TW201711828A - Method of manufacturing obliquely-stretched film capable of improving productivity while reducing occurrence of wrinkles - Google Patents

Method of manufacturing obliquely-stretched film capable of improving productivity while reducing occurrence of wrinkles Download PDF

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Publication number
TW201711828A
TW201711828A TW105116116A TW105116116A TW201711828A TW 201711828 A TW201711828 A TW 201711828A TW 105116116 A TW105116116 A TW 105116116A TW 105116116 A TW105116116 A TW 105116116A TW 201711828 A TW201711828 A TW 201711828A
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Taiwan
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film
temperature
group
region
width direction
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TW105116116A
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Chinese (zh)
Inventor
Shimpei Hatakeyama
Takashi Nanjiyou
Hirofumi Tanaka
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Konica Minolta Inc
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Publication of TW201711828A publication Critical patent/TW201711828A/en

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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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/045—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique in a direction which is not parallel or transverse to the direction of feed, e.g. oblique
    • 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
    • B29C31/00—Handling, e.g. feeding of the material to be shaped, storage of plastics material before moulding; Automation, i.e. automated handling lines in plastics processing plants, e.g. using manipulators or robots
    • B29C31/004—Arrangements for converting the motion of a material which is continuously fed to a working station in a stepwise motion
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/20—Opening, closing or clamping
    • B29C33/202—Clamping means operating on closed or nearly closed mould parts, the clamping means being independently movable of the opening or closing means
    • 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
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/002—Panels; Plates; Sheets

Abstract

A method of manufacturing an obliquely-stretched film comprises an obliquely stretching step and a relaxing step. In the obliquely stretching step, the film conveying direction is changed halfway in the obliquely stretching region (Z2-2) so that the film is stretched obliquely with respect to the width direction. In the relaxing step, after the obliquely stretching step is completed, the residual stress of the film due to obliquely stretching is relieved in the relaxing zone (Z3) in which the film conveying direction is constant. In the obliquely stretching region (Z2-2), a first temperature distribution is formed in the way that the temperature of the leading side is lower by 1 to 15 DEG C than the temperature of the delay side. In the relaxing region (Z3), a second temperature distribution is formed in the way that the temperature of the leading side is higher by 5 to 30 DEG C than the temperature of the delay side. The temperature of the obliquely stretching region (Z2-2) is higher by 5 to 40 DEG C than the temperature of the relaxing region (Z3).

Description

斜面延伸薄膜之製造方法 Method for manufacturing beveled stretch film

本發明係有關使薄膜對於寬度方向於斜面方向延伸之斜面延伸薄膜之製造方法。 The present invention relates to a method for producing a beveled film which extends a film in a direction of a width in a direction of a slope.

過去以來，如亦稱為OLED(Organic light-Emitting Diode，有機發光二極體)之有機EL(Electro-Luminescence，電致發光)顯示裝置之自發光型顯示裝置備受矚目。OLED中，為了提高光掠出效率，而於顯示器之背面側設有鋁板等之反射體，故入射至顯示器之外光被該反射體反射而使圖像之對比度降低。 In the past, a self-luminous display device of an organic EL (Electro-Luminescence) display device such as an OLED (Organic Light-Emitting Diode) has been attracting attention. In the OLED, in order to improve the light-swept efficiency, a reflector such as an aluminum plate is provided on the back side of the display, so that light incident on the display is reflected by the reflector to lower the contrast of the image.

因此，為了提高因防止外光反射所致之明暗對比度，已知有使延伸薄膜與偏光器貼合構成圓偏光板，並將該圓偏光板配置於顯示器表面側。此時，上述圓偏光板係藉由以使對於偏光器之透過軸，延伸薄膜之面內慢軸以期望角度傾斜之方式，貼合偏光器與延伸薄膜而形成。 Therefore, in order to improve the contrast between light and dark caused by reflection of external light, it is known that a stretched film and a polarizer are bonded to each other to form a circularly polarizing plate, and the circularly polarizing plate is disposed on the display surface side. In this case, the circularly polarizing plate is formed by bonding a polarizer 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 polarizer.

不過，一般偏光器(偏光薄膜)係於長度方向以高倍率延伸而得者，其透過軸與寬度方向一致。且以往之相位差薄膜係藉由縱向延伸或橫向延伸而製造，原理 上面內慢軸成為對於薄膜長度方向為0°或90°之方向。因此，使如上述之偏光器之透過軸與延伸薄膜之慢軸以期望角度傾斜時，必須採用使長條偏光薄膜及/或延伸薄膜以特定角度切出而使薄膜片彼此逐片貼合之批式，而使生產性惡化。 However, a general polarizer (polarizing film) is obtained by extending at a high magnification in the longitudinal direction, and its transmission axis coincides with the width direction. And the conventional retardation film is manufactured by longitudinal extension or lateral extension, principle The upper inner slow axis becomes a direction of 0 or 90 for the longitudinal direction of the film. Therefore, when the transmission axis of the polarizer and the slow axis of the extended film are inclined at a desired angle, it is necessary to cut the long polarizing film and/or the stretch film at a specific angle so that the film sheets are attached one by one to each other. Batch type, which deteriorates productivity.

相對於此，已有各種提案於對於長度方向期望角度之方向(斜面方向)使薄膜延伸，使慢軸之方向於對於薄膜長度方向非於0°亦非於90°之方向自如地控制之長條狀斜面延伸薄膜之製造方法。例如專利文獻1之製造方法，係將樹脂薄膜自與延伸後之薄膜捲取方向不同方向捲出，並藉由一對把持具把持該樹脂薄膜兩端部並搬送。而且，就由於中途變更樹脂薄膜之搬送方向，而使樹脂薄膜於斜面方向延伸。藉此，製造於相對於長度方向超過0°且未達90°之期望角度具有慢軸之長條斜面延伸薄膜。 On the other hand, various proposals have been made to extend the film in the direction of the desired angle in the longitudinal direction (the direction of the slope) so that the direction of the slow axis is freely controlled in a direction other than 0° and not 90° with respect to the longitudinal direction of the film. A method of manufacturing a strip-shaped beveled stretch film. For example, in the manufacturing method of Patent Document 1, the resin film is wound up in a direction different from the direction in which the film is taken up, and the both ends of the resin film are held by a pair of grippers and conveyed. Further, the resin film is stretched in the oblique direction by changing the conveyance direction of the resin film in the middle. Thereby, a long beveled stretch film having a slow axis at a desired angle exceeding 0° and not reaching 90° with respect to the longitudinal direction is manufactured.

藉由使用此長條斜面延伸薄膜，可以輥對輥方式貼合長條偏光薄膜與長條斜面延伸薄膜而製造圓偏光板，使圓偏光板之生產性飛躍性提高。 By using the long beveled stretch film, a long polarizing film and a long beveled stretch film can be bonded to the roll to form a circular polarizing plate, and the productivity of the circular polarizing plate can be greatly improved.

不過，於中途變更薄膜搬送方向之所謂彎曲型斜面延伸機構中，把持薄膜兩端之一對把持具中，使一把持具相對先行，另一把持具相對延遲地行走。亦即，上述一對把持具於薄膜寬度方向非對稱地行走。因此，施加於薄膜之張力於寬度方向變不均一。具體而言，於薄膜寬度方向中，施加於薄膜之張力於把持具先行而行走之側(先行側)比把持具延遲行走之側(延遲側)更弱。其結 果，關於斜面延伸後之薄膜，於先行側膜厚變厚，另一方面於延遲側膜厚變薄，而於寬度方向產生膜厚差。 However, in the so-called curved bevel extending mechanism in which the film conveying direction is changed midway, one of the two ends of the holding film is held in the pair of grippers so that one gripper is advanced and the other gripper is relatively delayed. That is, the pair of grippers travel asymmetrically in the film width direction. Therefore, the tension applied to the film becomes uneven in the width direction. Specifically, in the film width direction, the tension applied to the film on the side where the gripper travels first (the leading side) is weaker than the side on which the gripper is delayed (the retard side). Its knot As a result, the film after the slope is extended has a thick film thickness on the leading side, and the film thickness on the retard side is thinned, and a film thickness difference occurs in the width direction.

因此，上述專利文獻1中，預先準備於寬度方向膜厚變化之薄膜，嘗試藉由使該薄膜斜面延伸而使斜面延伸後膜厚於寬度方向均一化。 Therefore, in the above-mentioned Patent Document 1, a film having a film thickness change in the width direction is prepared in advance, and it is attempted to make the film thickness thicker in the width direction by extending the slope of the film.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2010-173261號公報(參考請求項1、段落[0006]、[0010]、圖1~圖4等)。 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2010-173261 (refer to claim 1, paragraph [0006], [0010], FIG. 1 to FIG. 4, etc.).

不過，專利文獻1之方法，為了進行斜面延伸，有必要分開製作膜厚固定之薄膜與膜厚於寬度方向變化之薄膜，並使用膜厚變化之薄膜進行斜面延伸。如此，由於有必要特意事先製造、準備膜厚變化之薄膜，故斜面延伸薄膜之生產性低。又，藉由斜面延伸對薄膜賦予之應力無法適當緩和時，起因於該應力而容易使薄膜產生肋狀皺紋(表面凹凸不平)。因此，期望實現可減低皺紋發生並且提高斜面延伸薄膜之生產性之製法。 However, in the method of Patent Document 1, in order to perform the bevel extending, it is necessary to separately form a film having a film thickness and a film having a film thickness varying in the width direction, and to perform a bevel extending using a film having a film thickness. In this way, since it is necessary to intentionally manufacture and prepare a film having a film thickness change in advance, the productivity of the bevel stretch film is low. Further, when the stress applied to the film by the inclined surface extension cannot be appropriately alleviated, the film is likely to cause rib-like wrinkles (surface unevenness) due to the stress. Therefore, it is desirable to realize a method of reducing the occurrence of wrinkles and improving the productivity of a bevel stretched film.

