於一定之寬幅,之後被延伸,並在延伸結束後再度以一定之寬幅而被保持的形態。在拉幅機出口附近之鋏把持結束的附近處,為了對起因於將把持作開放一事所導致的基材振動作抑制,一般係進行寬幅之舒緩。 The form of extension, that is, the trajectory of holding the cymbal, is selected based on the optical properties or planarity of the film, and has various forms, but the multi-use is temporarily maintained at a certain width after the start of the control. It is then stretched and held in a certain width after the end of the extension. In the vicinity of the end of the gripper exit near the exit of the tenter, in order to suppress the vibration of the substrate caused by the opening of the gripper, the width is generally relieved.
雖然延伸之形態係以與延伸速度有所關連,但延伸速度,一般而言為10~1000(%/min),較佳為100~500(%/min)。此延伸速度,在鋏之軌跡為曲線的情況時並非為一定,而會在基材之前進方向上逐漸變化。 Although the extended form is related to the extension speed, the extension speed is generally 10 to 1000 (%/min), preferably 100 to 500 (%/min). This extension speed is not constant when the trajectory of the ridge is a curve, but gradually changes in the direction before the substrate.
進而,由上述之拉幅方式所得到的乾燥後之帶(薄膜),係接著被導入至二次乾燥裝置。在二次乾燥裝置內,係藉由在從側面觀察時被配置為交錯狀的複數之搬送輥來使帶被蛇行搬送,於此期間中,帶係藉由從二次乾燥裝置之頂板所吹入並從二次乾燥裝置之底部所排出的溫風而進行乾燥,並作為纖維素酯系樹脂之長條薄膜而被捲取機所捲取。 Further, the dried belt (film) obtained by the tenter method described above is then introduced into a secondary drying apparatus. In the secondary drying apparatus, the belt is serpentine conveyed by a plurality of conveying rollers arranged in a staggered shape when viewed from the side, and during this period, the belt is blown from the top plate of the secondary drying device. The mixture was dried by a warm air discharged from the bottom of the secondary drying device, and taken up by a coiler as a long film of a cellulose ester resin.
使帶乾燥之手段並無特別限制,而使用一般之熱風、紅外線、加熱輥、微波等。就簡便性的觀點係以藉由熱風來進行乾燥為佳。乾燥溫度,較佳為40~150℃,就使平面性、尺寸安定性改善的觀點,更佳為80~130℃。 The means for drying the belt is not particularly limited, and general hot air, infrared rays, heating rolls, microwaves, and the like are used. The viewpoint of simplicity is preferably drying by hot air. The drying temperature is preferably from 40 to 150 ° C, and the viewpoint of improving planarity and dimensional stability is more preferably 80 to 130 ° C.
如此般,在帶之乾燥步驟中,係將從支持體剝離的帶進一步乾燥,最終,使殘留溶劑量成為3質量%以下,較佳為1質量%以下,更佳為0.5質量%以下者,係就得到尺寸安定性為良好之薄膜的觀點而言為佳。 In the drying step of the belt, the belt which is peeled off from the support is further dried, and finally, the amount of the residual solvent is 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less. It is preferable from the viewpoint of obtaining a film having a good dimensional stability.
此等之從流延起直到後續乾燥為止的步驟,係可在空氣環境下進行,亦可在氮氣等之惰性氣體環境下進行。於此情況,當然是考慮溶劑之爆發臨界濃度,來實施乾燥環境。 The steps from the casting to the subsequent drying may be carried out in an air atmosphere or in an inert gas atmosphere such as nitrogen. In this case, of course, the critical concentration of the outbreak of the solvent is considered to carry out the drying environment.
另外,較佳為,對於結束搬送乾燥步驟之纖維素酯系樹脂之長條薄膜,於導入至捲取步驟的前段處,藉由壓花加工裝置,來進行在纖維素酯系樹脂之長條薄膜的兩側緣部形成壓花之加工。作為壓花加工裝置,例如係可利用於日本特開昭63-74850號公報中所記載之裝置。 Further, it is preferable that the long film of the cellulose ester-based resin which has been subjected to the transport drying step is subjected to a strip of the cellulose ester resin by the embossing apparatus at the front stage of the introduction to the winding step. The embossing is formed on both side edges of the film. The embossing processing apparatus can be used, for example, in the apparatus described in Japanese Laid-Open Patent Publication No. S63-74850.
關於在纖維素酯系樹脂之長條薄膜的製造中之捲取機係可為一般所使用者,可藉由定張力法、定轉矩法、錐度張力(Taper tension)法、內部應力為一定之程式張力控制法等的捲取方法來進行捲取。 The coiler in the manufacture of the long film of the cellulose ester resin can be used by a general user, and can be fixed by a constant tension method, a constant torque method, a taper tension method, and an internal stress. The winding method such as the program tension control method performs the winding.
捲取後之長條薄膜的膜厚,係依據使用目的而異,但膜厚範圍為20~200μm,以最近之薄型化傾向 而言,係以30~120μm之範圍為佳,尤其是以40~100μm之範圍為佳。 The film thickness of the long film after winding is different depending on the purpose of use, but the film thickness ranges from 20 to 200 μm, and the recent thinning tendency In particular, it is preferably in the range of 30 to 120 μm, particularly preferably in the range of 40 to 100 μm.
作為熔融流延製膜法,係存在著使用有T模之方法或膨脹法等之熔融押出法、壓延(calendaring)法、熱衝壓法、射出成形法等。其中,係以能夠使厚度參差縮小,容易加工為50~500μm左右之厚度,且能夠使膜厚參差或遲滯之參差縮小之使用T模的方法為佳。使用T模之押出方法,係以能夠將聚合物熔融之溫度來進行熔融,從T模來以薄膜狀(薄片狀)押出至冷卻筒上,並使其冷卻固化,再從冷卻筒剝離之方法,所得到之薄膜的厚度精確度優異,而可較佳使用。 As the melt casting film forming method, there are a melt extrusion method, a calendaring method, a hot stamping method, an injection molding method, and the like using a method using a T-die or an expansion method. Among them, a method in which the thickness variation is reduced, the thickness is easily processed to a thickness of about 50 to 500 μm, and the T-die can be reduced in which the thickness difference or the hysteresis is reduced. The T-die extrusion method is a method in which a polymer can be melted at a temperature at which the polymer is melted, and is extruded from a T-die into a cooling cylinder in a film form (sheet shape), cooled and solidified, and then peeled off from the cooling cylinder. The obtained film is excellent in thickness precision and can be preferably used.
熔融押出,係可藉由與在其他之聚酯等之熱塑性樹脂中所使用的條件相同之條件來進行。例如,係可將在熱風或真空或者減壓下乾燥後的纖維素酯,使用單軸或2軸型之押出機,以押出溫度200~300℃左右進行熔融,並藉由葉片圓盤型之濾網等來進行過濾而將異物去除,之後,從T模來流延為薄膜狀(薄片狀),並在冷卻筒上使其固化。在從供給斗而導入至押出機時,較佳係設為減壓下或惰性氣體環境下,以防止氧化分解等。 The melt extrusion can be carried out under the same conditions as those used in thermoplastic resins such as other polyesters. For example, the cellulose ester which has been dried under hot air or under vacuum or under reduced pressure can be melted by using a uniaxial or 2-axis type extruder at a temperature of about 200 to 300 ° C, and is formed by a blade disc type. The filter or the like is filtered to remove the foreign matter, and then cast from a T-die into a film shape (flaky shape) and solidified on a cooling cylinder. When it is introduced from the supply hopper to the extruder, it is preferable to prevent oxidative decomposition or the like under a reduced pressure or an inert gas atmosphere.
押出流量,較佳係構成為導入齒輪泵等來安定地進行。又,作為在異物之去除中所使用的濾網,係可較佳使用不鏽鋼纖維燒結濾網。不鏽鋼纖維燒結濾網,係 在作出使不鏽鋼纖維體複雜地交絡的狀態之後,進行壓縮並對於接觸部位進行燒結而一體化者,可藉由該纖維之粗細與壓縮量來改變密度,並對於過濾精度作調整。較佳係設為將過濾精度疏、密連續性地複數次重複的多層體。又,藉由採用使過濾精度逐漸提高之構成,或採用使過濾精度之疏、密重複的方法,由於係能夠延長濾網之過濾壽命,並且也能夠將異物或凝膠等之捕捉精度提昇,因此為佳。 The discharge flow rate is preferably configured to be carried out stably by introducing a gear pump or the like. Further, as the screen used for the removal of the foreign matter, a stainless steel fiber sintered sieve can be preferably used. Stainless steel fiber sintered filter After the stainless steel fiber body is in a state of being complicatedly entangled, and compression is performed and the contact portion is sintered and integrated, the density can be changed by the thickness and compression amount of the fiber, and the filtration precision can be adjusted. It is preferable to use a multilayer body in which filtration precision is repeated and densely repeated plural times. In addition, by adopting a configuration in which the filtration accuracy is gradually increased, or a method in which the filtration accuracy is repeated and densely repeated, the filtration life of the filter can be extended, and the capturing accuracy of foreign matter, gel, or the like can be improved. Therefore it is better.
若在模處產生有傷痕或異物附著,則會有發生筋狀之缺陷的情況。如此之缺陷係被稱為模線,為了使模線等之表面的缺陷縮小,較佳為,從押出機起至模的配管,係設為將樹脂之滯留部盡可能地減少的構造。又,較佳係使用在模之內部或唇部盡可能不存在有傷痕者。由於會有從樹脂而在模周邊析出揮發性成分並成為模線之發生之原因的情況,因此較佳係將包含揮發性成分之環境作吸引。又,由於在施加靜電等之裝置也會有發生析出的情況,因此較佳係施加交流電流或藉由其他之加熱手段來防止析出。 If there is a flaw or a foreign matter adhering to the mold, there is a case where a rib-like defect occurs. Such a defect is called a mold line, and in order to reduce the defects on the surface of the mold line or the like, it is preferable that the piping from the extruder to the mold is configured to reduce the retention portion of the resin as much as possible. Further, it is preferred to use as much as possible that there is no scratch in the interior of the mold or in the lip. Since a volatile component is precipitated from the resin and formed as a mold line in the periphery of the mold, it is preferable to attract the environment containing the volatile component. Further, since precipitation occurs in a device that applies static electricity or the like, it is preferable to apply an alternating current or to prevent precipitation by another heating means.
可塑劑等之添加劑係可預先與樹脂進行混合,亦可在押出機之途中混入。為了均勻地進行添加,係以使用靜態混合器等之混合裝置為佳。 The additive such as a plasticizer may be mixed with the resin in advance or may be mixed in the middle of the extruder. In order to carry out the addition uniformly, it is preferred to use a mixing device such as a static mixer.
冷卻筒之溫度,較佳係熱塑性樹脂之玻璃轉移溫度以下。為了使樹脂密著於冷卻筒上,較佳係使用藉由施加靜電來使其密著之方法、藉由風壓來使其密著之方 法、對於全寬幅或端部進行捏夾來使其密著之方法、藉由減壓來使其密著之方法等。 The temperature of the cooling cylinder is preferably below the glass transition temperature of the thermoplastic resin. In order to adhere the resin to the cooling cylinder, it is preferable to use a method in which it is adhered by applying static electricity, and it is adhered by wind pressure. A method of squeezing a full width or an end portion to make it dense, a method of adhering it by decompression, and the like.
藉由如此之熔融流延製膜法所成形的熱塑性樹脂之長條薄膜,係與藉由溶液流延製膜法所成形之長條薄膜不同,而具有厚度方向遲滯(Rt)為小之特徵,並且也會有成為需要採用與溶液流延製膜法不同之延伸條件的情況。為了得到所期望的光學物性,視情況,也會有將薄膜之前進方向的延伸與薄膜寬度方向的延伸之雙方同時進行或者是逐次進行的情況。又,視情況,也會有僅進行薄膜之寬度方向之延伸的情況。藉由此延伸操作,分子係被配向,薄膜係被調整為所需要的遲滯值。 The long film of the thermoplastic resin formed by the melt casting film forming method is different from the long film formed by the solution casting film forming method, and has a characteristic that the thickness direction retardation (Rt) is small. There is also a case where it is necessary to adopt an extension condition different from the solution casting film forming method. In order to obtain desired optical properties, depending on the case, both the extension of the film in the forward direction and the extension in the film width direction may be performed simultaneously or sequentially. Further, depending on the case, there may be cases where only the width direction of the film is extended. By this extension operation, the molecular system is aligned and the film is adjusted to the desired hysteresis value.
本實施形態之長條薄膜,在藉由熔融流延製膜法而製造的情況,作為能夠使用的紫外線吸收劑,係可使用與在由前述之溶液流延製膜法所致之長條薄膜的製造方法中所使用者大致相同者。 In the case where the long film of the present embodiment is produced by a melt casting film forming method, as the usable ultraviolet absorber, a long film which is formed by the above-described solution casting film forming method can be used. The user of the manufacturing method is substantially the same.
此等之紫外線吸收劑的摻合量,較佳係相對於熱塑性樹脂,為0.01~10質量%之範圍,進而以0.1~5質量%為佳。若使用量過少,則會有紫外線吸收效果並不充分的情況,相反地若過多,則會有薄膜之透明性劣化的情況。紫外線吸收劑較佳係熱安定性為高者。 The blending amount of the ultraviolet absorber is preferably in the range of 0.01 to 10% by mass based on the thermoplastic resin, and more preferably 0.1 to 5% by mass. If the amount used is too small, the ultraviolet absorbing effect may be insufficient. On the other hand, if the amount is too large, the transparency of the film may be deteriorated. The ultraviolet absorber is preferably one having a high thermal stability.
於長條薄膜中,較佳係添加用以賦予薄膜之潤滑性的微粒子。作為所使用的微粒子,只要是具有熔融時之耐熱性,則不論是無機化合物或者有機化合物之何者均可,例如,作為無機化合物,較佳係包含矽之化合物、 二氧化矽、氧化鋁、氧化鋯、碳酸鈣、滑石、黏土、燒成高嶺土、燒成矽酸鈣、水合矽酸鈣、矽酸鋁、矽酸鎂及磷酸鈣等,更佳係包含矽之無機化合物或氧化鋯。其中,就可將霧度抑制為小之觀點而言,係以使用二氧化矽為特別理想。在將長條薄膜藉由熔融流延製膜法而製造的情況,作為所使用的消光劑,亦可使用與在由前述之溶液流延製膜法所致之長條薄膜的製造方法中所使用者大致相同者。 In the long film, fine particles for imparting lubricity to the film are preferably added. The fine particles to be used may be any of an inorganic compound or an organic compound as long as it has heat resistance at the time of melting. For example, as the inorganic compound, a compound containing ruthenium is preferable. Ceria, alumina, zirconia, calcium carbonate, talc, clay, calcined kaolin, calcined calcium citrate, hydrated calcium citrate, aluminum citrate, magnesium citrate and calcium phosphate, etc. Inorganic compound or zirconia. Among them, it is particularly preferable to use cerium oxide from the viewpoint of suppressing the haze to be small. In the case where the long film is produced by a melt casting film forming method, the matting agent to be used may be used in a method for producing a long film obtained by the above-described solution casting film forming method. The users are roughly the same.
於本實施形態中之長條薄膜的厚度為1~400μm,較佳為20~200μm,更佳為30~120μm,特佳為40~100μm之範圍。 The thickness of the long film in the present embodiment is 1 to 400 μm, preferably 20 to 200 μm, more preferably 30 to 120 μm, and particularly preferably 40 to 100 μm.
長條薄膜之寬幅,雖無特別限定,但可設為500~4000mm,較佳為1000~2000mm。 The width of the long film is not particularly limited, but may be 500 to 4000 mm, preferably 1000 to 2000 mm.
長條薄膜之在傾斜延伸時之延伸溫度下的較佳之彈性率,以楊氏率(Young’s modulus)表示,係為0.01MPa以上5000MPa以下,更佳為0.1MPa以上500MPa以下。若彈性率過低,則延伸時、延伸後之收縮率係變低,皺折係變得難以消除。又,若彈性率過高,則在延伸時所施加之張力係變大,並成為有必要將保持薄膜之兩側緣部的部分之強度提高,對於後續步驟之拉幅的負荷係變大。 The preferred elastic modulus at the elongation temperature at the time of oblique stretching of the long film is 0.01 MPa to 5000 MPa, more preferably 0.1 MPa to 500 MPa, as expressed by Young's modulus. When the modulus of elasticity is too low, the shrinkage ratio at the time of stretching and stretching is low, and the wrinkle system is difficult to eliminate. Further, when the modulus of elasticity is too high, the tension applied during stretching becomes large, and it is necessary to increase the strength of the portion holding the both side edges of the film, and the load for the tenter in the subsequent step becomes large.
作為長條薄膜係可使用無配向者,亦可供給預先具備有配向之薄膜。又,若有必要,則長條薄膜之配 向的寬度方向之分布亦可成為弓狀,亦即成為所謂的曲折(bowing)狀。關鍵在於,能夠將長條薄膜之配向狀態,調整為能夠使在結束後續步驟之延伸的位置之薄膜的配向成為所期望之配向的狀態。 As the long film system, a non-aligned person can be used, and a film having an alignment in advance can be supplied. Also, if necessary, the strip film The distribution in the width direction of the direction may also be arcuate, that is, a so-called bowing shape. The key point is that the alignment state of the long film can be adjusted so that the alignment of the film at the position where the subsequent step is extended can be in a desired alignment state.
接著,針對製造將上述之長條薄膜相對於寬度方向而朝向傾斜方向延伸的長條狀之傾斜配向薄膜(傾斜延伸薄膜)之傾斜配向薄膜之製造方法及製造裝置進行說明。 Next, a method and a manufacturing apparatus for producing an inclined alignment film which is an elongated oblique alignment film (inclined stretch film) which extends the above-mentioned elongated film in the oblique direction with respect to the width direction will be described.
接著,針對將上述之長條薄膜相對於寬度方向而朝向傾斜方向延伸並製造長條狀之傾斜配向薄膜,並且將該傾斜配向薄膜之寬度方向的兩端部切斷而去除,再取剩餘之製品部作為光學薄膜的光學薄膜之製造方法及製造裝置進行說明。 Then, the elongated film is stretched in the oblique direction with respect to the width direction to form an elongated oblique alignment film, and both ends of the oblique alignment film in the width direction are cut and removed, and the remaining portion is removed. The product part will be described as a method of manufacturing an optical film of an optical film and a manufacturing apparatus.