本發明係為解決上述問題點而完成者，其目的在於提供於中途改變薄膜搬送方向進行斜面延伸時，可減低皺紋發生且提高生產性之斜面延伸薄膜之製造方法。 The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing a bevel-stretched film which can reduce the occurrence of wrinkles and improve productivity when the film transport direction is changed in the middle of the process.

本發明之上述目的可藉由以下構成達成。亦即，關於本發明之一側面之斜面延伸薄膜之製造方法，其特徵為具有斜面延伸步驟，其係以一對把持具把持薄膜寬度方向之兩端而搬送前述薄膜，同時於斜面延伸區域使前述薄膜之搬送方向於中途改變，藉由使一把持具相對先行，並使另一把持具相對延遲，使前述薄膜對於寬度方向往斜面方向延伸，且於前述斜面延伸步驟結束後，進一步具有緩和步驟，其係於前述薄膜之搬送方向固定之緩和區域，使斜面延伸產生之前述薄膜之殘留應力緩和；於前述薄膜之寬度方向中，將斜面延伸時使前述一對把持具之一者先行而行走之側設為先行側，將另一者延遲行走之側設為延遲側時，前述斜面延伸區域中，於前述先行側與前述延遲側之間，以前述先行側之溫度比前述延遲側之溫度低1~15℃之方式形成第1溫度分佈，於前述緩和區域中，於前述先行側與前述延遲側之間，以前述先行側之溫度比前述延遲側之溫度高5~30℃之方式形成第2溫度分佈，前述斜面延伸區域之溫度比前述緩和區域之溫度高5~40℃。 The above object of the present invention can be achieved by the following constitution. That is, the method for producing a beveled stretched film according to one aspect of the present invention is characterized in that the step of extending the bevel is carried out by holding a pair of grippers at both ends in the width direction of the film to convey the film while the bevel extending region The conveying direction of the film is changed in the middle, and the film is extended in the direction of the slope direction by the relative advance of the holder, and the other holder is relatively delayed, and further relaxed after the step of extending the slope a step of relaxing a residual region in which the film is conveyed in a direction in which the film is conveyed, and relaxing the residual stress of the film caused by the slope extending; and extending the slope to extend one of the pair of grippers in the width direction of the film When the side to be traveled is the leading side and the side where the other is delayed is the retard side, in the inclined surface extending region, the temperature on the preceding side is higher than the retard side between the preceding side and the retard side The first temperature distribution is formed in such a manner that the temperature is lower by 1 to 15 ° C, and the preceding side and the extension are in the relaxation region. Between the side, at a temperature of the high temperature side of the leading side of 5 ~ 30 ℃ the temperature profile is formed than the second delay, the ramp area stretching temperature higher than the temperature of the relaxation region 5 ~ 40 ℃.

依據上述製造方法，即使於途中改變薄膜搬送方向進行斜面延伸時，亦可減低皺紋發生且提高薄膜生產性。 According to the above production method, even when the film transport direction is changed to be inclined on the way, the occurrence of wrinkles can be reduced and the film productivity can be improved.

Ci‧‧‧把持具(先行側之把持具) Ci‧‧‧ holding tools (first side control)

Co‧‧‧把持具(延遲側之把持具) Co‧‧‧ holding tool (delay side handle)

M1‧‧‧第1位置 M1‧‧‧1st position

M2‧‧‧第2位置 M2‧‧‧2nd position

M3‧‧‧中間點 M3‧‧‧ intermediate point

T1、T2、T3、T4、T5、T6‧‧‧溫度 T1, T2, T3, T4, T5, T6‧‧‧ temperatures

Z2-2‧‧‧斜面延伸區域 Z2-2‧‧‧Slope extension

Z3‧‧‧緩和區域 Z3‧‧‧ mitigation area

圖1係示意性顯示本發明實施形態之斜面延伸薄膜之製造裝置之概略構成。 Fig. 1 is a view schematically showing the schematic configuration of a manufacturing apparatus of a beveled stretch film according to an embodiment of the present invention.

圖2係示意性顯示上述製造裝置之延伸部之鐵道圖型之一例之俯視圖。 Fig. 2 is a plan view schematically showing an example of a railway pattern of an extension portion of the above-described manufacturing apparatus.

圖3係示意性顯示上述延伸部之斜面延伸區域及緩和區域之自延遲側至先行側之溫度分佈之說明圖。 Fig. 3 is an explanatory view schematically showing a temperature distribution of a slope extending region and a relaxation region of the extending portion from the retard side to the leading side.

圖4係顯示上述斜面延伸區域之溫度分佈(第1溫度分佈)之例的圖表。 Fig. 4 is a graph showing an example of a temperature distribution (first temperature distribution) of the inclined surface extending region.

圖5係顯示上述緩和區域之溫度分佈(第2溫度分佈)之例的圖表。 Fig. 5 is a graph showing an example of a temperature distribution (second temperature distribution) of the above-mentioned relaxation region.

圖6係示意性顯示於上述斜面延伸區域及上述緩和區域中分別配置加熱部之狀態之說明圖。 Fig. 6 is an explanatory view schematically showing a state in which the heating portions are respectively disposed in the inclined surface extending region and the tempered region.

圖7係示意性顯示用以形成上述第2溫度分佈而配置於延伸部之排氣部之配置例的說明圖。 FIG. 7 is an explanatory view schematically showing an arrangement example of an exhaust portion disposed in the extension portion for forming the second temperature distribution.

圖8係分別顯示斜面延伸步驟後及緩和步驟後之薄膜剖面之說明圖。 Fig. 8 is an explanatory view showing a cross section of the film after the step of extending the slope and after the easing step, respectively.

圖9係顯示應用由上述製造裝置所製造之斜面延伸薄膜之有機EL圖像顯示裝置之概略構成之剖面圖。 Fig. 9 is a cross-sectional view showing a schematic configuration of an organic EL image display device to which a beveled stretch film produced by the above-described manufacturing apparatus is applied.

圖10係顯示應用上述斜面延伸薄膜之液晶顯示裝置之概略構成之剖面圖。 Fig. 10 is a cross-sectional view showing a schematic configuration of a liquid crystal display device to which the above-described beveled stretch film is applied.

若針對本發明實施之一形態，基於圖式說明則如下。又，本說明書中，數值範圍記為A~B時，係其數值範圍內包含下限A及上限B之值者。 For one embodiment of the present invention, the description based on the drawings is as follows. Further, in the present specification, when the numerical range is denoted by A to B, the values of the lower limit A and the upper limit B are included in the numerical range.

本實施形態之長條狀之斜面延伸薄膜(亦稱為長條斜面延伸薄膜或僅稱為斜面延伸薄膜)之製造方法係將包含熱塑性樹脂之長條狀坯片薄膜於相對於寬度方向及長度方向斜面方向延伸而製造長條斜面延伸薄膜之長條斜面延伸薄膜之製造方法。 The long beveled stretch film (also referred to as a long bevel stretch film or simply a bevel stretch film) of the present embodiment is a method for manufacturing a long strip film comprising a thermoplastic resin in a width direction and a length. A method of manufacturing a long beveled stretch film which is formed by extending a direction of a beveled surface to form a long beveled stretch film.

長條斜面延伸薄膜之配向方向亦即慢軸方向係於薄膜面內(垂直於厚度方向之面內)，對於薄膜寬度方向成為超過0°且未達90°之角度之方向(自動地成為對於薄膜長度方向成為超過0°且未達90°之角度之方向)。慢軸由於通常係於延伸方向或與延伸方向呈直角之方向展現，故藉由於對於薄膜寬度方向於超過0°且未達90°之方向進行延伸，而製造具有該慢軸之長條斜面延伸薄膜。長條斜面延伸薄膜之寬度方向與慢軸所成之角度亦即配向角於超過0°且未達90°之範圍，可以期望角度任意設定。 The direction in which the long beveled stretched film is oriented, that is, the direction of the slow axis is in the plane of the film (in the plane perpendicular to the thickness direction), and the direction in which the film width direction exceeds 0° and is less than 90° (automatically becomes The length direction of the film becomes a direction exceeding 0° and not at an angle of 90°). Since the slow axis is generally present in a direction extending or at a right angle to the extending direction, a long bevel extending with the slow axis is produced by extending in a direction in which the film width direction exceeds 0° and is less than 90°. film. The angle formed by the width direction of the strip-shaped bevel extending film and the slow axis, that is, the angle of alignment is more than 0° and less than 90°, and the desired angle can be arbitrarily set.

本實施形態中，所謂長條係指對於薄膜寬度具有至少5倍左右以上之長度者，較好為具有10倍或其以上之長度，具體而言，可認為具有捲繞成捲筒狀而保管 或搬運之程度之長度者(薄膜捲筒)。 In the present embodiment, the term "length" means a length of at least about 5 times the width of the film, and preferably has a length of 10 times or more. Specifically, it is considered to be wound in a roll shape and stored. Or the length of the degree of handling (film reel).

長條斜面延伸薄膜可藉由製膜長條狀未配向薄膜後將其暫時捲繞於捲芯上作成捲繞體(坯片薄膜)，自該捲繞體將坯片薄膜供給於斜面延伸步驟而製造，亦可不捲取製膜後之長條薄膜，而自製膜步驟連續供給於斜面延伸步驟而製造者。製膜步驟與斜面延伸步驟連續進行時可將延伸後之薄膜膜厚或光學值結果反饋並變更製膜條件而獲得期望之長條斜面延伸薄膜故而較佳。且，藉由連續製造長條斜面延伸薄膜，可獲得期望長度之長條斜面延伸薄膜。 The strip-shaped bevel-stretching film can be formed by winding a strip-shaped unaligned film and then temporarily winding it on a winding core to form a wound body (blank film), and feeding the green sheet film to the inclined surface extending step from the winding body Alternatively, the long film after film formation may be unwound, and the self-made film step is continuously supplied to the bevel extending step to be manufactured. When the film forming step and the step of extending the bevel are continuously performed, it is preferable to feed back the film thickness or optical value of the film after the extension and change the film forming conditions to obtain a desired long bevel stretch film. Moreover, by continuously manufacturing the elongated bevel extending film, a long beveled stretch film of a desired length can be obtained.