第1圖係示意性顯示光學薄膜之製造裝置1的概略構成之平面圖。製造裝置1,係從長條薄膜之搬送方向上游側起,依序具備有薄膜送出部2、搬送方向變更部3、導引輥4、延伸部5、導引輥6、搬送方向變更部7、薄膜切斷裝置8、以及薄膜捲取部9。另外,針對延伸部5及薄膜切斷裝置8之詳細內容係後述。 Fig. 1 is a plan view schematically showing a schematic configuration of an optical film manufacturing apparatus 1. In the manufacturing apparatus 1, the film feeding portion 2, the conveying direction changing portion 3, the guide roller 4, the extending portion 5, the guide roller 6, and the conveying direction changing portion 7 are sequentially provided from the upstream side in the conveying direction of the long film. The film cutting device 8 and the film winding unit 9. The details of the extension portion 5 and the film cutting device 8 will be described later.
薄膜送出部2,係將上述之長條薄膜送出並供給至延伸部5者。此薄膜送出部2,係可與長條薄膜之製膜裝置相互獨立地構成,亦可作一體性地構成。於前者之情況,係在長條薄膜之製膜後,一度捲取於卷芯上,並將成為捲繞體者裝填於薄膜送出部2,藉此,長條薄膜被從薄膜送出部2送出。另一方面,於後者之情況,薄膜送出部2,係成為在製膜長條薄膜之後,並不將該長條薄膜捲取,而是對延伸部5作送出。 The film feeding portion 2 feeds the above-described long film and supplies it to the extending portion 5. The film feeding portion 2 can be configured independently of the film forming device of the long film, or can be integrally formed. In the case of the former, after the film formation of the long film, the film is once wound up on the winding core, and the wound body is loaded into the film feeding portion 2, whereby the long film is sent out from the film feeding portion 2. . On the other hand, in the latter case, the film feeding portion 2 does not take up the long film after the film is formed, but feeds the extending portion 5.
搬送方向變更部3,係將從薄膜送出部2所送出的長條薄膜之搬送方向變更為朝向作為傾斜延伸拉幅機之延伸部5的入口之方向者。如此之搬送方向變更部3,例如係包含藉由一面搬送薄膜一面折返來使搬送方向變更之旋轉棒(turn bar)、或使該旋轉棒在與薄膜相平行之面內旋轉的旋轉台而構成。 The conveyance direction changing unit 3 changes the conveyance direction of the long film fed from the film feed unit 2 to the direction of the entrance of the extension portion 5 which is an obliquely extending tenter. The conveyance direction changing unit 3 includes, for example, a turn bar that changes the conveyance direction while being conveyed by the conveyance film, or a rotary table that rotates the rotary bar in a plane parallel to the film. .
藉由在搬送方向變更部3將長條薄膜之搬送方向如上述般地變更,除了能夠將製造裝置1全體之寬幅更加縮窄以外,亦成為能夠對於薄膜之送出位置及角度作細緻的控制,而成為能夠得到膜厚、光學值之參差為小的長條傾斜配向薄膜。又,若將薄膜送出部2及搬送方向變更部3設為可移動(可滑動、可旋轉),則能夠有效地防止在延伸部5處挾持長條薄膜之寬度方向的兩端部之左右的鋏(把持具)之對於薄膜的咬入不良。 In the conveyance direction changing unit 3, the conveyance direction of the long film is changed as described above, and the width of the entire manufacturing apparatus 1 can be further narrowed, and the position and angle of the film can be finely controlled. In addition, a long oblique alignment film having a small film thickness and a small difference in optical value can be obtained. In addition, when the film feeding portion 2 and the conveying direction changing portion 3 are movable (slidable and rotatable), it is possible to effectively prevent the left and right ends of the long film from being stretched at the extending portion 5 in the width direction.铗 (handle) is poorly bitten into the film.
另外,上述之薄膜送出部2,亦可成為能夠以對於延伸部5之入口而以既定角度送出長條薄膜的方式來 進行滑動及旋轉。於此情況,亦可成為將搬送方向變更部3之設置省略的構成。 Further, the film delivery unit 2 described above may be configured to be capable of ejecting a long film at a predetermined angle with respect to the entrance of the extending portion 5. Slide and rotate. In this case, the configuration in which the transport direction changing unit 3 is omitted may be omitted.
導引輥4,係為了使長條薄膜之行走時的軌道安定化,而在延伸部5之上游側至少被設置有1根。另外,導引輥4,係可藉由挾持薄膜之上下一對的輥對來構成,亦可藉由複數之輥對來構成。最接近延伸部5之入口的導引輥4,係為對於薄膜之行走作導引的被動輥,並經由未圖示之軸承部而分別被旋轉自如地軸支持。作為導引輥4之材質係可使用周知之材質。另外,為了防止對於薄膜造成傷痕,較佳係在導引輥4之表面上施加陶瓷塗敷,或藉由對於鋁等之輕金屬施加鉻電鍍等來將導引輥4輕量化。 The guide roller 4 is provided at least one upstream side of the extending portion 5 in order to stabilize the track when the long film is traveling. Further, the guide roller 4 may be constituted by holding a pair of roller pairs on the upper and lower sides of the film, or may be constituted by a plurality of roller pairs. The guide roller 4 closest to the entrance of the extending portion 5 is a passive roller that guides the traveling of the film, and is rotatably supported by a shaft portion (not shown). As the material of the guide roller 4, a well-known material can be used. Further, in order to prevent scratches on the film, it is preferable to apply a ceramic coating on the surface of the guide roller 4, or to apply weight chrome plating or the like to a light metal such as aluminum to lighten the guide roller 4.
又,較佳為,在較最接近延伸部5之入口的導引輥4而更上游側之輥之中的其中1根,係與橡膠輥作壓接並進行捏夾。藉由設為如此之捏夾輥,係成為能夠對於在薄膜之流動方向上的送出張力之變動作抑制。 Further, it is preferable that one of the rollers on the upstream side of the guide roller 4 closest to the inlet of the extending portion 5 is pressed against the rubber roller and pinched. By setting such a nip roller, it is possible to suppress the change in the tension in the flow direction of the film.
在最接近延伸部5之入口的導引輥4之兩端(左右)之一對的軸承部,係分別設置有第1張力檢測裝置、第2張力檢測裝置作為用以檢測在該輥而於薄膜所產生的張力之薄膜張力檢測裝置。作為薄膜張力檢測裝置,例如係可使用負載胞(load cell)。作為負載胞,係可使用拉伸或壓縮型之周知者。負載胞,係藉由被安裝在撓曲源之撓度計來將作用在受力點處的荷重轉換為電性訊號並檢測出來的裝置。 A bearing portion of one of the opposite ends (left and right) of the guide roller 4 closest to the entrance of the extending portion 5 is provided with a first tension detecting device and a second tension detecting device for detecting the roller. A film tension detecting device for tension generated by a film. As the film tension detecting device, for example, a load cell can be used. As the load cell, a known type of stretched or compressed type can be used. The load cell is a device that converts the load acting at the force point into an electrical signal and detects it by a deflection meter installed on the deflection source.
負載胞,係藉由被設置在最接近延伸部5之入口的導引輥4之左右的軸承部,而將行走中之薄膜所作用在輥處之力,亦即將在薄膜之兩側緣近旁所產生的於薄膜前進方向上之張力左右相互獨立地檢測出來。另外,亦可在構成輥之軸承部的支持體直接安裝撓度計,並構成為根據在該支持體所產生的撓曲來檢測荷重,亦即檢測薄膜張力。所產生的撓曲與薄膜張力之間的關係,係預先被計測出來而為既知。 The load cell is placed on the left and right bearing portions of the guide roller 4 disposed closest to the entrance of the extension portion 5, and the force of the film under walking acting on the roller is also near the sides of the film. The tension generated in the advancing direction of the film is detected independently of each other. Further, a deflection gauge may be directly attached to the support body constituting the bearing portion of the roller, and the load may be detected based on the deflection generated by the support, that is, the film tension may be detected. The relationship between the resulting deflection and the film tension is known in advance and is known.
在從薄膜送出部2或搬送方向變更部3被供給至延伸部5的薄膜之位置及搬送方向從朝向延伸部5之入口的位置及搬送方向而偏離的情況,係成為會因應於此偏離量而在最接近延伸部5之入口的導引輥4之薄膜之兩側緣近旁的張力產生差異。因而,藉由設置如上述般之薄膜張力檢測裝置來檢測上述之張力差,而可判別該偏離之程度。亦即,若薄膜之搬送位置及搬送方向為適當(若為朝向延伸部5之入口的位置及方向),則作用在上述導引輥4之荷重,係會於軸方向之兩端成為大略均等,但若非為適當,則會在左右而於薄膜張力產生差異。 The position of the film supplied from the film feeding portion 2 or the conveying direction changing portion 3 to the extending portion 5 and the direction in which the conveying direction deviates from the position toward the inlet of the extending portion 5 and the conveying direction are caused by the amount of deviation. On the other hand, the tension near the side edges of the film of the guide roller 4 closest to the entrance of the extending portion 5 is different. Therefore, the above-described tension difference can be detected by providing the film tension detecting device as described above, and the degree of the deviation can be determined. In other words, if the transport position and the transport direction of the film are appropriate (in the position and direction toward the entrance of the extension portion 5), the load acting on the guide roller 4 is substantially equal at both ends in the axial direction. However, if it is not appropriate, there will be a difference in film tension between the left and right.
因而,若以使最接近延伸部5之入口的導引輥4之左右的薄膜張力差成為相等的方式,例如藉由上述之搬送方向變更部3而來適當地調整薄膜之位置及搬送方向(相對於延伸部5之入口的角度),則由延伸部5之入口部的把持具所致之薄膜的把持會安定,而可減少把持具鬆脫等的障礙之發生。進而,可使由延伸部5所致之傾斜 延伸後的薄膜之寬幅方向上的物性安定。 Therefore, the film position and the conveyance direction of the film are appropriately adjusted by, for example, the above-described conveyance direction changing unit 3 so that the film tension difference between the right and left sides of the guide roller 4 closest to the entrance of the extension portion 5 is equal. With respect to the angle of the entrance of the extension portion 5, the holding of the film by the grip of the entrance portion of the extension portion 5 is stabilized, and the occurrence of an obstacle such as loosening of the gripper can be reduced. Further, the tilt caused by the extension portion 5 can be made The physical properties of the stretched film in the width direction are stable.
導引輥6,係為了使藉由延伸部5而被傾斜延伸的薄膜之行走時的軌道安定,而在延伸部5之下游側至少被設置有1根。 The guide roller 6 is provided with at least one downstream side of the extending portion 5 in order to stabilize the track during traveling of the film which is obliquely extended by the extending portion 5.
搬送方向變更部7,係將從延伸部5所搬送之延伸後的薄膜之搬送方向變更為朝向薄膜捲取部9之方向者。 The conveyance direction changing unit 7 changes the conveyance direction of the film which has been extended from the extension unit 5 to the direction toward the film winding unit 9.
在此,為了與配向角(薄膜之面內遲相軸之方向)之微調整或製品的種類變化相對應,係成為必須進行在延伸部5之入口的薄膜前進方向與延伸部5之出口的薄膜前進方向間所成之角度的調整。為了進行此角度調整,係成為必須藉由搬送方向變更部3來變更所製膜的薄膜之前進方向而將薄膜導引至延伸部5之入口,及/或藉由搬送方向變更部7來變更從延伸部5之出口所導出的薄膜之前進方向並使薄膜回到薄膜捲取部9之方向。 Here, in order to slightly adjust the alignment angle (the direction of the retardation axis in the in-plane of the film) or the type of the product, it is necessary to perform the film advancing direction at the entrance of the extending portion 5 and the exit of the extending portion 5. The adjustment of the angle between the advancing directions of the film. In order to adjust the angle, it is necessary to change the film advance direction of the film formed by the conveyance direction changing unit 3 to guide the film to the entrance of the extension portion 5, and/or to change by the conveyance direction changing unit 7. The film leading from the outlet of the extension 5 advances in the direction and returns the film to the direction of the film take-up portion 9.
又,在生產性或產率的觀點,較佳係將製膜及傾斜延伸連續性地進行。在連續進行製膜步驟、傾斜延伸步驟、捲取步驟的情況,藉由以搬送方向變更部3及/或搬送方向變更部7來變更薄膜之前進方向並在製膜步驟與捲取步驟中使薄膜之前進方向一致,也就是說,藉由如第1圖中所示般,使從薄膜送出部2送出的薄膜之前進方向(送出方向)與即將要藉由薄膜捲取部9被捲取之前的薄膜之前進方向(捲取方向)一致,而可使相對於薄膜前進方向之裝置全體的寬幅縮小。 Further, from the viewpoint of productivity or productivity, it is preferred to carry out the film formation and the oblique stretching continuously. When the film forming step, the tilting step, and the winding step are continuously performed, the film direction advancement direction is changed by the conveyance direction changing unit 3 and/or the conveyance direction changing unit 7, and is made in the film forming step and the winding step. The film advances in the same direction, that is, the film is fed from the film feeding portion 2 in the forward direction (feeding direction) and is about to be taken up by the film winding portion 9 as shown in Fig. 1. The previous film advance direction (winding direction) is uniform, and the width of the entire device relative to the film advancement direction can be reduced.
另外,雖然係並不一定必須在製膜步驟與捲取步驟中使薄膜之前進方向一致,但較佳係以成為不會使薄膜送出部2和薄膜捲取部9相干涉之佈局的方式,來藉由搬送方向變更部3及/或搬送方向變更部7來變更薄膜之前進方向。 Further, although it is not always necessary to make the film advance direction in the film forming step and the winding step, it is preferable to adopt a configuration in which the film feeding portion 2 and the film winding portion 9 do not interfere with each other. The film direction advancement direction is changed by the conveyance direction changing unit 3 and/or the conveyance direction changing unit 7.
作為如上述般之搬送方向變更部3、7,係可藉由使用氣流輥(airtflow roll)或氣動旋棒(air trunbar)等的周知之手法來實現。 The conveyance direction changing sections 3 and 7 as described above can be realized by a well-known technique such as an air flow roll or an air trunbar.
薄膜捲取部9,係將從延伸部5經由搬送方向變更部7及薄膜切斷裝置8所搬送的薄膜(光學薄膜)進行捲取者,例如藉由捲揚裝置、積聚裝置、驅動裝置等而構成。薄膜捲取部9,較佳係為了調整薄膜之捲取位置,而為可在橫方向上進行滑動的構造。 The film winding unit 9 winds up the film (optical film) conveyed from the extending portion 5 via the conveying direction changing unit 7 and the film cutting device 8, and is, for example, a hoisting device, an accumulating device, a driving device, or the like. And constitute. The film take-up portion 9 is preferably configured to be slidable in the lateral direction in order to adjust the winding position of the film.
薄膜捲取部9,係成為能夠以相對於延伸部5之出口以既定角度來拉取薄膜的方式而對於薄膜之拉取位置及角度作細緻的控制。藉此,成為能夠得到膜厚、光學值之參差為小的長條傾斜配向薄膜。又,成為能夠有效地防止薄膜之皺折的發生,並且,由於薄膜之捲取性提昇,因此成為能夠以長條狀態來捲取薄膜。 The film take-up portion 9 is capable of finely controlling the drawing position and angle of the film so that the film can be pulled at a predetermined angle with respect to the exit of the extending portion 5. As a result, a long oblique alignment film having a small film thickness and a small difference in optical value can be obtained. Moreover, it is possible to effectively prevent the occurrence of wrinkles of the film, and since the take-up property of the film is improved, the film can be wound up in a long state.
此薄膜捲取部9,係構成將藉由延伸部5被延伸並搬送的薄膜以一定之張力來作拉取之拉取部。另外,在延伸部5與薄膜捲取部9之間,亦可設置用以將薄膜以一定之張力作拉取之拉取輥。又,亦可使上述之導引輥6具有作為上述拉取輥之功能。 The film take-up portion 9 constitutes a drawing portion for pulling a film which is extended by the extending portion 5 and conveyed by a certain tension. Further, between the extending portion 5 and the film winding portion 9, a pulling roller for pulling the film at a certain tension may be provided. Further, the above-described guide roller 6 may have a function as the above-described pull roller.
於本實施形態中,延伸後之薄膜的拉取張力T(N/m),係以在100N/m<T<300N/m,較佳為150N/m<T<250N/m之間進行調整。在上述之拉曲張力為100N/m以下時,係容易發生薄膜之鬆弛或皺折,並且遲滯、配向角之薄膜寬幅方向上的分布也會惡化。相反地,若拉取張力成為300N/m以上,則配向角之薄膜寬幅方向上的參差會惡化,而使寬幅產率(寬幅方向上之取得效率)惡化。 In the present embodiment, the drawing tension T (N/m) of the stretched film is adjusted between 100 N/m < T < 300 N/m, preferably 150 N/m < T < 250 N/m. . When the above-mentioned tensile tension is 100 N/m or less, the film is liable to be loosened or wrinkled, and the distribution in the width direction of the film having hysteresis and alignment angle is also deteriorated. On the other hand, when the pulling tension is 300 N/m or more, the unevenness in the width direction of the film of the alignment angle is deteriorated, and the wide-yield (efficiency in the width direction) is deteriorated.