作為坯片薄膜中所含之熱塑性樹脂可使用纖維素酯系樹脂、脂環式烯烴聚合物系樹脂(COP)、聚碳酸酯系樹脂(PC)等。 A cellulose ester resin, an alicyclic olefin polymer resin (COP), a polycarbonate resin (PC), or the like can be used as the thermoplastic resin contained in the green sheet film.

將上述坯片薄膜斜面延伸所得之斜面延伸薄膜可應用於如配戴偏光太陽眼鏡而可視認之液晶顯示裝置。亦即，對於比液晶層更靠視認側之偏光板之偏光器，進一步於其視認側貼合斜面延伸薄膜而構成圓偏光板。此時，以使斜面延伸薄膜之慢軸與偏光器之透過軸成為45°之方式將兩者貼合。以該構成，使自液晶層射出並透過視認側之偏光器之直線偏光藉由斜面延伸薄膜(作為λ/4薄膜之功能)轉換為圓偏光。因此，觀察者配戴偏光太陽眼鏡觀察液晶顯示裝置之顯示圖像時，即使偏光器之透過軸與偏光太陽眼鏡之透過軸成為任何角度，均可將平行於偏光太陽眼鏡之透過軸之光成分導入觀察者眼睛並觀察顯示 圖像。因此，可抑制因所觀察之角度(因偏光太陽眼鏡之透過軸方向)而難以見到顯示圖像之情況。 The beveled stretch film obtained by extending the above-mentioned blank film obliquely can be applied to a liquid crystal display device which can be visually recognized by wearing polarized sunglasses. In other words, the polarizer of the polarizing plate which is closer to the viewing side than the liquid crystal layer is further bonded to the viewing side to form a circularly polarizing plate. At this time, the two are bonded so that the slow axis of the bevel extending film and the transmission axis of the polarizer are 45 degrees. With this configuration, the linearly polarized light that is emitted from the liquid crystal layer and transmitted through the polarizer on the viewing side is converted into circularly polarized light by a beveled stretched film (functioning as a λ/4 film). Therefore, when the observer wears polarized sunglasses to observe the display image of the liquid crystal display device, even if the transmission axis of the polarizer and the transmission axis of the polarized sunglasses are at any angle, the light component parallel to the transmission axis of the polarized sunglasses can be used. Import the observer's eyes and observe the display image. Therefore, it is possible to suppress the display image from being hard to see due to the observed angle (the direction of the transmission axis of the polarized sunglasses).

如此，將斜面延伸薄膜應用於偏光太陽眼鏡對應之液晶顯示裝置之圓偏光板時，期望於斜面延伸薄膜之視認側形成用以保護表面之硬塗層。 Thus, when the beveled stretch film is applied to a circularly polarizing plate of a liquid crystal display device corresponding to polarized sunglasses, it is desirable to form a hard coat layer for protecting the surface on the viewing side of the beveled stretched film.

以下，參考適當圖式具體說明本發明之實施樣態。 Hereinafter, embodiments of the present invention will be specifically described with reference to the appropriate drawings.

<纖維素酯系樹脂> <Cellulose ester resin>

本實施形態之坯片薄膜所用之纖維素酯系樹脂薄膜舉例為含有滿足下述式(1)及(2)之纖維素醯化物且含有以下述通式(A)表示之化合物者。 The cellulose ester-based resin film used for the green sheet film of the present embodiment is exemplified by a compound containing a cellulose halide satisfying the following formulas (1) and (2) and containing a compound represented by the following formula (A).

式(1)2.0≦Z1≦3.0 Formula (1) 2.0≦Z1≦3.0

式(2)0≦X≦3.0 Equation (2)0≦X≦3.0

(式(1)及(2)中，Z1表示纖維素醯化物之總醯基取代度，X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)。 (In the formulae (1) and (2), Z1 represents the total thiol substitution degree of the cellulose oxime, and X represents the sum of the propylene group substitution degree and the butyl thiol group substitution degree of the cellulose oxime).

以下，針對通式(A)詳細說明。通式(A)中，L1及L2各獨立表示單鍵或2價連結基。作為L1及L2舉例為例如下述構造。(下述R表示氫原子或取代基)。 Hereinafter, the general formula (A) will be described in detail. In the formula (A), L 1 and L 2 each independently represent a single bond or a divalent linking group. Examples of L 1 and L 2 are, for example, the following structures. (The following R represents a hydrogen atom or a substituent).

作為L1及L2較好為-O-、-COO-、-OCO-。 L 1 and L 2 are preferably -O-, -COO-, or -OCO-.

R1、R2及R3各獨立表示取代基。以R1、R2及R3表示之取代基之具體例舉例為鹵原子(氟原子、氯原子、溴原子、碘原子等)、烷基(甲基、乙基、正丙基、異丙基、第三丁基、正辛基、2-乙基己基等)、環烷基(環己基、環庚基、4-正-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、丙炔基等)、芳基(苯基、對-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、第三丁氧基、正-辛氧基、2-甲氧基乙氧基等)、芳氧基(苯氧基、2-甲基苯氧基、4-第三丁基苯氧基、3-硝基苯氧基、2-十四烷醯基胺基苯氧基等)、醯氧基(甲醯氧基、乙醯氧基、丙醯氧基、硬脂醯氧基、苯甲醯氧基、對-甲氧基 苯羰氧基等)、胺基(胺基、甲胺基、二甲胺基、苯胺基、N-甲基-苯胺基、二苯基胺基等)、醯基胺基(甲醯胺基、乙醯胺基、特戊醯胺基、月桂醯胺基、苯甲醯胺基等)、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、對-甲基苯基磺醯基胺基等)、巰基、烷硫基(甲硫基、乙硫基、正-十六烷硫基等)、芳硫基(苯硫基、對-氯苯硫基、間-甲氧基苯硫基等)、胺磺醯基(N-乙基胺磺醯基、N-(3-十二烷氧基丙基)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、特戊醯基、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-正-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 are exemplified by a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (methyl group, ethyl group, n-propyl group, or isopropyl group). Base, tributyl, n-octyl, 2-ethylhexyl, etc.), cycloalkyl (cyclohexyl, cycloheptyl, 4-n-dodecylcyclohexyl, etc.), alkenyl (vinyl, alkenyl) Propyl, etc.), cycloalkenyl (2-cyclopenten-1-yl, 2-cyclohexen-1-yl, etc.), alkynyl (ethynyl, propynyl, etc.), aryl (phenyl, p. -tolyl, naphthyl, etc.), heterocyclic group (2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, etc.), cyano, hydroxy, nitro, carboxy, alkoxy (methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy, etc.), aryloxy (phenoxy, 2-methylbenzene) Oxyl group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecylideneaminophenphenoxy group, etc.), decyloxy group (methyloxy group, ethoxy group, Acryloxy, stearyloxy, benzhydryloxy, p-methoxyphenylcarbonyloxy, etc.), amine group (amine group, methylamino group, dimethylamino group, anilino group, N-methyl group) Alkyl-anilino Diphenylamino group, etc., mercaptoamino group (formammine, etidamine, pentamidine, lauryl, benzhydryl, etc.), alkyl and arylsulfonyl Amino (methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonate Mercaptoamine, etc., mercapto, alkylthio (methylthio, ethylthio, n-hexadecanethio, etc.), arylthio (phenylthio, p-chlorophenylthio, meta-methoxy Alkyl sulfenyl, etc., sulfonyl (N-ethylamine sulfonyl, N-(3-dodecyloxypropyl)amine sulfonyl, N,N-dimethylamine sulfonyl , N-ethinylsulfonyl, N-benzhydrylsulfonyl, N-(N'-phenylaminecarbamimidino)sulfonyl, etc., sulfo, fluorenyl (acetamidine) Base, tert-amyl, benzhydryl, etc.), aminomethyl group (amine methyl sulfonyl, N-methylamine methyl sulfhydryl, N,N-dimethylamine carbhydryl, N,N-di - n-octylamine methyl sulfhydryl, N-(methylsulfonyl)amine carbaryl, etc.).

作為R1及R2較好為經取代或未取代之苯基、經取代或未取代之環己基，更好為具有取代基之苯基、具有取代基之環己基，又更好為於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 more preferably 4 a phenyl group having a substituent and a cyclohexyl group having a substituent at the 4-position.

作為R3較好為氫原子、鹵素原子、烷氧基、烯基、芳基、雜芳基、羥基、羧基、烷氧基、芳氧基、醯氧基、氰基、胺基，更好為氫原子、鹵素原子、烷基、氰基、烷氧基。 R 3 is preferably a hydrogen atom, a halogen atom, an alkoxy group, an alkenyl group, an aryl group, a heteroaryl 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表示氫原子或取代基，但(I)Wa及Wb亦可相互鍵結形成環， (II)Wa及Wb之至少一者亦可具有環構造，或(III)Wa及Wb之至少一者亦可為烯基或炔基。 Wa and Wb represent a hydrogen atom or a substituent, but (I) Wa and Wb may also bond to each other to form a ring. (II) At least one of Wa and Wb may have a ring structure, or at least one of (III) Wa and Wb may be an alkenyl group or an alkynyl group.