又,於本實施形態中,較佳係將上述拉取張力T的變動以未達±5%之精度來作控制,更佳係以未達±3%之精度來作控制。若上述拉取張力T之變動為±5%以上,則在寬幅方向及流動方向(搬送方向)上的光學特性之參差會變大。作為將上述拉取張力T之變動控制在上述範圍內之方法,係可列舉下述方法:測定被施加在延伸部5之出口側之最初的輥(導引輥6)之荷重,亦即薄膜之張力,並以使該值會成為一定的方式,來藉由一般性之PID控制方式而控制拉取輥或薄膜捲取部9之捲取輥的旋轉速度。作為測定上述荷重之方法係可列舉:在導引輥6之軸承部安裝負載胞並測定施加在導引輥6處之荷重,亦即薄膜之張力的方法。作為負載胞係可使用拉伸型或壓縮型之周知者。 Further, in the present embodiment, it is preferable that the fluctuation of the pulling tension T is controlled with an accuracy of less than ± 5%, and more preferably with an accuracy of less than ± 3%. When the variation of the pulling tension T is ±5% or more, the difference in optical characteristics in the wide direction and the flow direction (transport direction) becomes large. As a method of controlling the fluctuation of the pulling tension T within the above range, a method of measuring the load applied to the first roller (guide roller 6) on the outlet side of the extending portion 5, that is, a film, is exemplified. The tension is controlled so that the value of the winding roller of the take-up roll or film take-up portion 9 is controlled by a general PID control method. As a method of measuring the load, a method of attaching a load cell to the bearing portion of the guide roller 6 and measuring the load applied to the guide roller 6, that is, the tension of the film, is exemplified. A known type of stretch type or compression type can be used as the load cell system.
另外,在將長條狀之光學薄膜捲取之前,在防止薄膜彼此之結塊的目的上,亦可將遮罩薄膜重疊於光學薄膜上並同時進行捲取,亦可一面在藉由捲取而重疊的 光學薄膜之至少其中一方(較佳為雙方)的端部貼合膠帶等一面進行捲取。作為遮罩薄膜,只要是可保護光學薄膜者則無特別限定,例如,可列舉:聚對苯二甲酸乙二酯薄膜、聚乙烯薄膜、聚丙烯薄膜等。 In addition, before the strip-shaped optical film is taken up, the mask film may be superposed on the optical film and simultaneously wound up, or may be wound up by the purpose of preventing the film from agglomerating with each other. Overlapping At least one of the optical films (preferably both) is attached to the end of the tape or the like. The mask film is not particularly limited as long as it can protect the optical film, and examples thereof include a polyethylene terephthalate film, a polyethylene film, and a polypropylene film.
又,在將光學薄膜捲取之前,係亦可成為藉由於該薄膜之至少其中一面(較佳為兩面)的寬度方向之兩端部,形成被稱為滾花部或是壓花部之相較於薄膜面而更為增高的部分(凸部),來防止在將薄膜捲取時之薄膜彼此的結塊。另外,滾花部之高度及形狀,亦可在寬度方向之兩端部為不同(亦可為非對稱)。 Further, before the optical film is wound up, a phase called a knurling portion or an embossing portion may be formed by both end portions in the width direction of at least one side (preferably two surfaces) of the film. A portion (protrusion) that is higher than the film surface to prevent agglomeration of the films when the film is taken up. Further, the height and shape of the knurled portion may be different (may be asymmetrical) at both ends in the width direction.
接著,針對上述之延伸部5之詳細內容進行說明。第2圖,係示意性顯示延伸部5之軌形態的其中一例之平面圖。但此係為其中一例,延伸部5之構成並不被限定於此。 Next, the details of the above-described extension portion 5 will be described. Fig. 2 is a plan view schematically showing an example of the rail form of the extending portion 5. However, this is an example, and the configuration of the extension portion 5 is not limited thereto.
於本實施形態中,作為延伸部5,係使用可進行傾斜延伸之拉幅機(傾斜延伸機)來進行。此拉幅機,係將長條薄膜加熱至可進行延伸之任意之溫度並進行傾斜延伸的裝置。此拉幅機,係具備有加熱區域Z、左右一對之軌Ri、Ro、以及將沿著軌Ri、Ro行走的薄膜進行搬送之多數個把持具Ci、Co(在第2圖中,係僅圖示1組把持具)。另外,針對加熱區域Z之詳細內容係後述。軌Ri、Ro,係分別將複數之軌部藉由連結部來作連結而構成 (第2圖中之白圈係連結部之其中一例)。把持具Ci、Co,係藉由將薄膜之寬度方向的兩端作把持之鋏而構成。 In the present embodiment, the extension portion 5 is formed by a tenter (inclined stretcher) that can be tilted and extended. This tenter is a device that heats a long strip of film to any temperature at which it can be extended and obliquely extends. The tenter includes a heating zone Z, a pair of left and right rails Ri, Ro, and a plurality of grippers Ci and Co that transport the film traveling along the rails Ri and Ro (in the second figure, Only one set of grippers is shown). In addition, the details of the heating zone Z will be described later. The rails Ri and Ro respectively form a plurality of rail portions connected by a connecting portion. (An example of the white ring system connecting portion in Fig. 2). The grippers Ci and Co are configured by holding both ends of the film in the width direction.
於第2圖中,長條薄膜之送出方向D1,係與延伸後之光學薄膜的捲取方向D2相異,並在與捲取方向D2之間成送出角度θ i之角度。送出角度θ i,係可在超過0°未達90°的範圍內,任意設定為所期望的角度。 In Fig. 2, the feeding direction D1 of the long film is different from the winding direction D2 of the stretched optical film, and is at an angle of the angle θ i between the winding direction D2 and the winding direction D2. The delivery angle θ i can be arbitrarily set to a desired angle within a range of more than 0° and less than 90°.
如此般,由於送出方向D1與捲取方向D2不同,因此拉幅機之軌形態係成為左右非對稱之形狀,薄膜之搬送路徑係在途中彎曲。又,成為能夠因應於對應製造之長條傾斜配向薄膜賦予的配向角度θ、延伸倍率等,來手動或自動調整軌形態。於在本實施形態之製造方法中所使用之傾斜延伸機,較佳係成為可自由地設定構成軌Ri、Ro之各軌部及軌連結部的位置並任意地變更軌形態。 In this manner, since the feeding direction D1 is different from the winding direction D2, the rail shape of the tenter is asymmetrical to the left and right, and the film transport path is curved on the way. Further, the rail shape can be manually or automatically adjusted in accordance with the alignment angle θ, the stretch ratio, and the like which are applied to the long oblique alignment film to be manufactured. In the tilting stretcher used in the manufacturing method of the present embodiment, it is preferable to be able to freely set the positions of the rail portions and the rail connecting portions constituting the rails Ri and Ro and to arbitrarily change the rail shape.
於本實施形態中,拉幅機之複數之把持具Ci、Co,係與前後之把持具Ci、Co保持一定的間隔,而成為以一定速度行走。把持具Ci、Co之行走速度係可適當選擇,但通常為1~150m/分鐘。於本實施形態中,考慮到薄膜之生產性,較佳係設為20~100m/分鐘。左右一對之把持具Ci、Co的行走速度之差,係行走速度之通常1%以下,較理想係為0.5%以下,更佳為0.1%以下。此係因為若在延伸步驟出口處於薄膜之左右有前進速度差,則在延伸步驟出口會產生皺折、偏向,因此左右之把持具Ci、Co之速度差,係要求實質為相同速度之故。在一般 的拉幅裝置等中,因應於驅動鏈條之鏈輪的齒之週期、驅動馬達之頻率等,係存在有以秒以下之尺度所產生的速度不均,有時會產生數%之不均,但此等並不符合於本實施形態中所述之速度差。 In the present embodiment, the plurality of grippers Ci and Co of the tenter are kept at a constant speed while maintaining a constant interval between the grippers Ci and Co. The walking speed of the holding device Ci and Co can be appropriately selected, but it is usually 1 to 150 m/min. In the present embodiment, in consideration of the productivity of the film, it is preferably 20 to 100 m/min. The difference between the traveling speeds of the pair of left and right grippers Ci and Co is usually 1% or less, and preferably 0.5% or less, more preferably 0.1% or less. This is because if there is a difference in the advance speed between the left and right sides of the film at the exit of the stretching step, wrinkles and deflections occur at the exit of the stretching step. Therefore, the difference in speed between the left and right grippers Ci and Co is required to be substantially the same speed. In general In the tenter device or the like, depending on the period of the teeth of the sprocket for driving the chain, the frequency of the drive motor, etc., there is a speed unevenness which is generated on a scale of seconds or less, and unevenness may be generated by several %. However, these do not conform to the speed difference described in this embodiment.
於在本實施形態之製造方法中所使用的延伸機,特別是在薄膜之搬送成為傾斜的部位,於對於把持具之軌跡作限制的軌處,有時會要求有較大的彎曲率。在避免起因於急遽之彎曲所導致的把持具彼此間之干涉、或局部性之應力集中的目的上,較理想為,在彎曲部,把持具之軌跡係成為描繪出曲線。 In the stretching machine used in the manufacturing method of the present embodiment, in particular, in a portion where the conveyance of the film is inclined, a large bending rate may be required at a rail that restricts the trajectory of the gripper. For the purpose of avoiding interference between the grippers or local stress caused by the sharp bending, it is preferable that the trajectory of the gripper is drawn as a curve in the curved portion.
如此般,為了對長條薄膜賦予傾斜方向之配向所使用的傾斜延伸拉幅機,較佳係藉由使軌形態多樣性變化,而可自由地設置薄膜之配向角,進而可將薄膜之配向軸(遲相軸)涵蓋薄膜之寬幅方向地來左右均等地以高精度配向,且亦可以高精度來控制薄膜厚度或遲滯的拉幅機。 In this way, in order to impart an obliquely extending tenter for the alignment of the long film in the oblique direction, it is preferable to freely set the alignment angle of the film by changing the shape of the rail, thereby further aligning the film. The shaft (slow phase axis) covers the width direction of the film to be equally aligned to the right and left, and the tenter can also control the film thickness or hysteresis with high precision.
接著,針對在延伸部5之延伸動作進行說明。長條薄膜,係藉由左右之把持具Ci、Co而使其之兩端被把持,並伴隨著把持具Ci、Co之行走而在加熱區域Z內被搬送。左右之把持具Ci、Co,係在延伸部5之入口部(圖中A之位置),在相對於薄膜之前進方向(送出方向D1)而略垂直的方向上相互對向,並在左右非對稱之軌Ri、Ro上分別行走,而在延伸結束時之出口部(圖中B之位置)將所把持的薄膜釋放。被從把持具Ci、Co釋 放的薄膜,係藉由前述之薄膜捲取部9而被捲取於卷芯上。一對之軌Ri、Ro,係分別具有無端狀之連續軌道,在拉幅機之出口部將薄膜之把持釋放後的把持具Ci、Co,係成為在外側之軌上行走並依序回到入口部。 Next, the extension operation of the extension portion 5 will be described. The long film is held at both ends by the left and right grippers Ci and Co, and is transported in the heating zone Z along with the walking of the grippers Ci and Co. The left and right grippers Ci and Co are in the entrance portion of the extension portion 5 (the position in the figure A), and are opposed to each other in a direction slightly perpendicular to the advance direction (feeding direction D1) of the film, and are not in the right direction. The symmetrical rails Ri and Ro respectively travel, and the exiting portion (the position of B in the figure) releases the held film at the end of the extension. It is released from the holding device Ci, Co The discharged film is taken up on the winding core by the film winding portion 9 described above. The pair of rails Ri and Ro each have a continuous track with no end, and the grippers Ci and Co which are released after the holding of the film at the exit portion of the tenter are walked on the outer rail and are sequentially returned. Entrance department.
此時,由於軌Ri、Ro係為左右非對稱,因此在第2圖之例中,於圖中A的位置相對向的左右之把持具Ci、Co,係隨著在軌Ri、Ro上行走,而成為在軌Ri側(內軌側)上行走之把持具Ci會相對於在軌Ro側(外軌側)上行走之把持具Co而先行前進的位置關係。 At this time, since the rails Ri and Ro are asymmetrical to the left and right, in the example of Fig. 2, the grips Ci and Co which are opposite to each other in the position of A in the figure follow the rails Ri and Ro. On the other hand, the gripper Ci that is traveling on the rail Ri side (inner rail side) advances in a positional relationship with respect to the gripper Co that travels on the rail Ro side (outer rail side).
亦即,當在圖中A之位置在相對於薄膜之送出方向D1而略垂直的方向上相對向之把持具Ci、Co當中,其中一方之把持具Ci先到達薄膜之延伸結束時的位置B時,連結把持具Ci、Co的直線係相對於與薄膜之捲取方向D2略垂直的方向而作角度θ L之傾斜。基於以上之動作,長條薄膜係成為相對於寬度方向而以θ L的角度作傾斜延伸。在此,略垂直係表示落於90±1°之範圍內。 That is, when the position of A in the figure is relatively perpendicular to the direction in which the film is fed in the direction D1, the holders Ci, Co, one of the grippers Ci first reaches the position B at the end of the extension of the film. At this time, the straight line connecting the grippers Ci and Co is inclined at an angle θ L with respect to a direction slightly perpendicular to the winding direction D2 of the film. Based on the above operation, the long film is formed to extend obliquely at an angle of θ L with respect to the width direction. Here, a slightly vertical system means falling within the range of 90 ± 1 °.
在傾斜延伸步驟中,薄膜之搬送速度亦可為1~150m/分鐘。就使薄膜之生產性提昇的觀點而言,薄膜之搬送速度較理想為10~120m/分鐘,更理想為20~100m/分鐘。 In the oblique stretching step, the film transport speed may be 1 to 150 m/min. The film transport speed is preferably from 10 to 120 m/min, more preferably from 20 to 100 m/min, from the viewpoint of improving the productivity of the film.
接著,針對上述之加熱區域Z之詳細內容進行說明。延伸部5之加熱區域Z,係藉由預熱區域Z1、延伸區域Z2以及舒緩區域Z3所構成。在延伸部5,藉由把持具Ci、Co被把持的薄膜,係依序通過預熱區域Z1、延 伸區域Z2、舒緩區域Z3。於本實施形態中,預熱區域Z1與延伸區域Z2係藉由隔壁而被區隔,延伸區域Z2與舒緩區域Z3係藉由隔壁而被區隔。另外,在預熱區域Z1、延伸區域Z2、舒緩區域Z3之各者的區域內,係亦可適當設置隔壁(亦可將各區域之內部進一步藉由隔壁來作分割)。 Next, the details of the above-described heating zone Z will be described. The heating zone Z of the extension 5 is constituted by a preheating zone Z1, an extension zone Z2 and a soothing zone Z3. In the extension portion 5, the film held by the holding members Ci and Co is sequentially passed through the preheating zone Z1. Stretch zone Z2, sooth zone Z3. In the present embodiment, the preheating zone Z1 and the extension zone Z2 are partitioned by the partition walls, and the extension zone Z2 and the soothing zone Z3 are partitioned by the partition walls. Further, in the region of each of the preheating zone Z1, the extension zone Z2, and the soothing zone Z3, a partition wall may be appropriately provided (the inside of each zone may be further divided by the partition wall).
預熱區域Z1,係在加熱區域Z之入口部,使把持薄膜之兩端的把持具Ci、Co在左右(在薄膜寬幅方向上)保持一定之間隔而行走之區域。 The preheating zone Z1 is an area at the entrance of the heating zone Z, and the grippers Ci and Co holding the both ends of the film are held at a predetermined interval between the left and right (in the film width direction).
延伸區域Z2,係使把持薄膜之兩端的把持具Ci、Co之間隔展開直到成為既定之間隔為止之區域。此時,係進行如同上述一般之傾斜延伸,但是,係亦可因應於需要,而在傾斜延伸之前後,進行縱方向或橫方向之延伸。 The extension zone Z2 is an area in which the distance between the grippers Ci and Co at both ends of the grip film is developed until a predetermined interval is reached. At this time, the general oblique extension is performed as described above, but the longitudinal direction or the lateral direction may be extended after the oblique extension before, depending on the necessity.
舒緩區域Z3,係進行在延伸區域Z2中之傾斜延伸步驟之後,使起因於傾斜延伸殘留在薄膜上的應力(殘留應力)藉由後述之溫度設定來舒緩的舒緩步驟之區域。在舒緩區域Z3中,由於傾斜延伸薄膜之光學軸(遲相軸)係被固定,因此舒緩區域Z3亦被稱為熱固定區域。在舒緩區域Z3中,係可使兩端之把持具Ci、Co相互保持平行地行走,亦可以在使薄膜於寬度方向上收縮之後再保持平行的方式來行走。無論如何,在舒緩區域Z3中,薄膜之搬送路徑並不會如傾斜延伸區域Z2-2般地彎曲,薄膜之搬送方向係為一定。 The soothing zone Z3 is a zone in which the stress (residual stress) remaining on the film due to the oblique extension is relieved by the temperature setting described later after the oblique stretching step in the extending region Z2. In the soothing zone Z3, since the optical axis (late phase axis) of the obliquely extending film is fixed, the soothing zone Z3 is also referred to as a heat fixing zone. In the soothing zone Z3, the grippers Ci and Co at both ends can be moved in parallel with each other, or can be walked in such a manner that the film is contracted in the width direction and then kept parallel. In any case, in the soothing zone Z3, the film transport path does not bend as in the obliquely extending region Z2-2, and the film transport direction is constant.
另外,延伸後之薄膜,在通過舒緩區域Z3之後,亦可通過將區域內之溫度設定為構成薄膜之熱塑性樹脂的玻璃轉移溫度Tg(℃)以下之區間(冷卻區域)。 Further, after the stretched film passes through the soothing zone Z3, the temperature in the region may be set to a range (cooling region) equal to or lower than the glass transition temperature Tg (° C.) of the thermoplastic resin constituting the film.
較佳為,相對於熱塑性樹脂之玻璃轉移溫度Tg,預熱區域Z1之溫度係被設定為Tg~Tg+60℃,延伸區域Z2之溫度係被設定為Tg~Tg+50℃,舒緩區域Z3及冷卻區域之溫度係被設定為Tg-40~Tg+30℃。 Preferably, the temperature of the preheating zone Z1 is set to Tg~Tg+60°C with respect to the glass transition temperature Tg of the thermoplastic resin, and the temperature of the extension zone Z2 is set to Tg~Tg+50°C, soothing zone Z3 The temperature in the cooling zone was set to Tg-40~Tg+30 °C.
另外,預熱區域Z1、延伸區域Z2及舒緩區域Z3之長度係可適當選擇,相對於延伸區域Z2之長度,預熱區域Z1之長度通常為50~200%,舒緩區域Z3之長度通常為50~150%。 In addition, the lengths of the preheating zone Z1, the extension zone Z2, and the soothing zone Z3 may be appropriately selected. The length of the preheating zone Z1 is usually 50 to 200% with respect to the length of the extension zone Z2, and the length of the soothing zone Z3 is usually 50. ~150%.