以Wa及Wb表示之取代基之具體例舉例為鹵原子(氟原子、氯原子、溴原子、碘原子等)、烷基(甲基、乙基、正丙基、異丙基、第三丁基、正辛基、2-乙基己基等)、環烷基(環己基、環庚基、4-正-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、丙炔基等)、芳基(苯基、對-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、第三丁氧基、正-辛氧基、2-甲氧基乙氧基等)、芳氧基(苯氧基、2-甲基苯氧基、4-第三丁基苯氧基、3-硝基苯氧基、2-十四烷醯基胺基苯氧基等)、醯氧基(甲醯氧基、乙醯氧基、丙醯氧基、硬脂醯氧基、苯甲醯氧基、對-甲氧基苯羰氧基等)、胺基(胺基、甲胺基、二甲胺基、苯胺基、N-甲基-苯胺基、二苯基胺基等)、醯基胺基(甲醯胺基、乙醯胺基、特戊醯胺基、月桂醯胺基、苯甲醯胺基等)、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、對-甲基苯基磺醯基胺基等)、巰基、烷硫基(甲硫基、乙硫基、正-十六烷硫基等)、芳硫基(苯硫基、對-氯苯硫基、間-甲氧基苯硫基等)、胺磺醯基(N-乙基胺磺醯基、N-(3-十二烷氧基丙基)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、三甲基乙醯基苯甲醯基等)、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-正-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 are exemplified by a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, and third group). Base, n-octyl, 2-ethylhexyl, etc.), cycloalkyl (cyclohexyl, cycloheptyl, 4-n-dodecylcyclohexyl, etc.), alkenyl (vinyl, allyl, etc.), Cycloalkenyl (2-cyclopenten-1-yl, 2-cyclohexen-1-yl, etc.), alkynyl (ethynyl, propynyl, etc.), aryl (phenyl, p-tolyl, naphthalene Base, etc.), heterocyclic group (2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, etc.), cyano group, hydroxy group, nitro group, carboxyl group, alkoxy group (methoxy group, Ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy, etc.), aryloxy (phenoxy, 2-methylphenoxy, 4- a third butyl phenoxy group, a 3-nitrophenoxy group, a 2-tetradecylideneaminophenoxy group, etc.), a decyloxy group (methyl methoxy group, an ethoxy group, a propyl oxy group, Stearyloxy, benzylideneoxy, p-methoxyphenylcarbonyloxy, etc.), amine group (amine group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, Diphenyl Amino group, etc., mercaptoamine group (formammine group, etidamine group, pentamidine group, laurylamine, benzylamino group, etc.), alkyl group and arylsulfonylamino group ( Methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamine Base, etc., fluorenyl, alkylthio (methylthio, ethylthio, n-hexadecanethio, etc.), arylthio (phenylthio, p-chlorophenylthio, m-methoxyphenylthio Alkylsulfonyl (N-ethylamine sulfonyl, N-(3-dodecyloxypropyl)amine sulfonate Base, N,N-dimethylaminesulfonyl, N-ethinylsulfonyl, N-benzamidesulfonyl, N-(N'-phenylaminecarbamyl)amine sulfonate Sulfhydryl, etc.), sulfo group, mercapto group (ethylidene group, trimethylethyl benzhydryl group, etc.), amine carbenyl group (amine methyl sulfonyl group, N-methyl carbamoyl group, N, N - dimethylamine-methyl indenyl, N,N-di-n-octylamine indenyl, N-(methylsulfonyl)amine, indenyl, and the like.

上述取代基亦可進一步以上述基取代。 The above substituent may be further substituted with the above group.

(I)Wa及Wb亦可相互鍵結形成環時，該環較好為含氮5員環或含硫5員環。且通式(A)特佳為以下述通式(1)或通式(2)表示之化合物。 (I) When Wa and Wb are also 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 formula (A) is particularly preferably a compound represented by the following formula (1) or (2).

通式(1)中，A1及A2各獨立表示-O-、-S-、-NRx-(Rx表示氫原子或取代基)或-CO-。以Rx表示之取代基之例與上述Wa及Wb表示之取代基之具體例同義。作為Rx較好為氫原子、烷基、芳基、雜環基。 In the 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 synonymous with 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.

通式(1)中，X表示第14~16族之非金屬原 子。作為X較好為=O、=S、=NRc、=C(Rd)Re。此處，Rc、Rd、Re表示取代基，其例與上述Wa及Wb表示之取代基之具體例同義。L1、L2、R1、R2、R3、n與通式(A)之L1、L2、R1、R2、R3、n同義。 In the formula (1), X represents a non-metal atom of Groups 14 to 16. X is preferably =O, =S, =NRc, and =C(Rd)Re. Here, Rc, Rd, and Re represent a substituent, and examples thereof are synonymous with specific examples of the substituents represented by Wa and Wb described above. L 1, L 2, R 1 , R 2, L R 3, n in the general formula (A) of the 1, L 2, R 1, R 2, R 3, n synonymous.

通式(2)中，Q1表示-O-、-S-、-NRy-(Ry表示氫原子或取代基)、-CRaRb-(Ra及Rb表示氫原子或取代基)或-CO-。此處，以Ry、Ra、Rb表示取代基，其例與上述Wa及Wb表示之取代基之具體例同義。 In the 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, the substituent is represented by Ry, Ra, and Rb, and the examples are the same as the specific examples of the substituent represented by the above Wa and Wb.

Y表示取代基。以Y表示之取代基之例與上述Wa及Wb表示之取代基之具體例同義。作為Y較好為芳基、雜環基、烯基、炔基。 Y represents a substituent. Examples of the substituent represented by Y are synonymous with the specific examples of the substituent represented by the above Wa and Wb. Y is preferably an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group.

以Y表示之芳基舉例為苯基、萘基、蒽基、菲基、聯苯基等，較好為苯基、萘基，更好為苯基。 The aryl group represented by Y is exemplified by a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, a biphenyl group, etc., preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

作為雜環基舉例為呋喃基、吡咯基、噻吩基、吡啶基、噻唑基、苯并噻唑基等之含有至少一個氮原 子、氧原子、硫原子等雜原子之雜環基，較好為呋喃基、吡咯基、噻吩基、吡啶基、噻唑基。 Examples of the heterocyclic group include a furyl group, a pyrrolyl group, a thienyl group, a pyridyl group, a thiazolyl group, a benzothiazolyl group and the like which contain at least one nitrogen source. The heterocyclic group of a hetero atom such as an oxygen atom or a sulfur atom is preferably a furyl group, a pyrrolyl group, a thienyl group, a pyridyl group or a thiazolyl group.

該等芳基或雜環基可具有至少一個取代基。作為該取代基舉例為鹵素原子、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。 The aryl or heterocyclic group may have at least one substituent. The substituent is exemplified by 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, an alkylsulfonyl group having 1 to 6 carbon atoms, and a carboxyl group. a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, and a carbon number of 2 to 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與通式(A)之L1、L2、R1、R2、R3、n同義。 L 1, L 2, R 1 , R 2, L R 3, n in the general formula (A) of the 1, L 2, R 1, R 2, R 3, n synonymous.

(II)通式(A)中Wa及Wb之至少一個具有環構造時之具體例較好為下述通式(3)。 (II) In the general formula (A), a specific example in which at least one of Wa and Wb has a ring structure is preferably the following formula (3).

通式(3)中，Q3表示=N-或=CRz-(Rz表示 氫原子或取代基)，Q4表示第14~16族之非金屬原子。Z表示與Q3及Q4一起形成環之非金屬原子群。 In the formula (3), Q 3 represents =N- or =CRz- (Rz represents a hydrogen atom or a substituent), and Q 4 represents a non-metal atom of Groups 14 to 16. Z represents a group of non-metal atoms forming a ring together with Q 3 and Q 4 .

由Q3及Q4與Z形成之環亦可進而與其他環縮環。由Q3及Q4與Z形成之環較好為與苯環縮環之含氮5員環或6員環。 The ring formed by Q 3 and Q 4 and Z may further be condensed with other rings. The ring formed by Q 3 and Q 4 and Z is preferably a nitrogen-containing 5-membered ring or a 6-membered ring which is condensed with a benzene ring.

L1、L2、R1、R2、R3、n與通式(A)之L1、L2、R1、R2、R3、n同義。 L 1, L 2, R 1 , R 2, L R 3, n in the general formula (A) of the 1, L 2, R 1, R 2, R 3, n synonymous.

(III)Wa及Wb之至少一個為烯基或炔基時，該等較好為具有取代基之乙烯基或乙炔基。 (III) When 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.

上述通式(1)、通式(2)及通式(3)表示之化合物中，特佳為以通式(3)表示之化合物。 Among the compounds represented by the above formula (1), formula (2) and formula (3), a compound represented by the formula (3) is particularly preferred.

通式(3)表示之化合物之耐熱性及耐光性比通式(1)表示之化合物優異，與通式(2)表示之化合物相比，對於有機溶劑之溶解性或與聚合物之相溶性良好。 The compound represented by the formula (3) is superior in heat resistance and light resistance to the compound represented by the formula (1), and has solubility in an organic solvent or compatibility with a polymer as compared with a compound represented by the formula (2). good.

以通式(A)表示之化合物可調整為適於賦予期望波長分散性及滲透防止性之量而含有，但作為添加量較好對於纖維素衍生物含有1~15質量%，尤其較好含有2~10質量%。若為該範圍，則可對上述纖維素衍生物賦予充分之波長分散性及滲透防止性。 The compound represented by the formula (A) can be adjusted so as to be contained in an amount suitable for imparting desired wavelength dispersibility and penetration prevention. However, the amount of the compound is preferably 1 to 15% by mass, particularly preferably the cellulose derivative. 2 to 10% by mass. When it is this range, sufficient wavelength dispersibility and penetration prevention property can be provided with respect to the said cellulose derivative.

又，通式(1)、通式(2)及通式(3)表示之化合物可參考已知方法獲得。具體而言可參考Journal of Chemical Crystallography(1997)；27(9)；512-526；日本特開2010-31223號公報、日本特開2008-107767號公報等而合成。 Further, the compounds represented by the formula (1), the formula (2) and the formula (3) can be obtained by referring to a known method. Specifically, it can be synthesized by referring to Journal of Chemical Crystallography (1997); 27 (9); 512-526; Japanese Patent Laid-Open No. 2010-31223, and JP-A-2008-107767.

(關於纖維素醯化物) (About cellulose telluride)

本實施形態之纖維素醯化物薄膜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對於薄膜總質量(100質量%)較好以60~100質量%之範圍含有纖維素醯化物。且纖維素醯化物之總醯基取代度為2.0以上且未達3.0，更好為2.2~2.7。 The cellulose halide film of the present embodiment contains cellulose halide as a main component. For example, the cellulose oxime film of the present embodiment preferably contains cellulose oxime in a range of 60 to 100% by mass based on the total mass (100% by mass) of the film. Further, the degree of substitution of the total thiol group of the cellulose halide is 2.0 or more and less than 3.0, more preferably 2.2 to 2.7.

作為纖維素醯化物舉例為纖維素與碳數2~22左右之脂肪族羧酸及/或芳香族羧酸之酯，尤其較好為纖維素與碳數為6以下之低級脂肪酸之酯。 The cellulose halide is exemplified by 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 preferably an ester of cellulose and a lower fatty acid having 6 or less carbon atoms.

鍵結於纖維素之羥基之醯基可為直鏈亦可為分支，且亦可形成環。亦可進而取代其他取代基。於相同取代度時，上述碳數較多時雙折射率降低，故作為碳數較好於碳數2~6之醯基中選擇，丙醯基取代度及丁醯基取代度之總和為0以上且未達3.0。作為前述纖維素醯化物之碳數較好為2~4，更好碳數為2~3。 The thiol group bonded to the hydroxyl group of the cellulose may be a straight chain or a branch, and may also form a ring. It is also possible to replace other substituents. In the case of the same degree of substitution, when the carbon number is large, the birefringence is lowered. Therefore, the carbon number is preferably selected from the group of 2 to 6 carbon atoms, and the sum of the degree of substitution of the propyl group and the degree of substitution of the butyl group is 0 or more. Not up to 3.0. The carbon number of the cellulose halide is preferably from 2 to 4, and more preferably from 2 to 3.

具體而言，作為纖維素醯化物可使用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苯二甲酸酯般之除乙醯基以外又鍵結有丙醯基、丁醯基或苯二甲醯基之纖維素之混合脂肪酸酯。又，形成丁酸酯之丁醯基可為直鏈亦可為分支。 Specifically, as the cellulose halide, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate or cellulose acetate phthalate can be used. A mixed fatty acid ester of cellulose which is conjugated with a fluorenyl group, a butyl fluorenyl group or a dimethyl fluorenyl group in addition to an ethyl oxime group. Further, the butyl group forming the butyrate may be a straight chain or a branch.

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，上述纖維素醯化物較好為同時滿足下述之數式(i)及數式(ii)者。 Further, the cellulose halide preferably satisfies the following formula (i) and formula (ii).

式(i)2.0≦X+Y<3.0 Formula (i) 2.0≦X+Y<3.0

式(ii)0≦X<3.0 Formula (ii) 0≦X<3.0

式中，Y表示乙醯基之取代度，X表示丙醯基或丁醯基或其混合物之取代度。 In the formula, Y represents the degree of substitution of the ethyl group, and X represents the degree of substitution of the propyl group or the butyl group or a mixture thereof.

為了獲得實現目的之光學特性，亦可混合使用取代度不同之樹脂。作為此時之混合比較好為1：99~99：1(質量比)。 In order to obtain the optical characteristics for the purpose of realization, a resin having a different degree of substitution may be used in combination. As a mixture at this time, it is preferably 1:99 to 99:1 (mass ratio).

上述中，尤其較好使用纖維素乙酸酯丙酸酯作為纖維素醯化物。纖維素乙酸酯丙酸酯較好為0≦Y≦2.5且0.5≦X≦3.0(但2.0≦X+Y<3.0)，更好為0.5≦Y≦2.0且1.0≦X≦2.0(但2.0≦X+Y<3.0)。又，醯基之取代度係根據ASTM(American Society for Testing and Materials；美國試驗材料協會)所策定發行之規格之一的ASTM-D817-96而測定。 Among the above, cellulose acetate propionate is particularly preferably used as the cellulose halide. The cellulose acetate propionate 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 was measured in accordance with ASTM-D817-96, one of the specifications issued by ASTM (American Society for Testing and Materials).

纖維素醯化物之數平均分子量若為60000~300000之範圍，則所得薄膜之機械強度變強故較佳。更好使用數平均分子量為70000~200000之纖維素醯化物。 When the number average molecular weight of the cellulose halide is in the range of 60,000 to 300,000, the mechanical strength of the obtained film becomes strong, which is preferable. It is more preferable to use a cellulose halide having a number average molecular weight of 70,000 to 200,000.

纖維素醯化物之重量平均分子量(Mw)及數平均分子量(Mn)係使用凝膠滲透層析儀(GPC)測定。測定條件如下。又，本測定方法亦可使用作為本實施形態之其他聚合物之測定方法。 The weight average molecular weight (Mw) and number average molecular weight (Mn) of the cellulose halide were measured using a gel permeation chromatography (GPC). The measurement conditions are as follows. Further, as the measurement method, a measurement method of another polymer of the present embodiment can also be used.

溶劑：二氯甲烷；管柱：Shodex K806、K805、K803G(昭和電工股份有限公司製)3根連接使用；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；校正曲線：使用標準聚苯乙烯STK standard polystyrene(TOSOH股份有限公司製)Mw=1000000~500之13個樣品所得之校正曲線。13個樣品大致等間隔使用。 Solvent: dichloromethane; column: Shodex K806, K805, K803G (manufactured by Showa Denko Co., Ltd.) 3 connections; column temperature: 25 ° C; sample concentration: 0.1% by mass; detector: RI Model 504 (GL (manufactured by the company); pump: L6000 (manufactured by Hitachi, Ltd.); flow rate: 1.0 ml/min; calibration curve: 13 pieces of standard polystyrene STK standard polystyrene (manufactured by TOSOH Co., Ltd.) Mw=1000000~500 The calibration curve obtained from the sample. Thirteen samples were used at approximately equal intervals.

纖維素醯化物中之殘留硫酸含量以硫元素換算較好為0.1~45質量ppm之範圍。該等認為以鹽之形式含有。殘留硫酸含量超過45質量ppm時，熱延伸時或熱延伸後之開縫時有易於斷裂之傾向。又，殘留硫酸含量更好為1~30質量ppm之範圍。殘留硫酸含量可依據ASTM-D817-96規定之方法測定。 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. These are considered to be contained in the form of salt. When the residual sulfuric acid content exceeds 45 ppm by mass, there is a tendency to be easily broken at the time of slitting at the time of heat stretching or 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 in accordance with the method specified in ASTM-D817-96.

且，纖維素醯化物中之游離酸含量較好為1~500質量ppm。若為上述範圍，則由於與上述一樣不易斷裂故較佳。又，游離酸含量較好為1~100質量ppm之範圍，進而不易斷裂。尤其較佳為1~70質量ppm之範圍。游離酸含量可依據ASTM-D817-96規定之方法測定。 Further, the free acid content in the cellulose halide is preferably from 1 to 500 ppm by mass. If it is the above range, it is preferable because it is not easily broken as described above. Further, the free acid content is preferably in the range of 1 to 100 ppm by mass, and is not easily broken. It is particularly preferably in the range of 1 to 70 ppm by mass. The free acid content can be determined in accordance with the method specified in ASTM-D817-96.

藉由充分進行合成之纖維素醯化物之洗淨， 可使殘留硫酸含量及游離酸含量在上述範圍而較佳。 By thoroughly performing the washing of the synthesized cellulose halide, The residual sulfuric acid content and the free acid content are preferably in the above range.

作為纖維素醯化物之纖維素原料並未特別限定，舉例為棉短纖維、木漿、洋麻等。又，由該等所得之纖維素醯化物係分別以任意比例混合使用。 The cellulose raw material of the cellulose halide is not particularly limited, and examples thereof include cotton staple fiber, wood pulp, and kenaf. Further, the cellulose oxime compounds obtained by the above are used in combination at any ratio.

纖維素醯化物可藉由習知方法製造。具體而言，例如可參考日本特開平10-45804號公報中記載之方法合成。 Cellulose halides can be produced by conventional methods. Specifically, for example, it can be synthesized by the method described in JP-A-10-45804.

又，纖維素醯化物受到纖維素醯化物中之微量金屬成分之影響。該等微量金屬成分認為與製造步驟中使用之水有關係，但較好如成為不溶性核之成分越少越好。尤其鐵、鈣、鎂等之金屬離子會有與具有含有有機酸性基之可能性之聚合物分解物等形成鹽而形成不溶物之情況，故較少較佳。又，鈣(Ca)成分易與羧酸或磺酸等酸性成分且與多數配位基易形成配位化合物(亦即錯合物)，而有形成源自多數不溶鈣之渣滓(不溶性沉澱、混濁)之虞，故較少較佳。 Further, the cellulose halide is affected by a trace amount of metal components in the cellulose halide. These trace metal components are considered to be related to the water used in the production step, but it is preferred that the components which are insoluble cores are as small as possible. In particular, metal ions such as iron, calcium, and magnesium may form a salt with a polymer decomposition product or the like having an organic acid group to form an insoluble matter, which is less preferable. Further, the calcium (Ca) component is easily formed with 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 a plurality of ligands, and a residue derived from a majority of insoluble calcium is formed (insoluble precipitate, It is less preferred after turbidity.