又,若將延伸前之薄膜的寬幅設為Wo(mm),並將延伸後之薄膜的寬幅設為W(mm),則在延伸步驟中之延伸倍率R(W/Wo),較佳為1.1~3.0,更佳為1.3~2.0。若延伸倍率落在此範圍中,則由於薄膜之寬幅方向的厚度不均變小,故為佳。 Further, if the width of the film before stretching is set to Wo (mm), and the width of the film after stretching is set to W (mm), the stretching ratio R (W/Wo) in the extending step is Good is 1.1~3.0, better is 1.3~2.0. When the stretching ratio falls within this range, the thickness unevenness in the width direction of the film becomes small, which is preferable.
另外,在延伸部5之傾斜延伸的手法並不限定於上述之手法,例如亦可藉由如於日本特開2008-23775號公報中所揭示般之同時雙軸延伸來進行傾斜延伸。另外,同時雙軸延伸,係指將被供給之長條薄膜的寬度方向之兩端部藉由各把持具來把持,並一面使各把持具移動一面搬送長條薄膜,並且在將長條薄膜之搬送方向設為一定的狀態下,藉由使其中一方之把持具的移動速度與另外一方之把持具的移動速度相異,來將長條薄膜相對於寬度方 向而朝向傾斜方向延伸之方法。除此之外,亦可藉由如於日本特開2011-11434號公報中所揭示般之手法來進行傾斜延伸。 Further, the method of extending the slanting portion of the extending portion 5 is not limited to the above-described method, and the slanting extension may be performed by, for example, simultaneous biaxial stretching as disclosed in Japanese Laid-Open Patent Publication No. 2008-23775. In addition, the simultaneous biaxial stretching means that both end portions in the width direction of the long film to be supplied are gripped by the respective holders, and the long film is conveyed while moving the respective holders, and the long film is stretched. When the transport direction is set to a constant state, the long film is oriented to the width by changing the moving speed of one of the grippers to the moving speed of the other gripper. A method of extending toward an oblique direction. In addition to this, the oblique extension can be performed by a technique as disclosed in Japanese Laid-Open Patent Publication No. 2011-11434.
接著,針對薄膜切斷裝置8之詳細內容進行說明。第3圖係顯示薄膜切斷裝置8之概略構成之立體圖。薄膜切斷裝置8,係具有第1切斷部8a及第2切斷部8b,第1切斷部8a及第2切斷部8b係分別將藉由延伸部5而被傾斜延伸的長條傾斜配向薄膜F’之寬度方向的兩端部,亦即其中一方之端部Ta及另一方之端部Tb沿著長度方向來切斷。藉由第1切斷部8a及第2切斷部8b,從長條傾斜配向薄膜F’將端部Ta及另一方之端部Tb切斷並去除,藉此,可取得在寬度方向上於端部Ta與端部Tb之間所剩餘的薄膜部分(製品部)作為光學薄膜F。被切斷的端部Ta、Tb,係作為修整部而被回收至供料板(shooter,未圖示),並在接下來的薄膜之製膜中被再利用。又,第1切斷部8a及第2切斷部8b之寬度方向的位置,係因應於所取得的光學薄膜F之寬幅而作調整。 Next, the details of the film cutting device 8 will be described. Fig. 3 is a perspective view showing a schematic configuration of the film cutting device 8. The film cutting device 8 has a first cutting portion 8a and a second cutting portion 8b, and the first cutting portion 8a and the second cutting portion 8b are long strips that are obliquely extended by the extending portion 5, respectively. Both end portions of the oblique alignment film F' in the width direction, that is, one end portion Ta and the other end portion Tb are cut along the longitudinal direction. By the first cutting portion 8a and the second cutting portion 8b, the end portion Ta and the other end portion Tb are cut and removed from the long inclined alignment film F', whereby the width direction can be obtained. The film portion (product portion) remaining between the end portion Ta and the end portion Tb serves as the optical film F. The cut ends Ta and Tb are collected as a trimming portion to a supply plate (not shown), and are reused in the subsequent film formation. Moreover, the position in the width direction of the first cutting portion 8a and the second cutting portion 8b is adjusted in accordance with the width of the obtained optical film F.
第4圖係薄膜切斷裝置8之平面圖。第1切斷部8a及第2切斷部8b,係分別具有上刀10a(第2刀)和下刀10b(第1刀)。下刀10b,係相對於長條傾斜配向薄膜F’之薄膜面而被配置在其中一側(例如下側)並以沿著寬度方向配置之旋轉軸10b1為中心進行旋轉的 旋轉刀。上刀10a,係相對於長條傾斜配向薄膜F’之薄膜面而被配置在另外一側(例如上側)的旋轉刀。上刀10a之旋轉軸10a1,係在薄膜面內,相對於寬度方向而以與相對於下刀10b之束角θ 1(°)對應的角度作傾斜。另外,上述之束角,係指在薄膜面內而上刀10a與下刀10b所成之角度。 Fig. 4 is a plan view of the film cutting device 8. Each of the first cutting portion 8a and the second cutting portion 8b has an upper blade 10a (second blade) and a lower blade 10b (first blade). Lower blade 10b, the inclined line with respect to the alignment film strip F 'of the film plane is arranged on one side (e.g. lower side), and a rotation axis arranged along the width of the rotating blade rotation direction of the center 10b 1. The upper blade 10a is a rotary blade that is disposed on the other side (for example, the upper side) with respect to the film surface of the elongated oblique alignment film F'. The rotating shaft 10a 1 of the upper blade 10a is inclined in the film surface with respect to the width direction at an angle corresponding to the beam angle θ 1 (°) with respect to the lower blade 10b. Further, the above-mentioned toe angle refers to an angle formed by the upper blade 10a and the lower blade 10b in the film surface.
若將長條傾斜配向薄膜F’搬送至薄膜切斷裝置8,則長條傾斜配向薄膜F’係在被上刀10a和下刀10b所夾入的位置(切割點),藉由上刀10a及下刀10b之旋轉而被切斷。藉由一面將長條傾斜配向薄膜F’在長度方向上搬送一面切斷,長條傾斜配向薄膜F’係成為沿著長度方向被切斷。如此般,在薄膜切斷裝置8,係進行將長條傾斜配向薄膜F’之寬度方向的兩端部分別藉由第1切斷部8a及第2切斷部8b來切斷之切斷步驟。 When the long inclined alignment film F' is transported to the film cutting device 8, the long inclined alignment film F' is attached to the position (cutting point) sandwiched by the upper blade 10a and the lower blade 10b, by the upper blade 10a And the rotation of the lower blade 10b is cut. The long inclined alignment film F' is cut while being conveyed in the longitudinal direction while the long oblique alignment film F' is cut, and the long oblique alignment film F' is cut along the longitudinal direction. In the film cutting device 8, the cutting step of cutting the both end portions in the width direction of the long oblique alignment film F' by the first cutting portion 8a and the second cutting portion 8b is performed. .
在此,在上述之切斷步驟中,在第1切斷部8a及第2切斷部8b之各者,係如以下般地設定上刀10a和下刀10b之間的位置關係,而將長條傾斜配向薄膜F’切斷。亦即,於下刀10b之寬度方向的其中一側(例如薄膜中央側、薄膜內側)及另一側(與薄膜中央側相反側、薄膜外側)當中,隨著朝相對於下刀10b之束角θ 1增大的方向將上刀10a傾斜,在上刀10a之形成上述束角θ 1的面S和長條傾斜配向薄膜F’之配向方向所形成的角度θ 變小的側配置上刀10a。另外,上述之角度θ係設為0°<θ<90°之範圍。在第4圖所示之例中,上述角度θ變小 的側,係指於將長條傾斜配向薄膜F’之左側的端部Ta切斷之第1切斷部8a,係相對於下刀10b而為薄膜中央側(薄膜內側),於將長條傾斜配向薄膜F’之右側的端部Tb切斷之第2切斷部8b,係相對於下刀10b而為與薄膜中央側相反側(薄膜外側)。在切斷步驟中,係如上述般地配置上刀10a和下刀10b並將長條傾斜配向薄膜F’夾入,將長條傾斜配向薄膜F’切斷。 Here, in the above-described cutting step, the positional relationship between the upper blade 10a and the lower blade 10b is set as follows in each of the first cutting portion 8a and the second cutting portion 8b. The strip oblique alignment film F' is cut. That is, in one of the width direction of the lower blade 10b (for example, the film center side, the film inner side) and the other side (the side opposite to the film center side, the film outer side), with the bundle facing the lower blade 10b The direction in which the angle θ 1 increases increases the upper blade 10a, and the upper blade 10a is disposed on the side where the angle θ formed by the direction S of the upper blade 10a forming the beam angle θ 1 and the direction of the elongated oblique alignment film F' becomes smaller. 10a. Further, the above-described angle θ is set to a range of 0° < θ < 90°. In the example shown in Fig. 4, the above angle θ becomes small. The first cutting portion 8a that cuts the end portion Ta on the left side of the long obliquely oriented film F' is the film center side (the inside of the film) with respect to the lower blade 10b. The second cut portion 8b, which is cut at the end Tb on the right side of the inclined alignment film F', is opposite to the center side of the film (outside of the film) with respect to the lower blade 10b. In the cutting step, the upper blade 10a and the lower blade 10b are disposed as described above, and the long oblique alignment film F' is sandwiched, and the long oblique alignment film F' is cut.
第5圖係參考例之薄膜切斷裝置8’之平面圖。參考例之薄膜切斷裝置8’,係在第2切斷部8b,將於寬度方向上之下刀10b與上刀10a之間的位置關係,設為與第4圖相反,除此之外,係與第4圖之薄膜切斷裝置8相同的構成。也就是說,在參考例中,係成為下述構成:在第2切斷部8b,相對於下刀10b而於薄膜中央側配置上刀10a,並在與下刀10b之間而在薄膜中央側形成束角θ 1,並利用上刀10a與下刀10b將長條傾斜配向薄膜F’夾住並切斷。另外,束角θ 1之絕對值,係在第4圖和第5圖中設為相同。 Fig. 5 is a plan view of a film cutting device 8' of a reference example. The film cutting device 8' of the reference example is in the second cutting portion 8b, and the positional relationship between the lower blade 10b and the upper blade 10a in the width direction is opposite to that of the fourth figure. The same structure as the film cutting device 8 of Fig. 4. In other words, in the reference example, the upper cutting blade 10a is disposed on the center side of the film with respect to the lower blade 10b, and is disposed between the lower cutting blade 10b and the center of the film. The side forms a beam angle θ 1, and the upper obliquely directed film F' is sandwiched and cut by the upper blade 10a and the lower blade 10b. Further, the absolute value of the beam angle θ 1 is set to be the same in FIGS. 4 and 5 .
在參考例中,於第2切斷部8b,沿著上刀10a之面S的方向,係與長條傾斜配向薄膜F’之配向方向作大幅度交叉之方向。此時,若將長條傾斜配向薄膜F’之配向角(相對於寬度方向之配向方向所成之角度)設為(°),則在長條傾斜配向薄膜F’之薄膜面內,沿著面S之方向與配向方向之間所成的角度θ係為θ=(90°-)+θ 1。如此般,若角度θ為大,則長條傾斜配向薄膜F’之 傾斜方向的配向,在由第2切斷部8b所致之沿著長度方向所作的切斷時係會成為大的阻抗,於切斷時,長條傾斜配向薄膜F’係相對於第2切斷部8b(上刀10a、下刀10b)而相對性地成為易於被朝向配向方向彈開。其結果,長條傾斜配向薄膜F’的切斷狀態係會變差,在端部(切斷部)會產生鬚或起毛,並且在切斷時也會變得容易發生光學薄膜F之破斷。 In the reference example, the direction of the surface S of the upper blade 10a in the second cutting portion 8b is a direction in which the direction of the alignment of the long oblique alignment film F' greatly intersects. At this time, if the alignment angle of the long oblique alignment film F' (the angle formed by the alignment direction with respect to the width direction) is set (°), in the film plane of the strip-shaped oblique alignment film F', the angle θ formed between the direction along the plane S and the alignment direction is θ=(90°- ) + θ 1. When the angle θ is large, the alignment of the elongated oblique alignment film F′ in the oblique direction is a large impedance when the second cutting unit 8 b is cut along the longitudinal direction. At the time of cutting, the long inclined alignment film F' is relatively easily slid toward the alignment direction with respect to the second cutting portion 8b (the upper blade 10a and the lower blade 10b). As a result, the cut state of the long inclined alignment film F' is deteriorated, and whiskers or fuzzing are generated at the end portion (cut portion), and the breakage of the optical film F is also likely to occur at the time of cutting. .
相對於此,在第4圖之構成中,不論是在第1切斷部8a或在第2切斷部8b,均於薄膜面內,沿著上刀10a之面S的方向與長條傾斜配向薄膜F’之配向方向之間所成的角度θ係為θ=(90°-)-θ 1,而為較第5圖(參考例)之角度θ更小。也就是說,在第4圖之構成中,於寬度方向上,上刀10a,由於是相對於下刀10b而位置在更接近長條傾斜配向薄膜F’之配向方向之側,因此上述之角度θ係成為較第5圖之構成更小。 On the other hand, in the configuration of Fig. 4, both the first cutting portion 8a and the second cutting portion 8b are inclined in the direction of the surface S of the upper blade 10a in the film surface. The angle θ between the alignment directions of the alignment film F' is θ=(90°- ) - θ 1, which is smaller than the angle θ of Fig. 5 (reference example). That is, in the configuration of Fig. 4, in the width direction, the upper blade 10a is positioned closer to the alignment direction of the elongated oblique alignment film F' with respect to the lower blade 10b, so the above angle The θ system is smaller than the configuration of Fig. 5.
如此般,由於是使上刀10a位置在更靠近配向方向之側並切斷長條傾斜配向薄膜F’,因此長條傾斜配向薄膜F’之由傾斜方向之配向所致的切斷時之阻抗,相較於藉由第5圖之構成來切斷的情況係變得更小,於切斷時,係可對於長條傾斜配向薄膜F’相對於第1切斷部8a及第2切斷部8b而相對性地被朝向配向方向彈開的情形作抑制。其結果,係使長條傾斜配向薄膜F’的切斷狀態提昇,並能夠抑制在端部產生鬚或起毛,又,也能夠抑制切斷時之光學薄膜F之破斷。進而,由於係可對於長條傾斜 配向薄膜F’在切斷時而被朝向配向方向彈開的情形作抑制,因此可抑制切斷後之光學薄膜的傾斜前進,並可使捲取光學薄膜時的卷端面相互對齊,而可使捲取形態成為良好。 In this manner, since the upper blade 10a is positioned closer to the direction of the alignment direction and the long oblique alignment film F' is cut, the impedance of the elongated oblique alignment film F' due to the alignment in the oblique direction is obtained. It is smaller than the case of cutting by the configuration of Fig. 5, and it is possible to cut the oblique alignment film F' with respect to the first cutting portion 8a and the second cutting at the time of cutting. The portion 8b is relatively restrained from being bounced toward the alignment direction. As a result, the cut state of the long inclined alignment film F' is improved, and it is possible to suppress the occurrence of whiskers or fuzzing at the end portions, and also to suppress the breakage of the optical film F at the time of cutting. Furthermore, since the system can be tilted for long strips The alignment film F' is suppressed from being bounced in the alignment direction at the time of cutting, so that the tilting advancement of the optical film after the cutting can be suppressed, and the winding end faces when the optical film is taken up can be aligned with each other, and the roll can be rolled. Take the form to be good.
另外,本實施形態之長條傾斜配向薄膜,亦可為從擺動捲繞而成之長條薄膜的捲繞體將長條薄膜送出並朝相對於寬度方向傾斜的方向延伸而成之長條傾斜延伸薄膜。上述之擺動捲繞,係指一面使卷芯或薄膜之至少其中一方在寬度方向上作週期性的振動(oscillate),一面將薄膜捲取在卷芯上的手法。如此之擺動捲繞,係為了達成將被捲取的薄膜之結塊(薄膜彼此之相互貼附)或黑帶(black band,周方向上之帶狀的痕跡)的情形降低的目的,而進行者。 Further, the long obliquely oriented film of the present embodiment may be a long inclined body in which a long film is fed from a wound body of a long film which is wound and wound, and which is extended in a direction inclined with respect to the width direction. Extend the film. The above-described oscillating winding refers to a method of winding a film onto a winding core while causing at least one of the core or the film to periodically oscillate in the width direction. Such a wobble winding is performed for the purpose of reducing the agglomeration of the film to be wound up (the films are attached to each other) or the black band (the band in the circumferential direction). By.
被擺動捲繞的長條薄膜係在寬度方向之端部,存在有微小的膜厚偏差。其原因在於,在捲取狀態中,長條薄膜之端部中,於卷芯方向上超出的部位,並未被上下之薄膜按壓,於進入至卷芯方向之內側的部位,則會被上下之薄膜所按壓,因此如此之按壓之有無會成為在膜厚上的差異而顯現。 The long film which is oscillated and wound is attached to the end portion in the width direction, and there is a slight variation in film thickness. The reason for this is that, in the winding state, the portion of the end portion of the long film that is beyond the winding core direction is not pressed by the upper and lower films, and the portion that enters the inner side of the winding core direction is up and down. Since the film is pressed, the presence or absence of such a press will appear as a difference in film thickness.
在上刀10a與下刀10b之間的切斷位置(slitting point),若成為切斷對象之薄膜的膜厚變動,則起因於該膜厚之變動,於切斷時薄膜會成為更容易被朝向配向方向而彈開。因而,能夠藉由如第4圖中所示般之上刀10a及下刀10b之配置來對切斷時之長條傾斜配向薄 膜F’的朝向配向方向之彈開作抑制並使切割狀態提昇的本實施形態之切斷方法,在長條傾斜配向薄膜為將被擺動捲繞而成的長條薄膜進行傾斜延伸之長條傾斜配向薄膜的情況係非常有效。 When the film thickness of the film to be cut is changed at the slitting point between the upper blade 10a and the lower blade 10b, the film thickness becomes more likely to be changed at the time of cutting. Bounces toward the alignment direction. Therefore, it is possible to obliquely align the strips at the time of cutting by the arrangement of the upper blade 10a and the lower blade 10b as shown in Fig. 4 In the cutting method of the embodiment in which the opening of the film F' in the direction of the alignment is suppressed and the cutting state is improved, the long obliquely oriented film is a strip which is obliquely extended by the long film which is oscillated and wound. The case of tilting the alignment film is very effective.
又,脂環式烯烴聚合物系樹脂,相較於纖維素酯系樹脂,由於其脆性係為低,而為脆弱,因此在切斷部容易因切斷而產生鬚或起毛,又,於切斷時也容易發生光學薄膜F之破斷。因而,可使長條傾斜配向薄膜F’之切割狀態提昇的上述之本實施形態之切斷方法,在長條傾斜配向薄膜包含脂環式烯烴聚合物系樹脂並將該長條傾斜配向薄膜之兩端部切斷的情況係成為非常有效。 In addition, the alicyclic olefin polymer-based resin is weaker than the cellulose ester-based resin because it is low in brittleness, so that it is liable to be cut or fluffed in the cut portion, and is cut. The breaking of the optical film F is also likely to occur at the time of breaking. Therefore, the cutting method of the above-described embodiment in which the cutting state of the long inclined alignment film F' can be improved is such that the long obliquely oriented film contains the alicyclic olefin polymer resin and the strip is obliquely aligned to the film. It is very effective to cut both ends.
另外,第4圖中所示之束角θ 1,例如係只要在0°<θ 1<1°之間適當設定即可。又,上刀10a之刀鋒的角度θ 2,例如係只要在30°~60°之間適當設定即可。 Further, the beam angle θ 1 shown in Fig. 4 may be appropriately set as long as it is between 0 ° < θ 1 < 1 °. Further, the angle θ 2 of the blade edge of the upper blade 10a may be appropriately set, for example, between 30° and 60°.
另外,於以上內容中,雖將作為第1刀之下刀10b以使旋轉軸10b1沿著寬度方向的方式來配置,並將作為第2刀之上刀10a以使旋轉軸10a1相對於寬度方向而傾斜的方式來配置,但亦可與此相反地,將上刀10a以使旋轉軸10a1沿著寬度方向的方式來配置,並將下刀10b以使旋轉軸10b1相對於寬度方向而傾斜的方式來配置。也就是說,亦可將上刀10a作為第1刀來處理,並將下刀10b作為第2刀來處理。 In addition, in the above, the first blade lower blade 10b is disposed such that the rotation axis 10b 1 is along the width direction, and the second blade upper blade 10a is set such that the rotation axis 10a 1 is opposed to Arranged in a manner of being inclined in the width direction, but conversely, the upper blade 10a is disposed such that the rotating shaft 10a 1 is along the width direction, and the lower blade 10b is oriented such that the rotating shaft 10b 1 is opposite to the width Configure the direction and tilt. In other words, the upper blade 10a can be handled as the first blade, and the lower blade 10b can be handled as the second blade.
於本實施形態之長條傾斜配向薄膜中,較佳為,配向角θ係相對於捲取方向而以例如大於0°且未達90°之範圍傾斜,並至少在1300mm之寬幅中,寬度方向之面內遲滯Ro的參差為2nm以下,配向角θ之參差為未達0.6°。又,前述長條傾斜配向薄膜之以波長550nm所測定的面內遲滯值Ro(550),較佳為80nm以上160nm以下之範圍,更佳為90nm以上150nm以下之範圍。 In the strip-shaped oblique alignment film of the present embodiment, it is preferable that the alignment angle θ is inclined with respect to the winding direction in a range of, for example, more than 0° and less than 90°, and at least in a width of 1300 mm, and a width. The variation of the retardation Ro in the plane of the direction is 2 nm or less, and the deviation of the alignment angle θ is less than 0.6°. Further, the in-plane hysteresis value Ro (550) measured at a wavelength of 550 nm of the long oblique alignment film is preferably in the range of 80 nm or more and 160 nm or less, more preferably in the range of 90 nm or more and 150 nm or less.
亦即,於本實施形態之長條傾斜配向薄膜中,面內遲滯Ro的參差,係在寬幅方向之至少1300mm中而為2nm以下,較佳為1nm以下。藉由將面內遲滯Ro的參差設為上述範圍,在將從長條傾斜配向薄膜所取得的長條狀之光學薄膜與偏光元件作貼合而作成圓偏光板,並將此適用在有機EL畫像顯示裝置中時,係能夠抑制在黑顯示時之因外光反射光的漏洩所導致之顏色不均。又,在將上述光學薄膜例如作為液晶顯示裝置用之相位差薄膜來使用的情況,係亦成為可使顯示品質成為良好。 In other words, in the long oblique alignment film of the present embodiment, the variation of the in-plane retardation Ro is 2 nm or less, preferably 1 nm or less, in at least 1300 mm in the wide direction. By setting the variation of the in-plane retardation Ro to the above range, a long optical film obtained by elongating the oblique alignment film and a polarizing element are bonded together to form a circular polarizing plate, and this is applied to an organic EL. In the case of the image display device, color unevenness due to leakage of external light reflected light during black display can be suppressed. In addition, when the optical film is used as, for example, a retardation film for a liquid crystal display device, the display quality can be improved.
又,於本實施形態之長條傾斜配向薄膜中,配向角θ之參差,係在寬幅方向之至少1300m中而為未達0.6°,較佳為未達0.4°,最佳為未達0.2°。若將配向角θ之參差為超過0.6°的上述光學薄膜與偏光元件作貼合而作成圓偏光板,並將此安置在有機EL顯示裝置等之畫像顯示裝置中,則會產生光漏洩,而會有使明暗之對比降低的情形。 Further, in the long oblique alignment film of the present embodiment, the difference in the alignment angle θ is less than 0.6° in the width direction of at least 1300 m, preferably less than 0.4°, and most preferably less than 0.2. °. When the optical film having a difference in the alignment angle θ of more than 0.6° is bonded to the polarizing element to form a circularly polarizing plate, and this is placed in an image display device such as an organic EL display device, light leakage occurs. There will be situations where the contrast between light and dark is reduced.
本實施形態之長條傾斜配向薄膜的面內遲滯 Ro,係依據所使用之顯示裝置的設計來選擇最適值。另外,前述Ro,係對於面內遲相軸方向之折射率nx與在面內和前述遲相軸相正交之方向的折射率ny之間的差乘上薄膜之平均厚度d後的值(Ro=(nx-ny)×d)。 In-plane retardation of the long oblique alignment film of this embodiment Ro, according to the design of the display device used to select the optimum value. Further, the above Ro is a value obtained by multiplying the difference between the refractive index nx in the in-plane slow axis direction and the refractive index ny in the direction orthogonal to the in-plane and the late-phase axis by the average thickness d of the film ( Ro = (nx - ny) × d).
本實施形態之長條傾斜配向薄膜的平均厚度,就機械性強度等之觀點而言為1~400μm,較佳為10~200μm,更佳為10~60μm,特佳為15~45μm。 The average thickness of the elongated oblique alignment film of the present embodiment is from 1 to 400 μm, preferably from 10 to 200 μm, more preferably from 10 to 60 μm, particularly preferably from 15 to 45 μm, from the viewpoint of mechanical strength and the like.
本實施形態之長條傾斜配向薄膜亦可於其之表面上具有功能層。作為功能層係可考慮抗反射層、低折射率層、硬塗層、光散射層、光擴散層、抗靜電層、導電層、電極層、雙折射層、表面能量調整層、UV吸收層、色材層、耐水層、特定之氣體阻障層、耐熱層、磁性層、抗氧化層、保護塗層等。 The elongated oblique alignment film of this embodiment may also have a functional layer on the surface thereof. As the functional layer, an antireflection layer, a low refractive index layer, a hard coat layer, a light scattering layer, a light diffusion layer, an antistatic layer, a conductive layer, an electrode layer, a birefringent layer, a surface energy adjustment layer, a UV absorbing layer, A color material layer, a water resistant layer, a specific gas barrier layer, a heat resistant layer, a magnetic layer, an oxidation resistant layer, a protective coating, and the like.
本實施形態之圓偏光板係依序層合有偏光板保護薄膜、偏光元件、λ/4薄膜,λ/4薄膜之遲相軸與偏光元件之吸收軸(或是透射軸)之間所成的角度係為45°。λ/4薄膜,係可藉由將本實施形態之長條傾斜配向薄膜的兩端部切斷後所得到的光學薄膜(長條傾斜延伸薄膜)來構成。在將本實施形態之圓偏光板使用在有機EL顯示裝置中的情況,上述之偏光板保護薄膜、偏光元件、λ/4薄膜,係分別對應於第6圖之保護薄膜313、偏光元件311、λ/4薄膜316。於本實施形態中,較佳為,長條狀 偏光板保護薄膜、長條狀偏光元件、長條狀λ/4薄膜,係依此順序被層合形成。 In the circularly polarizing plate of the present embodiment, a polarizing plate protective film, a polarizing element, and a λ/4 film are laminated in this order, and a retardation axis of the λ/4 film and an absorption axis (or a transmission axis) of the polarizing element are formed. The angle is 45°. The λ/4 film can be formed by cutting an optical film (long obliquely extending film) obtained by cutting both ends of the long oblique alignment film of the present embodiment. In the case where the circularly polarizing plate of the present embodiment is used in an organic EL display device, the polarizing plate protective film, the polarizing element, and the λ/4 film are respectively corresponding to the protective film 313 and the polarizing element 311 of FIG. λ/4 film 316. In the present embodiment, it is preferably elongated A polarizing plate protective film, a long strip-shaped polarizing element, and a long strip-shaped λ/4 film are laminated in this order.
又,在將本實施形態之圓偏光板使用在液晶顯示裝置中的情況,上述之偏光板保護薄膜、偏光元件、λ/4薄膜,係分別對應於第7圖之保護薄膜506、偏光元件501、λ/4薄膜503。由於在顯示胞401之外側(視覺辨認側),係配置有保護薄膜506、偏光元件501,在偏光元件501之更外側(視覺辨認側),係配置有λ/4薄膜503,因此從顯示胞401所射出並透過偏光元件501之後的直線偏光,係藉由λ/4薄膜503而被轉換為圓偏光或橢圓偏光。因而,當觀察者裝著偏光墨鏡並對於顯示裝置400之顯示畫像作觀察的情況,不論是在以何種角度來作觀察的情況(不論偏光元件501之透射軸(與吸收軸相垂直)與偏光墨鏡之透射軸產生有何種程度之偏移),均可將與偏光墨鏡之透射軸相平行之光的成分導引至觀察者之眼睛並使其觀察到顯示畫像,而可抑制因觀察之角度而導致難以觀看到顯示畫像的情形。 In the case where the circularly polarizing plate of the present embodiment is used in a liquid crystal display device, the polarizing plate protective film, the polarizing element, and the λ/4 film are respectively corresponding to the protective film 506 and the polarizing element 501 of FIG. λ/4 film 503. The protective film 506 and the polarizing element 501 are disposed on the outer side (visual identification side) of the display cell 401, and the λ/4 film 503 is disposed on the outer side (visual identification side) of the polarizing element 501. The linearly polarized light that is emitted from 401 and transmitted through the polarizing element 501 is converted into circularly polarized light or elliptically polarized light by the λ/4 film 503. Therefore, when the observer wears the polarized sunglasses and observes the displayed image of the display device 400, regardless of the angle at which the observation is made (regardless of the transmission axis of the polarizing element 501 (perpendicular to the absorption axis) What is the degree of shift of the transmission axis of the polarized sunglasses? The components of the light parallel to the transmission axis of the polarized sunglasses can be guided to the observer's eyes and observed to be displayed, and the observation can be suppressed. The angle makes it difficult to see the case where the portrait is displayed.
本實施形態之圓偏光板,作為偏光元件,係可使用將摻雜有碘或二色性染料之聚乙烯醇作延伸者,並以λ/4薄膜/偏光元件之構成來貼合而製造。偏光元件之膜厚為5~40μm,較佳為5~30μm,特佳為5~20μm。 In the circularly polarizing plate of the present embodiment, a polarizing element can be produced by laminating a polyvinyl alcohol doped with iodine or a dichroic dye and bonding it with a λ/4 film/polarizing element. The film thickness of the polarizing element is 5 to 40 μm, preferably 5 to 30 μm, and particularly preferably 5 to 20 μm.
偏光板係可藉由一般的方法來製作。經鹼性鹼化處理的λ/4薄膜,較佳係在將聚乙烯醇系薄膜於碘系溶液中進行浸漬延伸所製作的偏光元件之其中一面上,使 用完全鹼化型聚乙烯醇水溶液來貼合。 The polarizing plate can be produced by a general method. The alkali-alkaline-treated λ/4 film is preferably one side of a polarizing element produced by immersing and stretching a polyvinyl alcohol-based film in an iodine-based solution. The solution was adhered with a fully alkalized aqueous polyvinyl alcohol solution.
偏光板係可進一步於該偏光板之偏光板保護薄膜的相反面上貼合剝離薄膜而構成。保護薄膜及剝離薄膜,係為了在偏光板之出貨時、製品檢查時等對於偏光板作保護的目的所使用。 The polarizing plate can be further formed by laminating a release film on the opposite surface of the polarizing plate protective film of the polarizing plate. The protective film and the release film are used for the purpose of protecting the polarizing plate during shipment of the polarizing plate or during product inspection.
第6圖係顯示本實施形態之作為OLED的有機EL顯示裝置100之概略的構成之剖面圖。另外,有機EL顯示裝置100之構成係並不限定於此。 Fig. 6 is a cross-sectional view showing a schematic configuration of an organic EL display device 100 as an OLED of the present embodiment. In addition, the configuration of the organic EL display device 100 is not limited to this.
有機EL顯示裝置100,係藉由在有機EL元件101上經由接著層201來形成圓偏光板301所構成。有機EL元件101,係在使用有玻璃或聚醯亞胺等的基板111上,依序具有金屬電極112、發光層113、透明電極(ITO等)114、密封層115所構成。另外,金屬電極112亦可藉由反射電極與透明電極所構成。 The organic EL display device 100 is configured by forming a circularly polarizing plate 301 on the organic EL element 101 via the adhesion layer 201. The organic EL element 101 is composed of a metal electrode 112, a light-emitting layer 113, a transparent electrode (ITO or the like) 114, and a sealing layer 115, on a substrate 111 using glass or polyimide. In addition, the metal electrode 112 may also be formed by a reflective electrode and a transparent electrode.
圓偏光板301,係從有機EL元件101側,依序層合有λ/4薄膜316、接著層315、偏光元件311、接著層312、保護薄膜313、硬化層314,偏光元件311係被λ/4薄膜316與保護薄膜313所挾持。藉由以使偏光元件311之透射軸與由本實施形態的光學薄膜所成之λ/4薄膜316之遲相軸之間所成的角度成為約45°(或者135°)的方式來將兩者貼合,而構成圓偏光板301。 The circular polarizing plate 301 is formed by laminating a λ/4 film 316, an adhesive layer 315, a polarizing element 311, an adhesive layer 312, a protective film 313, and a hardened layer 314 from the side of the organic EL element 101, and the polarizing element 311 is λ. The /4 film 316 is held by the protective film 313. The angle between the transmission axis of the polarizing element 311 and the slow axis of the λ/4 film 316 formed of the optical film of the present embodiment is about 45 (or 135). The circular polarizing plate 301 is formed by lamination.
在上述之保護薄膜313,較佳係被層合有硬化 層314。硬化層314,係不僅具有防止有機EL顯示裝置100之表面的損傷之功能,亦具有防止因圓偏光板301所導致的翹曲之效果。進而,在硬化層314上亦可形成有抗反射層。有機EL元件101自體之厚度為1μm左右。 In the above protective film 313, it is preferable to laminate and harden Layer 314. The hardened layer 314 not only has a function of preventing damage of the surface of the organic EL display device 100, but also has an effect of preventing warpage caused by the circular polarizing plate 301. Further, an anti-reflection layer may be formed on the hardened layer 314. The organic EL element 101 has a thickness of about 1 μm.
在上述之構成中,若對於金屬電極112與透明電極114施加電壓,則對於發光層113而從金屬電極112及透明電極114當中成為陰極之電極注入電子,並從成為陽極之電極注入電洞,藉由使兩者在發光層113進行再結合,而產生與發光層113之發光特性相對應的可見光線之發光。在發光層113產生的光,係成為直接地、或在被金屬電極112反射之後,經由透明電極114及圓偏光板301而取出至外部。 In the above-described configuration, when a voltage is applied to the metal electrode 112 and the transparent electrode 114, electrons are injected from the metal electrode 112 and the electrode serving as the cathode among the metal electrode 112 and the transparent electrode 114, and a hole is injected from the electrode serving as the anode. By recombining the two in the light-emitting layer 113, light emission of visible light rays corresponding to the light-emitting characteristics of the light-emitting layer 113 is generated. The light generated in the light-emitting layer 113 is directly or after being reflected by the metal electrode 112, and is taken out to the outside through the transparent electrode 114 and the circularly polarizing plate 301.
一般而言,於有機EL顯示裝置中,係在透明基板上依序層合金屬電極與發光層與透明電極,而形成作為發光體之元件(有機EL元件)。在此,發光層,係各種之有機薄膜的層合體,已知有例如以由三苯基胺衍生物等所成的電洞注入層與由蒽等之螢光性之有機固體所成的發光層之層合體、或是以如此之發光層與由苝衍生物等所成之電子注入層之層合體、或是此等之電洞注入層、發光層、電子注入層之層合體等具有各種組合之構成。 In an organic EL display device, a metal electrode, a light-emitting layer, and a transparent electrode are sequentially laminated on a transparent substrate to form an element (organic EL element) as an illuminant. Here, the light-emitting layer is a laminate of various organic thin films, and for example, a light-emitting layer formed of a triphenylamine derivative or the like and a fluorescent organic solid such as ruthenium are known. The laminate of the layers, or a laminate of such an emission layer and an electron injection layer made of an anthracene derivative or the like, or a laminate of the hole injection layer, the light-emitting layer, and the electron injection layer, etc. The composition of the combination.