具體而言，關於鐵(Fe)成分，於纖維素醯化物中之含量較好為1質量ppm以下。且關於鈣(Ca)成分，於纖維素醯化物中之含量較好為60質量ppm以下，更好為0~30質量ppm。再者，關於鎂(Mg)成分，由於若過多則產生不溶分，故於纖維素醯化物中之含量較好為0~70質量ppm，特佳為0~20質量ppm。 Specifically, the content of the iron (Fe) component in the cellulose halide is preferably 1 ppm by mass or less. 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, since the magnesium (Mg) component is insoluble as much as possible, the content in the cellulose halide is preferably from 0 to 70 ppm by mass, particularly preferably from 0 to 20 ppm by mass.

又，鐵(Fe)成分之含量、鈣(Ca)成分之含量、鎂(Mg)成分之含量等之金屬成分之含量可將絕 對乾燥之纖維素醯化物以微消化濕式分解裝置以硫硝酸分解，以鹼熔融進行前處理後，使用ICP-AES(感應偶和電漿發光分光分析裝置)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 may be The dried cellulose oxime was decomposed with sulfuric acid by a micro-digestive wet decomposition apparatus, pretreated by alkali fusion, and analyzed by ICP-AES (inductive couple and plasma luminescence spectroscopic analyzer).

<脂環式烯烴聚合系樹脂> <Cycloaliphatic olefin polymerization resin>

作為本實施形態之坯片薄膜中使用之脂環式烯烴聚合物系樹脂可採用日本特開平05-310845號公報中記載之環狀烯烴無規多元共聚物、日本特開平05-97978號公報中記載之氫化聚合物、日本特開平11-124429號公報中記載之熱塑性二環戊二烯系開環聚合物及其氫化物等。 The alicyclic olefin polymer-based resin used in the green sheet film of the present embodiment can be a cyclic olefin random multicomponent copolymer described in JP-A-2005-310845, and JP-A-2005-97978 A hydrogenated polymer, a thermoplastic dicyclopentadiene ring-opening polymer described in JP-A-H11-124429, a hydrogenated product thereof, and the like.

脂環式烯烴聚合物系樹脂係具有飽和脂環烴(環烷)構造或不飽和脂環烴(環烯)構造之籠型脂環式構造之聚合物。構成脂環式構造之碳原子數並未特別限制，但通常為4~30個，較好為5~20個，更好為5~15個之範圍時，機械強度、耐熱性及長條薄膜之成形性之特性高度均衡而較佳。 The alicyclic olefin polymer-based resin is a polymer having a saturated alicyclic hydrocarbon (cycloalkane) structure or a caged alicyclic structure having an unsaturated alicyclic hydrocarbon (cycloolefin) structure. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15, mechanical strength, heat resistance, and long film. The properties of formability are highly balanced and preferred.

脂環式烯烴聚合物中含有脂環式構造之重複單位之比例只要適當選擇即可，較好為55重量%以上，更好為70重量%以上，特佳為90重量%以上。脂環式聚烯烴樹脂中具有脂環式構造之重複單位之比例若在該範圍，則由本實施形態之長條斜面延伸薄膜所得之相位差薄膜等之光學材料之透明性及耐熱性提高故而較佳。 The proportion of the repeating unit having an alicyclic structure in the alicyclic olefin polymer may be appropriately selected, and is preferably 55% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more. When the ratio of the repeating unit having an alicyclic structure in the alicyclic polyolefin resin is within this range, the transparency and heat resistance of the optical material such as the retardation film obtained from the long beveled film of the present embodiment are improved. good.

作為具有脂環構造之烯烴聚合物系樹脂可舉例為降冰片烯系樹脂、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該等之氫化物等。該等中，降冰片烯系樹脂由於透明性及成形性良好故可較好地使用。 Examples of the olefin polymer-based resin having an alicyclic structure include a norbornene-based resin, a monocyclic cyclic olefin resin, and a cyclic conjugate. A diene resin, a vinyl alicyclic hydrocarbon resin, and the like. Among these, the norbornene-based resin can be preferably used because of its excellent transparency and moldability.

作為降冰片烯系樹脂可舉例例如具有降冰片烯構造之單體之開環聚合物或具有降冰片烯構造之單體與其他單體之開環聚合物或該等之氫化物，具有降冰片烯構造之單體之加成聚合物或具有降冰片烯構造之單體與其他單體之加成共聚物或該等之氫化物等。該等中，具有降冰片烯構造之單體之開環(共)聚合物氫化物，基於透明性、成形性、耐熱性、低吸濕性、尺寸安定性及輕量性等之觀點，可特別好地使用。 As the norbornene-based resin, for example, a ring-opening polymer having a monomer of a norbornene structure or a ring-opening polymer of a monomer having a norbornene structure and other monomers or a hydride of the same, having a norbornene An addition polymer of an olefinic monomer or an addition copolymer of a monomer having a norbornene structure and another monomer, or a hydride of the same. Among these, a ring-opened (co)polymer hydride having a norbornene structure can be based on transparency, moldability, heat resistance, low moisture absorption, dimensional stability, and lightness. Particularly good to use.

使用如上述之降冰片烯系樹脂成形長條薄膜(坯片薄膜)之方法較好為溶液製膜法或熔融擠出法之製造方法。作為熔融擠出法舉例為使用模嘴之吹塑法等，但以生產性或厚度精度優異之方面較好為使用T模嘴之方法。 The method of forming a long film (blank film) using the norbornene-based resin as described above is preferably a method of producing a solution film forming method or a melt extrusion method. The melt extrusion method is exemplified by a blow molding method using a die, etc., but a method of using a T die is preferable in terms of productivity or thickness precision.

作為使用T模嘴之擠出成形法可藉由如日本特開2004-233604號公報中記載般使密著於冷卻滾筒時之熔融狀態之熱塑性樹脂保持於安定狀態之方法，可製造延遲或配向角之光學特性偏差小之長條薄膜。 As a method of extrusion molding using a T-die, a delay or alignment can be produced by a method in which a thermoplastic resin in a molten state adhered to a cooling drum is kept in a stable state as described in JP-A-2004-233604 A long film with a small deviation in optical properties of the corners.

具體而言，舉例為如下方法：1)以熔融擠出法製造長條薄膜時，使自模嘴擠出之薄片狀熱塑性樹脂於50kPa以下之壓力下密著於冷卻滾筒並拉取之方法；2)以熔融擠出法製造長條薄膜時，以包圍材料覆蓋自模嘴開 口部至最初密著之冷卻滾筒，將自包圍材料至模嘴開口部或最初密著之冷卻滾筒之距離設為100mm以下之方法；3)以熔融擠出法製造長條薄膜時，將與自模嘴開口部擠出之薄片狀熱塑性樹脂距離10mm以內之氛圍溫度加溫至特定溫度之方法；4)以滿足關係之方式將自模嘴擠出之薄片狀熱塑性樹脂於50kPa以下之壓力下密著於冷卻滾筒並拉取之方法；5)以熔融擠出法製造長條薄膜時，對於自模嘴開口部擠出之薄片狀熱塑性樹脂吹附與最初密著之冷卻滾筒之拉取速度之速度差為0.2m/s以下之風的方法。 Specifically, the method is as follows: 1) a method in which a sheet-like thermoplastic resin extruded from a nozzle is adhered to a cooling drum at a pressure of 50 kPa or less and drawn by a melt extrusion method; 2) When the long film is manufactured by melt extrusion, the film is covered with the surrounding material. The method from the mouth to the first cooling drum, the distance from the surrounding material to the opening of the nozzle or the first cooling drum is set to 100 mm or less; 3) when the long film is produced by melt extrusion, a method in which a sheet-like thermoplastic resin extruded from a nozzle opening portion is heated to a specific temperature from an atmosphere temperature within 10 mm; 4) a sheet-like thermoplastic resin extruded from a nozzle at a pressure of 50 kPa or less in a manner to satisfy a relationship a method of adhering to the cooling drum and pulling it; 5) when the long film is produced by the melt extrusion method, the drawing speed of the sheet-like thermoplastic resin extruded from the opening of the nozzle is closely attached to the first cooling drum A method in which the speed difference is 0.2 m/s or less.

該長條薄膜可為單層或2層以上之積層薄膜。積層薄膜可藉共擠出成形法、共澆鑄成形法、薄膜積層法、塗佈法等習知方法獲得。該等中較好為共擠出成形法、共澆鑄成形法。 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 conventional method such as a co-extrusion molding method, a co-cast molding method, a film lamination method, or a coating method. Among these, coextrusion molding method and co-cast molding method are preferred.

<聚碳酸酯系樹脂> <Polycarbonate resin>

本實施形態之坯片薄膜所用之聚碳酸酯系樹脂並未特別限制而可使用各種者，基於化學性質及物性之觀點較好為芳香族聚碳酸酯樹脂，特佳為雙酚A系聚碳酸酯樹脂。其中，更好使用於雙酚A中導入苯環、環己烷環及脂肪族烴基等之雙酚A衍生物者。再者，特佳為使用對於雙酚A之中央碳非對稱地導入上述官能基之衍生物所得之單位分子內之異向性減少之構造之聚碳酸酯樹脂。作為此種聚碳酸酯樹脂特佳為使用例如雙酚A之中央碳之2個甲基取代 為苯環者，例如雙酚A之各苯環之一的氫以甲基或苯基等對於中央碳非對稱地取代者所得之聚碳酸酯樹脂。 The polycarbonate resin used for the green sheet film of the present embodiment is not particularly limited and can be used in various forms, and is preferably an aromatic polycarbonate resin from the viewpoint of chemical properties and physical properties, and particularly preferably a bisphenol A-based polycarbonate. Ester resin. 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 preferably used. Further, a polycarbonate resin having a structure in which anisotropy in a unit molecule obtained by asymmetrically introducing a derivative of the above functional group to a central carbon of bisphenol A is used is particularly preferable. Particularly preferred as such a polycarbonate resin is the use of two methyl groups of a central carbon such as bisphenol A. In the case of a benzene ring, for example, hydrogen of one of the benzene rings of bisphenol A is a polycarbonate resin obtained by asymmetrically replacing a central carbon such as a methyl group or a phenyl group.