有機EL顯示裝置,係藉由對於透明電極與金屬電極施加電壓,而將電洞與電子注入於發光層,並使經由此等之電洞與電子間的再結合所產生之能量激勵螢光物質,而當被激勵的螢光物質回復至基礎狀態時輻射出光, 根據此原理,而進行發光。途中再結合之機制,係與一般之二極體相同,如根據此而可推測到一般,電流與發光強度,係相對於施加電壓而展現有伴隨著整流性之強的非線形性。 An organic EL display device injects a hole and electrons into a light-emitting layer by applying a voltage to a transparent electrode and a metal electrode, and excites a fluorescent substance by energy generated by recombination between the holes and the electrons. And radiating light when the excited fluorescent substance returns to the basic state, According to this principle, light is emitted. The mechanism of recombination on the way is the same as that of a general diode. As a general matter, it can be inferred that the current and the intensity of light emission exhibit a nonlinearity accompanying the rectifying property with respect to the applied voltage.
於有機EL顯示裝置中,為了將在發光層之發光取出,至少其中一方之電極係必須為透明,通常係將藉由氧化銦錫(ITO)等之透明導電體所形成的透明電極作為陽極來使用。另一方面,為了使電子注入成為容易並提高發光效率,在陰極中使用功函數為小的物質一事係為重要,通常係使用Mg-Ag、Al-Li等之金屬電極。 In the organic EL display device, in order to extract the light emitted from the light-emitting layer, at least one of the electrode layers must be transparent, and a transparent electrode formed of a transparent conductor such as indium tin oxide (ITO) is usually used as an anode. use. On the other hand, in order to facilitate electron injection and improve luminous efficiency, it is important to use a substance having a small work function in the cathode, and a metal electrode such as Mg-Ag or Al-Li is usually used.
於此種構成之有機EL顯示裝置中,發光層係藉由厚度10nm左右之極薄的膜來形成。因此,發光層亦與透明電極相同地使光大致完全地透過。其結果,在非發光時從透明基板之表面射入並透過透明電極與發光層而在金屬電極反射之光,由於會再度朝向透明基板之表面側射出,因此在從外部進行視覺辨認時,有機EL顯示裝置之顯示面看起來會如同鏡面一般。 In the organic EL display device having such a configuration, the light-emitting layer is formed by an extremely thin film having a thickness of about 10 nm. Therefore, the light-emitting layer also transmits light substantially completely in the same manner as the transparent electrode. As a result, when light is emitted from the surface of the transparent substrate and transmitted through the transparent electrode and the light-emitting layer during non-light-emitting, the light reflected on the metal electrode is again emitted toward the surface side of the transparent substrate, so that when visually recognized from the outside, the organic light is organic. The display surface of the EL display device looks like a mirror.
本實施形態之圓偏光板,係適於如此之外光反射會特別成為問題的有機EL顯示裝置。 The circularly polarizing plate of the present embodiment is suitable for an organic EL display device in which light reflection is particularly problematic.
亦即,在有機EL元件101之非發光時,藉由室內照明等而從有機EL元件101之外部所射入的外光,係會藉由圓偏光板301之偏光元件311而使一半被吸收,剩餘的一半則作為直線偏光而透過,並射入至λ/4薄膜316中。由於是以使偏光元件311之透射軸與λ/4薄膜 316之遲相軸以45°(或者135°)交叉的方式作配置,因此射入至λ/4薄膜316中之光,係藉由透過λ/4薄膜316而被轉換為圓偏光。 In other words, when the organic EL element 101 is not emitting light, external light incident from the outside of the organic EL element 101 by indoor illumination or the like is half absorbed by the polarizing element 311 of the circular polarizing plate 301. The remaining half is transmitted as a linearly polarized light and injected into the λ/4 film 316. Because the transmission axis of the polarizing element 311 and the λ/4 film are The retardation axes of 316 are arranged at 45[deg.] (or 135[deg.]) crossing so that the light incident into the λ/4 film 316 is converted into circularly polarized light by transmission through the λ/4 film 316.
從λ/4薄膜316所射出的圓偏光,當藉由有機EL元件101之金屬電極112作鏡面反射時,相位會180度反轉,並作為反向之圓偏光而被反射。此反射光,由於是藉由射入至λ/4薄膜316中而被轉換為與偏光元件311之透射軸垂直(與吸收軸平行)的直線偏光,因此在偏光元件311被全部吸收,成為不會射出至外部。也就是說,藉由圓偏光板301,係能夠降低在有機EL元件101之外光反射。 When the circularly polarized light emitted from the λ/4 film 316 is specularly reflected by the metal electrode 112 of the organic EL element 101, the phase is inverted by 180 degrees and reflected as a reverse circularly polarized light. Since the reflected light is converted into linearly polarized light perpendicular to the transmission axis of the polarizing element 311 (parallel to the absorption axis) by being incident on the λ/4 film 316, the polarizing element 311 is completely absorbed, and is not Will be shot to the outside. In other words, by the circular polarizing plate 301, light reflection outside the organic EL element 101 can be reduced.
第7圖係顯示本實施形態之作為液晶顯示裝置的顯示裝置400之概略的構成之剖面圖。顯示裝置400,係在顯示胞401之其中一面側配置偏光板402而構成。 Fig. 7 is a cross-sectional view showing a schematic configuration of a display device 400 as a liquid crystal display device of the embodiment. The display device 400 is configured by arranging a polarizing plate 402 on one side of the display cell 401.
另外,在液晶顯示裝置的情況,顯示胞401,係可視為藉由一對之基板來將液晶層挾持的液晶胞。另外,在相對於液晶胞之與偏光板402相反側,係設置有以與偏光板402成為正交偏光鏡狀態配置之其他的偏光板、和對於液晶胞進行照明之背光,但於第7圖中,係將該等之圖示省略。 Further, in the case of a liquid crystal display device, the display cell 401 can be regarded as a liquid crystal cell in which a liquid crystal layer is held by a pair of substrates. Further, on the opposite side of the liquid crystal cell from the polarizing plate 402, another polarizing plate disposed in a state of being orthogonal to the polarizing plate 402 and a backlight for illuminating the liquid crystal cell are provided, but in FIG. In the middle, the illustrations of these are omitted.
又,顯示裝置400,亦可在相對於偏光板402之與顯示胞401相反側具有前窗403。前窗403,係成為 顯示裝置400之外裝覆蓋構件者,例如由覆蓋玻璃所構成。在前窗403與偏光板402之間,係填充有例如由紫外線硬化型樹脂所成之填充材404。當不存在有填充材404的情況,由於在前窗403與偏光板402之間形成有空氣層,因此因在前窗403及偏光板402與空氣層之間的界面之光的反射,會有使顯示畫像之視覺辨認性降低的情況。但,藉由上述之填充材404,由於在前窗403與偏光板402之間不會形成空氣層,因此能夠避免因在上述界面之光的反射所導致之顯示畫像之視覺辨認性的降低。 Further, the display device 400 may have a front window 403 on the side opposite to the display cell 401 with respect to the polarizing plate 402. Front window 403 The display device 400 is provided with a cover member, for example, made of a cover glass. Between the front window 403 and the polarizing plate 402, a filler 404 made of, for example, an ultraviolet curable resin is filled. When the filler 404 is not present, since an air layer is formed between the front window 403 and the polarizing plate 402, there is a reflection of light at the interface between the front window 403 and the polarizing plate 402 and the air layer. The case where the visibility of the displayed image is lowered. However, according to the filler 404 described above, since the air layer is not formed between the front window 403 and the polarizing plate 402, it is possible to avoid a decrease in visibility of the display image due to reflection of light at the interface.
偏光板402,係具有使既定之直線偏光透過的偏光元件501。在偏光元件501之其中一面側(與顯示胞401相反側),係經由接著層502,而依序層合有λ/4薄膜503、和由紫外線硬化型樹脂所成之硬化層504。又,在偏光元件501之另外一面側(顯示胞401側),係經由接著層505而貼合有保護薄膜506。 The polarizing plate 402 has a polarizing element 501 that transmits a predetermined linear polarized light. On one side of the polarizing element 501 (opposite to the display cell 401), a λ/4 film 503 and a hardened layer 504 made of an ultraviolet curable resin are laminated in this order via the adhesive layer 502. Further, on the other surface side (the side of the display cell 401) of the polarizing element 501, a protective film 506 is bonded via the adhesive layer 505.
偏光元件501,例如係藉由將聚乙烯醇薄膜以二色性色素來染色並進行高倍率延伸所得到者。偏光元件501,係在進行鹼性處理(亦稱為鹼化處理)之後,於其中一面側經由接著層502而貼合λ/4薄膜503,並於另外一面側經由接著層505而貼合保護薄膜506。 The polarizing element 501 is obtained, for example, by dyeing a polyvinyl alcohol film with a dichroic dye and extending it at a high magnification. The polarizing element 501 is subjected to alkaline treatment (also referred to as alkalization treatment), and then the λ/4 film 503 is bonded to the one surface side via the adhesive layer 502, and the other layer side is bonded and protected via the adhesive layer 505. Film 506.
接著層502、505,例如係由聚乙烯醇接著劑(PVA接著劑、漿糊)所成之層,但亦可為由紫外線硬化型之接著劑(UV接著劑)所成之層。此等之接著劑,在塗佈於接著面上的狀態時為液體,藉由在塗佈後乾燥或者 藉由紫外線照射而硬化,而將兩者作接著。也就是說,接著層502、505,係藉由從液狀之狀態變化,來分別將偏光元件501與λ/4薄膜503、偏光元件501與保護薄膜506進行接著。如此般,接著層502、505,在藉由從液狀之狀態變化而將兩者接著的觀點,係與不產生此種狀態變化而將兩者接著之黏著層(於基材之上具有黏著劑之薄片狀的黏著層)不同。 Next, the layers 502 and 505 are, for example, a layer formed of a polyvinyl alcohol adhesive (PVA adhesive, paste), but may be a layer formed of an ultraviolet curing type adhesive (UV adhesive). These adhesives are liquids when applied to the surface of the adhesive surface, by drying after coating or It is hardened by ultraviolet irradiation, and the two are followed. That is, the subsequent layers 502 and 505 are respectively connected to the λ/4 film 503, the polarizing element 501, and the protective film 506 by changing from the liquid state. In this way, the layers 502 and 505 are adhered to each other by the change from the state of the liquid, and the adhesive layer is adhered to the substrate. The flaky adhesive layer of the agent is different.
λ/4薄膜503,係對於透射光賦予波長之1/4程度的面內相位差之層,於本實施形態中,例如係包含纖維素系樹脂(纖維素系聚合物)。另外,λ/4薄膜503,亦可代替纖維素系聚合物而包含聚碳酸酯系樹脂(聚碳酸酯系聚合物),亦可包含環烯烴系樹脂(環烯烴系聚合物)。但,就耐藥品性之觀點而言,λ/4薄膜503,係以包含纖維素系聚合物或聚碳酸酯系聚合物為理想。 In the present embodiment, the λ/4 film 503 is a layer containing a cellulose resin (cellulose-based polymer). In addition, the λ/4 film 503 may contain a polycarbonate resin (polycarbonate polymer) instead of the cellulose polymer, and may also contain a cycloolefin resin (cycloolefin polymer). However, the λ/4 film 503 is preferably a cellulose-based polymer or a polycarbonate-based polymer from the viewpoint of chemical resistance.
λ/4薄膜503係厚度為10μm~70μm之薄膜的λ/4薄膜。又,λ/4薄膜503之遲相軸與偏光元件501之吸收軸間所成之角度(交叉角)為30°~60°,藉此,從偏光元件501而來之直線偏光,係藉由λ/4薄膜503而被轉換為圓偏光或橢圓偏光。 The λ/4 film 503 is a λ/4 film of a film having a thickness of 10 μm to 70 μm. Further, the angle (crossing angle) between the slow axis of the λ/4 film 503 and the absorption axis of the polarizing element 501 is 30° to 60°, whereby the linear polarization from the polarizing element 501 is caused by The λ/4 film 503 is converted into circularly polarized or elliptically polarized light.
硬化層504(亦稱為硬塗層),係藉由活性能量線硬化型樹脂(例如紫外線硬化型樹脂)所構成。 The hardened layer 504 (also referred to as a hard coat layer) is composed of an active energy ray-curable resin (for example, an ultraviolet curable resin).
保護薄膜506,例如係藉由由纖維素系樹脂(纖維素系聚合物)、丙烯酸樹脂、環狀聚烯烴(COP)、聚碳酸酯(PC)所成之光學薄膜而構成。保護 薄膜506,雖單作為保護偏光元件501之背面側的薄膜而設置,但亦可作為可兼作為具有所期望之光學補償功能的相位差薄膜之光學薄膜而設置。 The protective film 506 is composed of, for example, an optical film made of a cellulose resin (cellulose polymer), an acrylic resin, a cyclic polyolefin (COP), or a polycarbonate (PC). protection The film 506 is provided as a film for protecting the back side of the polarizing element 501, but may be provided as an optical film which can also serve as a retardation film having a desired optical compensation function.
另外,在液晶顯示裝置的情況,相對於顯示胞401(液晶胞)而被配置在與偏光板402相反側的其他之偏光板,係將偏光元件之表面藉由2個的光學薄膜來挾持而構成,但作為上述之偏光元件及光學薄膜,係可使用與偏光板402之偏光元件501及保護薄膜506相同者。 Further, in the case of the liquid crystal display device, the polarizing plate disposed on the opposite side of the polarizing plate 402 with respect to the display cell 401 (liquid crystal cell) is held by the two optical films. In the above-described polarizing element and optical film, the same as the polarizing element 501 and the protective film 506 of the polarizing plate 402 can be used.
在此,上述之偏光元件501及λ/4薄膜503,亦可分別為長條狀。於此情況,λ/4薄膜503之遲相軸,係以相對於λ/4薄膜503之長度方向而作30°~60°之傾斜為理想。於此情況,係可將長條狀之λ/4薄膜503設為藉由傾斜延伸所製作的卷狀之薄膜,並將其藉由所謂的卷對卷方式來與卷狀之偏光元件501貼合,而製作長條狀之偏光板402。因而,相較於藉由將薄膜片一次一枚地作貼合之批次式來製作偏光板402的情況,係能夠使生產性大幅地提昇,並且亦能夠使良率大幅地改善。 Here, the above-described polarizing element 501 and λ/4 film 503 may each be elongated. In this case, the retardation axis of the λ/4 film 503 is preferably 30° to 60° with respect to the longitudinal direction of the λ/4 film 503. In this case, the long λ/4 film 503 can be formed into a roll-shaped film which is formed by oblique stretching, and is attached to the roll-shaped polarizing element 501 by a so-called roll-to-roll method. In combination, a strip-shaped polarizing plate 402 is produced. Therefore, in the case where the polarizing plate 402 is produced by a batch type in which the film sheets are bonded one at a time, the productivity can be greatly improved, and the yield can be greatly improved.
另外,在λ/4薄膜503之接著層502側,亦可設置用以使λ/4薄膜503之接著性提昇的易接著層。易接著層,係藉由在λ/4薄膜503之接著層502側進行易接著處理而形成。作為易接著處理,係存在有電暈(放電)處理、電漿處理、火焰處理、ITRO處理、輝光處理、臭氧處理、底塗處理等,但只要實施其中之至少1種即可。此等之易接著處理當中,就生產性的觀點而言,作為易接 著處理,係以電暈處理、電漿處理為佳。 Further, on the side of the adhesive layer 502 of the λ/4 film 503, an easy-adhesion layer for improving the adhesion of the λ/4 film 503 may be provided. The easy-adhesion layer is formed by performing an easy-on process on the adhesive layer 502 side of the λ/4 film 503. Although it is easy to carry out the treatment, there are corona (discharge) treatment, plasma treatment, flame treatment, ITRO treatment, glow treatment, ozone treatment, primer treatment, and the like, but at least one of them may be carried out. These are easy to handle, as far as productivity is concerned, as an easy connection The treatment is preferably corona treatment or plasma treatment.
以下,雖針對本發明之具體的實施例進行說明,但本發明並不受此等實施例所限制。另外,以下,雖使用「份」或「%」之表記,但若無特別說明,則此等係表示「質量份」或「質量%」者。 Hereinafter, the specific embodiments of the present invention are described, but the present invention is not limited by the embodiments. In addition, the following is a description of "parts" or "%", unless otherwise stated, these are "mass parts" or "% by mass".
藉由以下之方法而製作長條薄膜1。另外,長條薄膜1,係為纖維素酯系樹脂。 The long film 1 was produced by the following method. Further, the long film 1 is a cellulose ester resin.
將以上藉由溶解器進行50分鐘攪拌混合之後,藉由Manton Gaulin來進行分散,而調製出微粒子分散液1。 The mixture was stirred and mixed by a dissolver for 50 minutes, and then dispersed by Manton Gaulin to prepare a fine particle dispersion 1.
基於以下之組成,一面在裝入二氯甲烷之溶解槽中充分進行攪拌,一面將上述微粒子分散液緩慢地作添加。進而,以使二次粒子之粒徑成為既定之大小的方式,來藉由磨碎機進行分散。將其藉由日本精線(股)製之FINE MET NF進行過濾,而調製出微粒子添加液1。 The fine particle dispersion was slowly added while sufficiently stirring in a dissolution tank filled with methylene chloride based on the following composition. Further, the secondary particles have a particle size of a predetermined size and are dispersed by a grinder. This was filtered by FINE MET NF manufactured by Nippon Seisaku Co., Ltd. to prepare a fine particle addition liquid 1.
調製出下述組成之摻雜劑。首先,在加壓溶解槽中添加二氯甲烷與乙醇。接著,在裝入有溶劑之加壓溶解槽中,將纖維素乙酸酯一面攪拌一面投入。將其進行加熱,並一面攪拌一面使其完全溶解,再將其使用安積濾紙(股)製之安積濾紙No.244來進行過濾,而調製出主摻雜液。其後,以成為下述之比率的方式,來將主摻雜液和各材料投入至密閉容器中,並一面攪拌一面使其溶解,而調製出摻雜劑。另外,糖酯化合物及酯化合物,係使用藉由以下之合成例所合成的化合物。 A dopant of the following composition is prepared. First, dichloromethane and ethanol were added to the pressure dissolution tank. Next, the cellulose acetate was charged while stirring in a pressure-dissolving tank filled with a solvent. This was heated, and the mixture was completely dissolved while stirring, and then filtered using an filter paper No. 244 made of a filter paper (manufactured) to prepare a main dope. Thereafter, the main dope and each material are placed in a sealed container so as to have a ratio described below, and the dopant is dissolved while stirring to prepare a dopant. Further, as the sugar ester compound and the ester compound, a compound synthesized by the following synthesis examples is used.
藉由以下之步驟而合成糖酯化合物。 The sugar ester compound is synthesized by the following steps.
在具備有攪拌裝置、回流冷卻器、溫度計及氮氣導入管之四口燒瓶中,裝入蔗糖34.2g(0.1莫耳)、苯甲酸酐180.8g(0.6莫耳)、吡啶379.7g(4.8莫耳),並在攪拌下,一面使從氮氣導入管導入之氮氣起泡一面昇溫,以70℃進行5小時酯化反應。 In a four-necked flask equipped with a stirring device, a reflux condenser, a thermometer, and a nitrogen introduction tube, 34.2 g (0.1 mol) of sucrose, 180.8 g (0.6 mol) of benzoic anhydride, and 379.7 g of pyridine (4.8 mol) were charged. The mixture was heated while bubbling nitrogen gas introduced from the nitrogen gas introduction tube while stirring, and the esterification reaction was carried out at 70 ° C for 5 hours.
接著,將燒瓶內減壓至4×102Pa以下,並以60℃餾除過剩的吡啶之後,將燒瓶內減壓至1.3×10Pa以下,並進行昇溫至120℃,而餾除苯甲酸酐、所生成之苯甲酸的大部分。 Next, the pressure in the flask was reduced to 4 × 10 2 Pa or less, and the excess pyridine was distilled off at 60 ° C, and then the pressure in the flask was reduced to 1.3 × 10 Pa or less, and the temperature was raised to 120 ° C to distill off the benzoic anhydride. Most of the benzoic acid produced.
最後,在所分取的甲苯層中添加水100g,以常溫進行30分鐘的水洗,之後,分取甲苯層,並在減壓下(4×102Pa以下),以60℃餾除甲苯,而得到了化合物A-1、A-2、A-3、A-4及A-5之混合物(糖酯化合物)。 Finally, 100 g of water was added to the toluene layer to be separated, and the mixture was washed with water at normal temperature for 30 minutes. Thereafter, the toluene layer was separated, and toluene was distilled off at 60 ° C under reduced pressure (4 × 10 2 Pa or less). A mixture of the compounds A-1, A-2, A-3, A-4 and A-5 (sugar ester compound) was obtained.
在對於所得到的混合物藉由HPLC及LC-MASS進行解析的結果,A-1為1.3質量%,A-2為13.4質量%,A-3為13.1質量%、A-4為31.7質量%、A-5為40.5質量%。平均取代度為5.5。 As a result of analyzing the obtained mixture by HPLC and LC-MASS, A-1 was 1.3% by mass, A-2 was 13.4% by mass, A-3 was 13.1% by mass, and A-4 was 31.7% by mass. A-5 was 40.5 mass%. The average degree of substitution is 5.5.
裝置:日本分光(股)製管柱烘箱(JASCO CO-965)、偵測器(JASCO UV-970-240nm)、泵(JASCO PU-980)、除氣機(JASCO DG-980-50) Device: Japan spectrophotometer (JASCO CO-965), detector (JASCO UV-970-240nm), pump (JASCO PU-980), degassing machine (JASCO DG-980-50)
管柱:Inertsil ODS-3粒徑5μm 4.6×250mm(GL Sciences(股)製) Column: Inertsil ODS-3 particle size 5μm 4.6×250mm (GL Sciences system
管柱溫度:40℃ Column temperature: 40 ° C
流速:1ml/min Flow rate: 1ml/min
移動相:THF(1%醋酸):H2O(50:50) Mobile phase: THF (1% acetic acid): H 2 O (50:50)
注入量:3μl Injection volume: 3μl
裝置:LCQ DECA(Thermo Quest(股份有限公司)製) Device: LCQ DECA (Thermo Quest (manufactured by Thermo Quest)
離子化法:電噴灑游離化(ESI)法 Ionization method: electrospray ionization (ESI) method
Spray Voltage:5kV Spray Voltage: 5kV
Capillary溫度:180℃ Capillary temperature: 180 ° C
Vaporizer溫度:450℃ Vaporizer temperature: 450 ° C
藉由以下之步驟而合成酯化合物。 The ester compound is synthesized by the following steps.
將1,2-丙二醇251g、鄰苯二甲酸酐278g、己二酸91g、苯甲酸610g、作為酯化觸媒之鈦酸四異丙酯0.191g,裝入至具備有溫度計、攪拌器、緩急冷卻管之2L的四口燒瓶中,並在氮氣氣流中一面緩慢地攪拌一面昇溫至成為230℃為止。進行15小時之脫水縮合反應,反應結束後,以200℃將未反應之1,2-丙二醇作減壓餾除,藉此而得到酯化合物。酯化合物,係在使1,2-丙二醇、鄰苯二甲酸酐及己二酸縮合所形成的聚酯鏈之末端具有苯甲酸 之酯。酯化合物之酸價為0.10,數量平均分子量為450。 251 g of 1,2-propanediol, 278 g of phthalic anhydride, 91 g of adipic acid, 610 g of benzoic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst were placed in a thermometer, a stirrer, and a buffer. In a 2-L four-necked flask of a cooling tube, the temperature was raised to 230 ° C while slowly stirring in a nitrogen gas stream. The dehydration condensation reaction was carried out for 15 hours, and after completion of the reaction, the unreacted 1,2-propanediol was distilled off under reduced pressure at 200 ° C to obtain an ester compound. An ester compound having benzoic acid at the end of a polyester chain formed by condensing 1,2-propanediol, phthalic anhydride, and adipic acid Ester. The ester compound had an acid value of 0.10 and a number average molecular weight of 450.
接著,使用無端輸送帶流延裝置,在由不鏽鋼輸送帶所成之支持體上將摻雜劑均勻地流延。接著,在支持體上,使溶劑蒸發直至流延(鑄造)所成的帶中之殘留溶劑量成為75%為止,並將帶從支持體上剝離,再一面藉由多數之輥來進行搬送一面使乾燥結束,而得到寬幅1500mm、膜厚50μm之長條薄膜1。所製造的長條薄膜1,係藉由捲取裝置而以直線捲繞來進行捲取,並在沿著寬度方向而一旦切斷之後,藉由捲取裝置來以擺動捲繞而進行捲取。將對於長條薄膜1以直線捲繞來進行捲取者設為卷狀態1,並將對於長條薄膜1以擺動捲繞來進行捲取者設為捲繞體2。 Next, the dopant was uniformly cast on the support made of the stainless steel conveyor belt using an endless belt casting device. Next, the solvent was evaporated on the support until the amount of residual solvent in the tape formed by casting (casting) was 75%, and the tape was peeled off from the support, and then transferred by a plurality of rolls. The drying was completed to obtain a long film 1 having a width of 1500 mm and a film thickness of 50 μm. The manufactured long film 1 is wound by linear winding by a winding device, and is wound by a winding device after being wound once in the width direction. . When the long film 1 is wound in a straight line, the winding is performed in a roll state 1, and the wound film 2 is wound by winding the long film 1 in a wrap.
藉由以下之方法而製作長條薄膜2。另外,長條薄膜2,係為脂環式烯烴聚合物系樹脂(COP樹脂)。 The long film 2 was produced by the following method. Further, the long film 2 is an alicyclic olefin polymer resin (COP resin).
在氮環境下,於脫水後的環己烷500份中,將1-己烯1.2份、二丁基醚0.15份、三異丁基鋁0.30份在室溫裝入反應器中,進行混合之後,一邊保持在45℃,一邊花費2小時連續添加由三環[4.3.0.12,5]癸-3,7-二烯(二環戊二烯,以下,簡記為DCP)20份、1,4-甲撐-1,4,4a,9a-四氫茀(以下,簡記為MTF)140份、及 8-甲基-四環[4.4.0.12,5.17,10]-十二碳-3-烯(以下,簡記為MTD)40份所成之降莰烯系單體混合物、與六氯化鎢(0.7%甲苯溶液)40份,並進行聚合。於聚合溶液中添加丁基環氧丙基醚1.06份與異丙醇0.52份,使聚合觸媒惰性化,來停止聚合反應。 In a nitrogen atmosphere, 1.2 parts of 1-hexene, 0.15 parts of dibutyl ether, and 0.30 parts of triisobutylaluminum were charged into a reactor at room temperature in 500 parts of cyclohexane after dehydration, and mixed. While maintaining the temperature at 45 ° C, it was added continuously for 2 hours from the tricyclo [4.3.0.12,5]癸-3,7-diene (dicyclopentadiene, hereinafter, abbreviated as DCP) 20 parts, 1, 4 -methyl-1,4,4a,9a-tetrahydroanthracene (hereinafter, abbreviated as MTF) 140 parts, and 4-methyl-tetracyclo[4.4.0.12, 5.17,10]-dodec-3-ene (hereinafter abbreviated as MTD) 40 parts of a decene-based monomer mixture, and tungsten hexachloride ( 40 parts of a 0.7% toluene solution and polymerization was carried out. 1.06 parts of butyl epoxidized propyl ether and 0.52 parts of isopropyl alcohol were added to the polymerization solution to inertize the polymerization catalyst to stop the polymerization reaction.
接著,對於含有所得到的開環聚合物之反應溶液100份,添加環己烷270份,進而,作為氫化觸媒而添加鎳-氧化鋁觸媒(日揮化學公司製)5份,再藉由氫加壓至5MPa而一面攪拌一面加溫至溫度200℃後,進行4小時反應,而得到含有20%之DCP/MTF/MTD開環聚合物氫化聚合物之反應溶液。在藉由過濾而將氫化觸媒去除之後,將軟質聚合物(KURARAY公司製;SEPTON2002)及抗氧化劑(Ciba Specialty Chemicals公司製;IRGANOX1010)分別添加至所得到的溶液中並使其溶解(均為聚合物每100份為0.1份)。 Then, 270 parts of cyclohexane was added to 100 parts of the reaction solution containing the obtained ring-opening polymer, and further, 5 parts of a nickel-alumina catalyst (manufactured by Nippon Chemical Co., Ltd.) was added as a hydrogenation catalyst, and The hydrogen was pressurized to 5 MPa, and the mixture was heated to a temperature of 200 ° C while stirring, and then reacted for 4 hours to obtain a reaction solution containing 20% of a DCP/MTF/MTD ring-opening polymer hydrogenated polymer. After the hydrogenation catalyst was removed by filtration, a soft polymer (manufactured by KURARAY Co., Ltd.; SEPTON 2002) and an antioxidant (manufactured by Ciba Specialty Chemicals Co., Ltd.; IRGANOX 1010) were separately added to the obtained solution and dissolved (both of them). The polymer was 0.1 part per 100 parts).
接著,使用圓筒型濃縮乾燥器(日立製作所製)將作為溶劑之環己烷及其他之揮發性成分從溶液中去除,並將氫化聚合物以熔融狀態來從押出機押出為股(Strand)狀,並且在冷卻後進行鑄錠化來回收。在由聚合後之溶液中的殘留降莰烯類組成(由氣相層析法所得)來計算聚合物中之各降莰烯系單體的共聚合比率的結果為DCP/MTF/MTD=10/70/20,而與所裝入之組成大致相等。此開環聚合物氫化物之重量平均分子量(Mw)為31,000,分子量分布(Mw/Mn)為2.5,氫化率為99.9%, Tg為134℃。將所得到的開環聚合物氫化物之鑄錠,使用讓空氣流通的熱風乾燥器來以70℃進行2小時乾燥,而將水分去除。 Next, cyclohexane and other volatile components as a solvent are removed from the solution using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), and the hydrogenated polymer is extruded from the extruder into a strand in a molten state. It is shaped and is ingot after cooling to be recovered. The result of calculating the copolymerization ratio of each of the norbornene-based monomers in the polymer from the residual norbornene composition (obtained by gas chromatography) in the solution after polymerization was DCP/MTF/MTD=10. /70/20, which is approximately equal to the composition loaded. The ring-opening polymer hydride has a weight average molecular weight (Mw) of 31,000, a molecular weight distribution (Mw/Mn) of 2.5, and a hydrogenation rate of 99.9%. The Tg was 134 °C. The ingot of the obtained hydrogenated ring-opening polymer was dried at 70 ° C for 2 hours using a hot air dryer through which air was passed, to remove moisture.
接著,將前述鑄錠,使用具有衣架模頭(Coat hanger)型之T模的短軸押出機(三菱重工業股份有限公司製:螺桿直徑90mm、T模唇部材質為碳化鎢、與熔融樹脂間的剝離強度為44N)來進行熔融押出成形而製造出作為環烯烴聚合物薄膜的長條薄膜2(膜厚30μm)。押出成形,係在10,000級以下的無塵室內,以熔融樹脂溫度240℃、T模溫度240℃的成形條件來進行。所製造的長條薄膜2,係藉由捲取裝置以直線捲繞來進行捲取,並在沿著寬度方向而一旦切斷之後,藉由捲取裝置來以擺動捲繞而進行了捲取。將對於長條薄膜2以直線捲繞來進行捲取者設為卷狀態3,將對於長條薄膜2以擺動捲繞來進行捲取者設為捲繞體4。 Next, the ingot was subjected to a short-axis extruder having a T-die of a coat hanger type (manufactured by Mitsubishi Heavy Industries Co., Ltd.: a screw diameter of 90 mm, a T-die lip material made of tungsten carbide, and a molten resin) The peeling strength was 44 N), and the melt-extrusion molding was carried out to produce a long film 2 (film thickness: 30 μm) as a cycloolefin polymer film. The extrusion molding was carried out in a clean room of 10,000 or less, and was carried out under the molding conditions of a molten resin temperature of 240 ° C and a T-die temperature of 240 ° C. The manufactured long film 2 is wound by a winding device in a straight line, and is wound up by a winding device after being wound in the width direction. . The winding film 3 is wound in a straight line for winding the long film 2, and the winding body 4 is obtained by winding the long film 2 in a wobble.
將由纖維素酯系樹脂所成的長條薄膜1之捲繞體1(作直線捲繞者),安裝於第1圖之製造裝置1的薄膜送出部2,並從薄膜送出部2來將長條薄膜1送出,供給至延伸部5並進行傾斜延伸,而得到長條傾斜配向薄膜(長條傾斜延伸薄膜)1。此時,在延伸部5,係以使薄膜之配向角(遲相軸與寬度方向間所成之角度)成為略45°的方式,來進行傾斜延伸。此時之薄膜的搬送速度係設為 15m/分鐘。又,長條傾斜配向薄膜1之膜厚係35μm。 The wound body 1 (linearly wound) of the long film 1 made of a cellulose ester resin is attached to the film feeding portion 2 of the manufacturing apparatus 1 of Fig. 1 and is long from the film feeding portion 2 The strip film 1 is fed out, supplied to the extending portion 5, and stretched obliquely to obtain a long oblique alignment film (long obliquely extending film) 1. At this time, in the extension portion 5, the alignment angle of the film is made (An angle formed between the late phase axis and the width direction) is slightly 45°, and the tilting is performed. The conveying speed of the film at this time was set to 15 m/min. Further, the film thickness of the elongated oblique alignment film 1 was 35 μm.
接著,將藉由在延伸部5之傾斜延伸所取得的長條傾斜配向薄膜1,供給至第4圖中所示之薄膜切斷裝置8,並將長條傾斜配向薄膜1之寬度方向的兩端部切斷,而取得成為製品部之光學薄膜1。另外,在第4圖之薄膜切斷裝置8,束角θ 1,在第1切斷部8a係於IN側(薄膜內側)而設為0.01°,在第2切斷部8b係於OUT側(薄膜外側)而設為0.01°,角度θ 2係設為40°。所取得的光學薄膜1,係藉由薄膜捲取部9而被捲取於卷芯上。 Next, the elongated oblique alignment film 1 obtained by the oblique extension of the extending portion 5 is supplied to the film cutting device 8 shown in Fig. 4, and the two strips are obliquely aligned to the width direction of the film 1. The end portion was cut to obtain the optical film 1 which was a product portion. Further, in the film cutting device 8 of Fig. 4, the toe angle θ1 is set to 0.01° on the IN side (inside of the film) in the first cutting portion 8a, and is on the OUT side in the second cutting unit 8b. The outer side of the film was set to 0.01°, and the angle θ 2 was set to 40°. The obtained optical film 1 is wound up on a winding core by a film take-up portion 9.
將由纖維素酯系樹脂所成的長條薄膜1之捲繞體2(作擺動捲繞者),安裝於薄膜送出部2,並將長條薄膜1送出,藉由延伸部5來進行傾斜延伸,而得到長條傾斜配向薄膜2,之後,藉由第4圖之薄膜切斷裝置8來將薄膜之兩端部切斷,而取得成為製品部之光學薄膜2。除此之外,係與光學薄膜1之製作相同。 The wound body 2 (swing wrap) of the long film 1 made of a cellulose ester resin is attached to the film feed portion 2, and the long film 1 is fed out, and the stretched portion 5 is used to perform oblique extension. Then, the long oblique alignment film 2 is obtained, and then the both ends of the film are cut by the film cutting device 8 of Fig. 4, and the optical film 2 serving as the product portion is obtained. Other than that, it is the same as that of the optical film 1.
將由COP樹脂所成的長條薄膜2之捲繞體3(作直線捲繞者),安裝於薄膜送出部2,並將長條薄膜2送出,藉由延伸部5來進行傾斜延伸,而得到長條傾斜配向薄膜3,之後,藉由第4圖之薄膜切斷裝置8來將薄膜之兩端 部切斷,而取得成為製品部之光學薄膜3。除此之外,係與光學薄膜1之製作相同。 The wound body 3 of the long film 2 made of the COP resin (for linear winding) is attached to the film feeding portion 2, and the long film 2 is fed out, and the extending portion 5 is obliquely extended to obtain The strip is inclined to the alignment film 3, and then the ends of the film are separated by the film cutting device 8 of Fig. 4. The part is cut, and the optical film 3 which becomes a product part is acquired. Other than that, it is the same as that of the optical film 1.