具體為藉由光氣法或酯交換法自4,4’-二羥基二苯基烷或該等之鹵素取代體獲得者，舉例為例如4,4’-二羥基二苯基甲烷、4,4’-二羥基二苯基乙烷、4,4’-二羥基二苯基丁烷等。又，除此之外亦舉例為例如日本特開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號等所記載之聚碳酸酯系樹脂。 Specifically, it is obtained by a phosgene method or a transesterification method from 4,4'-dihydroxydiphenyl alkane or a halogen substituent thereof, for example, 4,4'-dihydroxydiphenylmethane, 4, 4'-dihydroxydiphenylethane, 4,4'-dihydroxydiphenylbutane, and the like. In addition, for example, JP-A-2006-215465, JP-A-2006-91836, JP-A-2005-121813, JP-A-2003-167121, and JP-A-2009 A polycarbonate-based resin described in, for example, Japanese Laid-Open Patent Publication No. 2012-67300, No. 00/26705, and the like.

聚碳酸酯樹脂亦可與聚烯烴系樹脂、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混合使用。又，亦可於使用纖維素乙酸酯系樹脂形成之樹脂薄膜之至少一面上積層含有聚碳酸酯系樹脂之樹脂層。 The polycarbonate resin may be used in combination with a transparent resin such as a polyolefin 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 surface of a resin film formed using a cellulose acetate resin.

聚碳酸酯系樹脂較好為玻璃轉移點(Tg)為110℃以上且吸水率(於23℃水中、24小時之條件下測定之值)為0.3%以下者。又，更好為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 more and a water absorption ratio (a value measured under conditions of 23 ° C in water and 24 hours) 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.

本實施形態可使用之聚碳酸酯系樹脂薄膜可藉習知方法製膜，其中較好為溶液澆鑄法或熔融澆鑄法。 The polycarbonate resin film which can be used in the present embodiment can be formed into a film by a conventional method, and among them, a solution casting method or a melt casting method is preferred.

<添加劑> <additive>

本實施形態之坯片薄膜亦可含有添加劑。作為添加劑 有可塑劑、紫外線吸收劑、延遲調整劑、抗氧化劑、劣化防止劑、剝離助劑、界面活性劑、染料、微粒子等。本實施形態中，關於微粒子以外之添加劑可於濃液(dope liquid)調製時添加，亦可於微粒子分散液調製時添加。 The green sheet film of the present embodiment may contain an additive. As an additive There are plasticizers, ultraviolet absorbers, retardation modifiers, antioxidants, deterioration inhibitors, release aids, surfactants, dyes, fine particles, and the like. In the present embodiment, the additive other than the fine particles may be added during the preparation of the dope liquid, or may be added during the preparation of the fine particle dispersion.

(可塑劑) (plasticizer)

作為添加於坯片薄膜之可塑劑舉例為苯二甲酸酯系、脂肪酸酯系、苯偏三酸酯系、磷酸酯系、聚酯系、糖酯系、丙烯酸系聚合物等。該等中，基於透濕性之觀點較好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 green sheet 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 type polymer. Among these, a plasticizer of a polyester type and a sugar ester type polymer is preferably used from the viewpoint of moisture permeability.

聚酯系可塑劑相較於苯二甲酸二辛酯等之苯二甲酸酯系之可塑劑，非移行性或耐萃取性優異。藉由根據用途選擇該等可塑劑或併用而可應用於廣範圍用途。作為丙烯酸系聚合物較好為丙烯酸或甲基丙烯酸烷酯之均聚物或共聚物。作為丙烯酸酯之單體舉例為例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸(i-、n-)丙酯、丙烯酸(n-、i-、s-、t-)丁酯、丙烯酸(n-、i-、s-)戊酯、丙烯酸(n-、i-)己酯、丙烯酸(n-、i-)庚酯、丙烯酸(n-、i-)辛酯、丙烯酸(n-、i-)壬酯、丙烯酸(n-、i-)肉豆蔻酯、丙烯酸(2-乙基己酯)、丙烯酸(ε-己內酯)、丙烯酸(2-羥基乙酯)、丙烯酸(2-羥基丙酯)、丙烯酸(3-羥基丙酯)、丙烯酸(4-羥基丁酯)、丙烯酸(2-羥基丁酯)、丙烯酸(2-甲氧基乙酯)、丙烯酸(2-乙氧基乙酯)等或上述丙烯酸酯變為甲基丙烯酸酯者。丙烯酸系聚 合物為上述單體之均聚物或共聚物，但較好含有30質量%以上之丙烯酸甲酯單體單位，且較好具有40質量%以上之甲基丙烯酸甲酯單體單位。特佳為丙烯酸甲酯或甲基丙烯酸甲酯之均聚物。 The polyester-based plasticizer is superior in non-migration property or extraction resistance to a phthalate-based plasticizer such as dioctyl phthalate. It can be applied to a wide range of applications by selecting these plasticizers according to the use or in combination. The acrylic polymer is preferably a homopolymer or a copolymer of acrylic acid or alkyl methacrylate. Examples of the acrylate monomer are, for example, methyl acrylate, ethyl acrylate, (i-, n-) propyl acrylate, (n-, i-, s-, t-) butyl acrylate, acrylic acid (n-, I-, s-) amyl ester, acrylic acid (n-, i-) hexyl ester, acrylic acid (n-, i-) heptyl ester, acrylic acid (n-, i-) octyl ester, acrylic acid (n-, i-) Oxime ester, acrylic acid (n-, i-) myristyl ester, acrylic acid (2-ethylhexyl ester), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl ester), acrylic acid (2-hydroxypropyl ester) ), acrylic acid (3-hydroxypropyl ester), acrylic acid (4-hydroxybutyl ester), acrylic acid (2-hydroxybutyl ester), acrylic acid (2-methoxyethyl ester), acrylic acid (2-ethoxyethyl ester) Or the above acrylate to methacrylate. Acrylic polymerization The compound is a homopolymer or a copolymer of the above monomer, but preferably contains 30% by mass or more of a methyl acrylate monomer unit, and preferably has 40% by mass or more of a methyl methacrylate monomer unit. Particularly preferred is a homopolymer of methyl acrylate or methyl methacrylate.

聚酯系可塑劑為一價至四價羧酸與一價至六價醇之反應物，主要可使用二價羧酸與二醇反應而得者。作為代表性二羧酸舉例為戊二酸、依康酸、己二酸、苯二甲酸、壬二酸、癸二酸等。且聚酯系可塑劑之較佳為芳香族末端酯系可塑劑。作為芳香族末端酯系可塑劑較好為具有使苯二甲酸、己二酸、至少一種苯單羧酸及至少一種碳數2~12之烷二醇反應之構造的酯化合物。作為最終化合物構造只要具有己二酸殘基及苯二甲酸殘基即可，製造酯化合物時，亦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, and can be mainly obtained by reacting a divalent carboxylic acid with a diol. Typical dicarboxylic acids are glutaric acid, isaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid and the like. Further, the polyester-based plasticizer is preferably an aromatic terminal ester-based plasticizer. The aromatic terminal ester-based plasticizer is preferably an ester compound having a structure in which phthalic acid, adipic acid, at least one benzene monocarboxylic acid, and at least one alkanediol having 2 to 12 carbon atoms are reacted. The final compound structure may have an adipic acid residue and a phthalic acid residue, and when the ester compound is produced, it may be reacted as an acid anhydride or an esterified product of a dicarboxylic acid.

作為苯單羧酸成分有例如苯甲酸、對-第三丁基苯甲酸、鄰甲苯酸、間甲苯酸、對甲苯酸、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，最好為苯甲酸。且，該等亦可分別使用一種或作為兩種以上之混合物使用。 Examples of the benzene monocarboxylic acid component include benzoic acid, p-t-butylbenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, and amine. Benzoic acid, ethoxylated benzoic acid, etc., are preferably benzoic acid. Further, these may be used alone or as a mixture of two or more.

作為碳數2~12之烷二醇成分舉例為乙二醇、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(3,3-二羥甲基戊烷)、2-正丁基-2-乙基-1,3-丙二醇(3,3-二羥甲基庚烷)、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。該等中特佳為1,2-丙二醇。該等之二醇可使用一種或以兩種以上之混合物使用。 Examples of the alkanediol component having 2 to 12 carbon atoms are ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 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-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dihydroxymethylglycol) Alkyl), 3-methyl-1,5-pentanediol, 1,6-hexane Alcohol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9- Decylene glycol, 1,10-nonanediol, 1,12-octadecanediol, and the like. Particularly preferred among these are 1,2-propanediol. These diols may be used alone or in combination of two or more.

芳香族末端酯系可塑劑可為寡聚酯、聚酯之類型之任一種，分子量宜為100~10000之範圍，更好為350~3000之範圍。且酸價為1.5mgKOH/g以下、羥基(hydroxyl)價為25mgKOH/g以下，更好酸價為0.5mgKOH/g以下、羥基(hydroxyl)價為15mgKOH/g以下者。 The aromatic terminal ester type plasticizer may be of any type of oligoester or polyester, and the molecular weight is preferably in the range of 100 to 10,000, more preferably in the range of 350 to 3,000. Further, the acid value is 1.5 mgKOH/g or less, the hydroxyl group value is 25 mgKOH/g or less, the acid value is preferably 0.5 mgKOH/g or less, and the hydroxyl group value is 15 mgKOH/g or less.

具體舉例為以下所示化合物等，但不限於該等。 Specific examples thereof include the compounds shown below, but are not limited thereto.