將由COP樹脂所成的長條薄膜2之捲繞體4(作擺動捲繞者),安裝於薄膜送出部2,並將長條薄膜2送出,藉由延伸部5來進行傾斜延伸,而得到長條傾斜配向薄膜4,之後,藉由第4圖之薄膜切斷裝置8來將薄膜之兩端部切斷,而取得成為製品部之光學薄膜4。除此之外,係與光學薄膜1之製作相同。 The wound body 4 (swing wrap) of the long film 2 made of the COP resin is attached to the film feeding portion 2, and the long film 2 is fed out, and the extending portion 5 is obliquely extended to obtain After the long film is inclined to the alignment film 4, the film cutting device 8 of Fig. 4 cuts both end portions of the film to obtain the optical film 4 serving as the product portion. Other than that, it is the same as that of the optical film 1.
將由纖維素酯系樹脂所成的長條薄膜1之捲繞體1(作直線捲繞者),安裝於薄膜送出部2,並將長條薄膜1送出,藉由延伸部5來進行傾斜延伸,而得到長條傾斜配向薄膜5,之後,藉由第5圖之薄膜切斷裝置8’來將薄膜之兩端部切斷,而取得成為製品部之光學薄膜5。除此之外,係與光學薄膜1之製作相同。另外,在第5圖之薄膜切斷裝置8’,束角θ 1,在第1切斷部8a及第2切斷部,係均為於IN側(薄膜內側)而設為-0.01°,角度θ 2係設為40°。 The wound body 1 of the long film 1 made of a cellulose ester resin (for linear winding) is attached to the film feeding portion 2, and the long film 1 is fed out, and the extending portion 5 is obliquely extended. Then, the long oblique alignment film 5 is obtained, and then the both ends of the film are cut by the film cutting device 8' of Fig. 5, and the optical film 5 serving as the product portion is obtained. Other than that, it is the same as that of the optical film 1. Further, in the film cutting device 8' of Fig. 5, the toe angle θ1 is set to -0.01° on the IN side (inside of the film) in the first cutting portion 8a and the second cutting portion. The angle θ 2 is set to 40°.
將由纖維素酯系樹脂所成的長條薄膜1之捲繞體2 (作擺動捲繞者),安裝於薄膜送出部2,並將長條薄膜1送出,藉由延伸部5來進行傾斜延伸,而得到長條傾斜配向薄膜6,之後,藉由第5圖之薄膜切斷裝置8’來將薄膜之兩端部切斷,而取得成為製品部之光學薄膜6。除此之外,係與光學薄膜5之製作相同。 Winding body 2 of long film 1 made of cellulose ester resin (Swing wrap), attached to the film feeding portion 2, and the long film 1 is fed out, and the extending portion 5 is obliquely extended to obtain the long oblique alignment film 6, and then, by the fifth figure The film cutting device 8' cuts both end portions of the film to obtain the optical film 6 which is a product portion. Other than that, it is the same as that of the optical film 5.
在光學薄膜1之製作中,束角θ 1,在第1切斷部8a係於IN側(薄膜內側)而設為0.5°,在第2切斷部8b係於OUT側(薄膜外側)而設為0.5°,角度θ 2係設為40°。除此之外,係與光學薄膜1之製作相同,而取得光學薄膜7。 In the production of the optical film 1, the beam angle θ1 is set to 0.5° on the IN side (inside of the film) in the first cut portion 8a, and is on the OUT side (outside the film) in the second cut portion 8b. Set to 0.5° and the angle θ 2 is set to 40°. Other than this, the optical film 7 was obtained in the same manner as the production of the optical film 1.
在各光學薄膜1~6之兩端部(切斷部),以目視來觀察鬚(鬚狀之纖維狀異物)之有無,並根據以下之基準來評估兩端部之狀態。 The presence or absence of the whisker-like fibrous foreign matter was visually observed at both end portions (cut portions) of the respective optical films 1 to 6, and the state of both end portions was evaluated based on the following criteria.
○:無鬚。 ○: No need.
×:有鬚。 ×: There is a need.
在各光學薄膜1~6之兩端部,以目視來觀察起毛之 有無,並根據以下之基準來評估兩端部之狀態。 At both ends of each of the optical films 1 to 6, the hair was observed by visual observation. Whether or not there is, and the status of both ends is evaluated based on the following criteria.
○:無起毛。 ○: No fluffing.
×:有起毛。 ×: There is fluffing.
以目視來觀察各光學薄膜1~6之兩端部,並根據以下之基準來評估切割狀態之良否。 The both end portions of each of the optical films 1 to 6 were visually observed, and the quality of the cut state was evaluated based on the following criteria.
○:切割狀態為相當良好,而沒有破斷之虞。 ○: The cutting state is quite good without breaking.
△:切割狀態為大致良好,而沒有破斷之虞。 △: The cutting state was substantially good without breaking.
×:切割狀態為不良,而有破斷之虞。 ×: The cutting state is bad, and there is a break.
表1係顯示針對各光學薄膜1~6之評估的結果。另外,於表1中,CE係指纖維素酯系樹脂,COP係指脂環式烯烴聚合物系樹脂。 Table 1 shows the results of evaluation for each of the optical films 1 to 6. In addition, in Table 1, CE means a cellulose ester type resin, and COP means an alicyclic olefin polymer type resin.
根據表1,可以得知,於光學薄膜5及6中,係於端部至少確認到起毛,並且端部之切割狀態亦為不良,相對於此,於光學薄膜1~4及7中,於端部並沒有鬚及起毛之發生,並且關於端部之切割狀態也可得到大致良好的結果。可推測到,其原因在於,在得到光學薄膜1~4及7時,由於使薄膜切斷裝置8之上刀10a相對於下刀10b而位在更靠近配向方向之側並切斷長條傾斜配向薄膜F’,因此長條傾斜配向薄膜F’之由傾斜方向之配向所致的切斷時之阻抗變小,於切斷時,長條傾斜配向薄膜F’係變得難以被彈開,其結果,切割狀態提昇,鬚或起毛之發生係被抑制。 According to Table 1, it can be seen that in the optical films 5 and 6, at least the fluffing was confirmed at the end portion, and the cut state of the end portion was also poor, whereas in the optical films 1 to 4 and 7, There is no need for the end of the hair to occur, and the cutting state of the end can also give a generally good result. It is presumed that the reason is that when the optical films 1 to 4 and 7 are obtained, the blade 10a of the film cutting device 8 is positioned closer to the alignment direction with respect to the lower blade 10b, and the long inclination is cut. Since the alignment film F' is disposed, the impedance of the elongated oblique alignment film F' at the time of cutting due to the alignment in the oblique direction becomes small, and the long oblique alignment film F' becomes difficult to be bounced at the time of cutting. As a result, the cutting state is increased, and the occurrence of hairiness or fuzzing is suppressed.
又,若在將被擺動捲繞的長條薄膜進行傾斜延伸之後,將薄膜之兩端部切斷,則會因為由擺動捲繞所致之膜厚偏差的影響,薄膜在切斷時係成為容易朝向配向方向彈開,此乃如先前所陳述。但,可推測到,藉由使用第4圖之構成的薄膜切斷裝置8來將薄膜切斷,由於薄膜之朝向配向方向的彈開係被抑制,因此在光學薄膜2、4,切割狀態之惡化係被抑制於最小限度,而能夠將切割狀態維持在大致良好。因而,使用第4圖之薄膜切斷裝置8來將薄膜切斷之方法,可以說特別是在將被擺動捲繞的長條薄膜進行傾斜延伸之後再將薄膜之兩端部切斷的情況係非常有效。 Further, when the long film which is oscillated and wound is obliquely stretched, and the both end portions of the film are cut, the film thickness is changed by the influence of the film thickness variation caused by the wobble winding. It is easy to bounce toward the alignment direction as previously stated. However, it is presumed that the film is cut by the film cutting device 8 having the configuration shown in Fig. 4, and since the film opening direction of the film in the alignment direction is suppressed, the optical films 2, 4 are cut. The deterioration is suppressed to a minimum, and the cutting state can be maintained substantially good. Therefore, the method of cutting the film by using the film cutting device 8 of Fig. 4 can be said to be particularly the case where the both ends of the film are cut after the elongated film which is oscillated and wound is obliquely extended. very effective.
又,COP樹脂,由於較纖維素酯系樹脂更脆弱,因此在切斷時容易發生鬚或起毛,並且也容易發生切 斷時之破斷,但包含COP樹脂之光學薄膜3及4的結果,由於與包含纖維素酯系樹脂之光學薄膜1及2的結果同等,因此可以說,使用第4圖之薄膜切斷裝置8來將薄膜切斷之方法,特別是在將包含COP樹脂之長條傾斜配向薄膜的兩端部切斷的情況係非常有效。 Further, since the COP resin is more fragile than the cellulose ester-based resin, it is liable to cause whisking or fuzzing at the time of cutting, and is also prone to cut. In the case of breaking the time, the results of the optical films 3 and 4 containing the COP resin are the same as those of the optical films 1 and 2 containing the cellulose ester resin. Therefore, it can be said that the film cutting device of Fig. 4 is used. The method of cutting the film is particularly effective in the case where the both ends of the long oblique alignment film containing the COP resin are cut.
又,根據光學薄膜1、7之結果,由於若束角θ 1越增大,則切割狀態之評估便會產生一個階段的惡化,因此可以說束角θ 1係以越小為越理想。 Further, as a result of the optical films 1 and 7, as the beam angle θ 1 increases, the evaluation of the cutting state is deteriorated in one stage. Therefore, it can be said that the beam angle θ 1 is preferably as small as possible.
另外,在以上說明中,雖針對將配向角為略45°之長條傾斜配向薄膜切斷的例子來進行說明,但確認到,即使配向角為略45°以外之角度,藉由使用與本實施形態相同之切斷方法,而可得到與本實施形態相同之效果。 In addition, in the above description, although the alignment angle is An example in which the oblique alignment film is cut off slightly 45° is described, but it is confirmed that even the alignment angle The angle similar to that of the present embodiment can be obtained at an angle other than 45°, and the same effects as those of the embodiment can be obtained.
另外,在以上說明中,雖針對使用包含纖維素酯系樹脂或COP樹脂之長條傾斜配向薄膜的例子來進行說明,但確認到,即使在將包含其他之樹脂(例如聚碳酸酯系樹脂、丙烯酸系樹脂)的長條傾斜配向薄膜作為切斷對象的情況,藉由使用與本實施形態相同之切斷方法,而可得到與本實施形態相同之效果。 In the above description, an example in which a long oblique alignment film including a cellulose ester resin or a COP resin is used has been described. However, it has been confirmed that other resins (for example, polycarbonate resins, When the long oblique alignment film of the acrylic resin is used as the object to be cut, the same effect as that of the present embodiment can be obtained by using the cutting method similar to that of the present embodiment.
以上所說明的本實施形態之光學薄膜之製造方法及製造裝置,係可如以下般地表現。 The method and apparatus for producing an optical film of the present embodiment described above can be expressed as follows.
1.一種光學薄膜之製造方法,係具有將長條傾斜配向薄膜之寬度方向的兩端部分別藉由第1切斷部及第2切斷部進行切斷的切斷步驟,前述長條傾斜配向薄膜在 薄膜面內相對於前述寬度方向的配向方向是傾斜的,取前述長條傾斜配向薄膜當中將前述兩端部切斷後剩餘的部分作為光學薄膜,其特徵在於,前述第1切斷部及前述第2切斷部分別含有第1刀及第2刀,前述第1刀,係配置於前述長條傾斜配向薄膜之薄膜面的一側,且將旋轉軸配置成沿著前述寬度方向;前述第2刀,係配置於前述薄膜面之另一側,在前述薄膜面內,以與相對於前述第1刀之束角對應的角度,使旋轉軸相對於前述寬度方向傾斜;在前述切斷步驟,在前述第1切斷部及前述第2切斷部各個,於前述第1刀之前述寬度方向的一側及另一側當中,隨著朝相對於前述第1刀的束角增大的方向將前述第2刀傾斜,在前述第2刀之形成前述束角的面和前述長條傾斜配向薄膜之前述配向方向所形成的角度變小的側配置前述第2刀,利用前述第1刀和前述第2刀將前述長條傾斜配向薄膜夾住並切斷。 1. A method for producing an optical film, comprising: a cutting step of cutting both end portions in a width direction of a long oblique alignment film by a first cutting portion and a second cutting portion, wherein the long inclination Alignment film The alignment direction of the film in the width direction is inclined, and the remaining portion of the long oblique alignment film is the optical film, and the first cutting portion and the first portion are Each of the cutting portions includes a first blade and a second blade, and the first blade is disposed on one side of the film surface of the long oblique alignment film, and the rotation axis is disposed along the width direction; a knife disposed on the other side of the film surface, wherein the rotation axis is inclined with respect to the width direction at an angle corresponding to a toe angle of the first blade in the film surface; and in the cutting step, Each of the first cutting portion and the second cutting portion increases in a direction toward a toe angle with respect to the first blade in one side and the other side in the width direction of the first blade. The second blade is inclined, and the second blade is disposed on a side where the angle formed by the surface of the second blade forming the toe angle and the alignment direction of the long oblique alignment film is small, and the first blade and the first blade are used. The aforementioned second knife will be long The strip oblique alignment film is clamped and cut.
2.如前述1所述之光學薄膜之製造方法,其中,前述長條傾斜配向薄膜,是從擺動捲繞而成之長條薄膜的捲繞體將前述長條薄膜送出後,朝相對於前述寬度方向傾斜的方向延伸而成之長條傾斜延伸薄膜。 2. The method for producing an optical film according to the above 1, wherein the long oblique alignment film is obtained by feeding the long film from a wound body of a long film which is oscillated and wound, and then A long obliquely extending film extending in a direction oblique to the width direction.
3.如前述1或2所述之光學薄膜之製造方法, 其中,前述長條傾斜配向薄膜係含有脂環式烯烴聚合物系樹脂。 3. The method for producing an optical film according to the above 1 or 2, The long obliquely oriented film contains an alicyclic olefin polymer resin.
4.一種光學薄膜之製造裝置,係具備將長條傾斜配向薄膜之寬度方向的兩端部分別切斷之第1切斷部及第2切斷部,前述長條傾斜配向薄膜在薄膜面內相對於寬度方向的配向方向是傾斜的,取前述長條傾斜配向薄膜當中將前述兩端部切斷後剩餘的部分作為光學薄膜,其特徵在於,前述第1切斷部及前述第2切斷部分別含有第1刀及第2刀,前述第1刀,係配置於前述長條傾斜配向薄膜之薄膜面的一側,且將旋轉軸配置成沿著前述寬度方向;前述第2刀,係配置於前述薄膜面之另一側,在前述薄膜面內,以與相對於前述第1刀的束角對應的角度,使旋轉軸相對於前述寬度方向傾斜,在其和前述第1刀之間將前述長條傾斜配向薄膜夾住並切斷;在前述第1切斷部及前述第2切斷部各個,於前述第1刀之前述寬度方向的一側及另一側當中,隨著朝相對於前述第1刀的束角增大的方向將前述第2刀傾斜,在前述第2刀之形成前述束角的面和前述長條傾斜配向薄膜之前述配向方向所形成的角度變小的側配置前述第2刀。 4. An apparatus for producing an optical film, comprising: a first cutting portion and a second cutting portion that cut both end portions in a width direction of a long oblique alignment film, wherein the long oblique alignment film is in a film surface The alignment direction with respect to the width direction is inclined, and the portion remaining after the both end portions are cut out of the long oblique alignment film is an optical film, and the first cutting portion and the second cutting portion are characterized. The first blade and the second blade are disposed, and the first blade is disposed on one side of the film surface of the long oblique alignment film, and the rotation axis is disposed along the width direction; and the second blade is disposed On the other side of the film surface, the rotation axis is inclined with respect to the width direction at an angle corresponding to the toe angle of the first blade in the film surface, and between the first blade and the first blade The long oblique alignment film is sandwiched and cut, and each of the first cutting portion and the second cutting portion is opposite to the other side in the width direction of the first blade. Increased beam angle of the first knife In the direction, the second blade is inclined, and the second blade is disposed on a side where the angle formed by the surface of the second blade forming the toe angle and the alignment direction of the long oblique alignment film is small.
本發明,係可利用在被使用於液晶顯示裝置 之偏光板中的光學薄膜之製造中。 The present invention can be utilized in a liquid crystal display device In the manufacture of optical films in polarizing plates.
1‧‧‧製造裝置 1‧‧‧ manufacturing equipment
2‧‧‧薄膜送出部 2‧‧‧Film delivery department
3‧‧‧搬送方向變更部 3‧‧‧Transfer Direction Change Department
4‧‧‧導引輥 4‧‧‧ Guide roller
5‧‧‧延伸部 5‧‧‧Extension
6‧‧‧導引輥 6‧‧‧ Guide roller
7‧‧‧搬送方向變更部 7‧‧‧Transfer Direction Change Department
8‧‧‧薄膜切斷裝置 8‧‧‧Film cutting device
9‧‧‧薄膜捲取部 9‧‧‧ Film Reeling Department
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JP6470828B1 (en) * | 2017-12-04 | 2019-02-13 | 住友化学株式会社 | Manufacturing method of polarizing plate with protective film |
JP6470829B1 (en) * | 2017-12-04 | 2019-02-13 | 住友化学株式会社 | Optical laminate and method for producing the same |
TWI656938B (en) * | 2017-12-11 | 2019-04-21 | 住華科技股份有限公司 | Cutting apparatus and cutting method using the same |
WO2019124096A1 (en) * | 2017-12-21 | 2019-06-27 | Dic株式会社 | Ester resin, plasticizer, cellulose ester resin composition, optical film, and liquid-crystal display device |
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JP7016269B2 (en) * | 2018-02-02 | 2022-02-04 | 日東電工株式会社 | Method for manufacturing stretched film |
JP2019174636A (en) * | 2018-03-28 | 2019-10-10 | コニカミノルタ株式会社 | Oblique stretched film, polarizer, irregular shaped display and method for manufacturing oblique stretched film |
WO2019198039A2 (en) * | 2018-04-14 | 2019-10-17 | Lohia Corp Limited | An integrated intelligent system and a method for estimating actual thickness of extruded films |
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