作為糖酯系化合物為纖維素酯以外之酯，且為下述單糖、二糖、三糖或寡糖等之糖的OH基全部或一部分經酯化之化合物，作為更具體之例示可舉例為以通式(4)表示之化合物等。 The sugar ester compound is an ester other than the cellulose ester, and is a compound in which all or a part of the OH group of the sugar of the following monosaccharide, disaccharide, trisaccharide or oligosaccharide is esterified, and more specific examples are exemplified. It is a compound represented by the formula (4) and the like.

式中，R1~R8表示氫原子、取代或未取代之碳數2~22之烷羰基或取代或未取代之碳數2~22之芳基碳基。R1~R8可相同亦可不同。 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 aryl carbon group having 2 to 22 carbon atoms. R 1 to R 8 may be the same or different.

以下更具體例示通式(4)所示之化合物(化合物1-1~化合物1-23)，但不限於該等。又，下表中平均取代度未達8.0時，R1~R8中之任一者表示氫原子。 The compound represented by the formula (4) (compound 1-1 to compound 1-23) is more specifically exemplified below, but is not limited thereto. Further, when the average degree of substitution in the following table is less than 8.0, any of R 1 to R 8 represents a hydrogen atom.

該等可塑劑相對於纖維素酯薄膜100質量份，較好添加0.5~30質量份。 These plasticizers are preferably added in an amount of 0.5 to 30 parts by mass based on 100 parts by mass of the cellulose ester film.

(延遲調整劑) (delay adjuster)

做為用於調整延遲而添加之化合物可使用如歐洲專利第911,656A2號說明書中記載之具有兩個以上芳香族環之芳香族化合物。 As the compound to be added for the adjustment of the retardation, an aromatic compound having two or more aromatic rings as described in the specification of European Patent No. 911,656A2 can be used.

又，亦可併用兩種以上之芳香族化合物。該芳香族化合物之芳香環中，除了芳香族烴環以外，特佳含有芳香族雜環。芳香族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 particularly 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.

(聚合物或寡聚物) (polymer or oligomer)

本實施形態之坯片薄膜較好含有纖維素酯與具有自羧基、羥基、胺基、醯胺基及磺酸基所選出之取代基且重量平均分子量為500~200,000之範圍內之乙烯系化合物之聚合物或寡聚物。該纖維素酯與該聚合物或寡聚物之含量之質量比較好於95：5~50：50之範圍內。 The green sheet film of the present embodiment preferably contains a cellulose ester and a vinyl compound having a substituent selected from a carboxyl group, a hydroxyl group, an amine group, a mercapto group and a sulfonic acid group and having a weight average molecular weight of 500 to 200,000. a polymer or oligomer. The content of the cellulose ester and the polymer or oligomer is preferably in the range of 95:5 to 50:50.

(霧化劑) (atomizing agent)

本實施形態中，可於坯片薄膜中含有微粒子作為霧化劑，藉此，可易於搬送及捲取坯片薄膜及使用其製造之長條斜面延伸薄膜。 In the present embodiment, fine particles can be contained as an atomizing agent in the green sheet film, whereby the green sheet film and the long beveled stretch film produced using the same can be easily conveyed and wound.

霧化劑粒徑較好為10nm~0.1μm之1次粒子或2次粒子。較好使用1次粒子之針狀比為1.1以下之略球狀之霧化劑。 The atomization agent preferably has a primary particle diameter or a secondary particle diameter of 10 nm to 0.1 μm. It is preferred to use a slightly spherical atomizing agent having a needle-to-needle ratio of 1.1 or less.

作為微粒子較好為含矽者，尤其較好為二氧化矽。本實施形態中較佳之二氧化矽微粒子可舉例為例如日本AEROSIL(股)製之以AEROSIL R972、R972V、R974、R812、200、200V、300、R202、OX50、TT600(以上為日本AEROSIL(股)製)之商品名銷售者，可較好地使用AEROSIL 200V、R972、R972V、R974、R202、R812。作為聚合物微粒子之例可舉例為聚矽氧樹脂、氟樹脂及丙烯酸樹脂。較好為聚矽氧樹脂，特佳為具有三次元網狀構造者。作為此種樹脂，可舉例為例如 TOSPEARL 103、TOSPEARL 105、TOSPEARL 108、TOSPEARL 120、TOSPEARL 145、TOSPEARL 3120及TOSPEARL 240(TOSHIBA SILICONE(股)製)。 The fine particles are preferably those containing ruthenium, and particularly preferably ruthenium dioxide. The preferred cerium oxide microparticles in the present embodiment can be exemplified by, for example, AEROSIL R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (hereinafter referred to as Japan AEROSIL). AEROSIL 200V, R972, R972V, R974, R202, and R812 can be preferably used as the seller of the product name. Examples of the polymer fine particles include polyoxyxylene resins, fluororesins, and acrylic resins. It is preferably a polyoxyxylene resin, and particularly preferably a three-dimensional network structure. As such a resin, for example, for example TOSPEARL 103, TOSPEARL 105, TOSPEARL 108, TOSPEARL 120, TOSPEARL 145, TOSPEARL 3120, and TOSPEARL 240 (TOSHIBA SILICONE).

二氧化矽微粒子較好為1次平均粒徑為20nm以下且視比重為70g/L以上者。1次粒子之平均粒徑更好為5~16nm，又更好為5~12nm。1次粒子平均粒徑越小，濁度越低而較佳。視比重較好為90~200g/L以上，更好為100~200g/L以上。視比重越大，越可製作高濃度之微粒子分散液，不發生濁度、凝集物而較佳。 The cerium oxide microparticles preferably have a primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g/L or more. The average particle diameter of the primary particles is preferably from 5 to 16 nm, more preferably from 5 to 12 nm. The smaller the average particle diameter of the primary particles, the lower the turbidity and the better. The apparent specific gravity is preferably 90 to 200 g/L or more, more preferably 100 to 200 g/L or more. The larger the specific gravity, the higher the concentration of the fine particle dispersion can be produced, and the turbidity and agglomerates do not occur, and it is preferable.

本實施形態之霧化劑添加量，坯片薄膜每1m2較好為0.01~1.0g，更好為0.03~0.3g，又更好為0.08~0.16g。 The amount of the atomizing agent to be added in the embodiment is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, even more preferably 0.08 to 0.16 g per 1 m 2 of the green film.

(其他添加劑) (other additives)

此外，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之熱安定劑。進而亦可添加界面活性劑、剝離促進劑、抗靜電劑、難燃劑、滑劑、油劑等。 Further, 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 slip agent, an oil agent, or the like may be added.

(張力軟化點) (tension softening point)

本實施形態之坯片薄膜被要求耐於在更高溫環境下使用。因此，坯片薄膜之張力軟化點若為105℃~145℃則顯示充分之耐熱性故而較佳，尤其較好為110℃~130℃。 The green sheet film of the present embodiment is required to be resistant to use in a higher temperature environment. Therefore, it is preferable that the tensile softening point of the green sheet film is from 105 ° C to 145 ° C to exhibit sufficient heat resistance, and particularly preferably from 110 ° C to 130 ° C.

張力軟化點之具體測定方法可使用例如 TENSILON試驗機(ORIENTEC公司製，RTC-1225A)，將試料薄膜切出120mm(長)×10mm(寬)，邊以10N之張力拉伸邊以30℃/min之升溫速度持續升溫，測定3次成為9N之時點之溫度，由其平均值求得。 A specific measurement method of the tension softening point can be used, for example. TENSILON test machine (RTC-1225A, manufactured by ORIENTEC Co., Ltd.), the sample film was cut into 120 mm (length) × 10 mm (width), and the film was continuously stretched at a temperature increase rate of 30 ° C / min while stretching at a tension of 10 N, and measured three times. The temperature at the time of becoming 9N is obtained from the average value.

(尺寸變化率) (dimension change rate)

將本實施形態之坯片薄膜斜面延伸後之薄膜使用於有機EL圖像顯示裝置時，為了不會發生因吸濕產生之尺寸變化所致之厚度不均或相位差值之變化及對比度降低或色不均之問題，斜面延伸薄膜之尺寸變化率(%)較好未達0.5%，更好未達0.3%。 When the film having the beveled surface of the green sheet of the present embodiment is used in an organic EL image display device, thickness variation or phase difference variation and contrast reduction are not caused in order to prevent dimensional change due to moisture absorption. The problem of uneven color, the dimensional change rate (%) of the beveled stretch film is preferably less than 0.5%, more preferably less than 0.3%.

(缺陷) (defect)

本實施形態之坯片薄膜係薄膜中缺陷較少較佳。此處所謂缺陷意指溶液製膜之乾燥步驟中因溶劑急遽蒸發所發生之薄膜中空洞(發泡缺陷)或因製膜原液中之異物或混入製膜中之異物所引起之薄膜中異物(異物缺陷)。 In the green sheet film of the present embodiment, defects are less preferable. The term "defect" as used herein means a film hollow (foaming defect) which occurs due to rapid evaporation of a solvent in a drying step of a solution film, or a foreign matter in a film caused by foreign matter in a film forming solution or foreign matter mixed in a film forming film ( Foreign body defects).

具體而言較好薄膜面內之直徑5μm以上之缺陷為1個/10cm見方以下。更好為0.5個/10cm見方以下，又更好為0.1個/10cm見方以下。 Specifically, it is preferable that the defect having a diameter of 5 μm or more in the plane of the film is 1/10 cm square or less. More preferably 0.5 /10 cm square, and more preferably 0.1 /10 cm square.

所謂上述缺陷之直徑於缺陷為圓形時表示其直徑，非圓形時缺陷之範圍係藉由下述方法以顯微鏡觀察而決定，設為其最大徑(外切圓直徑)。 The diameter of the above-mentioned defect indicates the diameter when the defect is a circle, and the range of the defect when it is not circular is determined by microscopic observation by the following method, and the maximum diameter (circumscribed circle diameter) is set.

缺陷範圍於缺陷為氣泡或異物時，為以微分 干涉顯微鏡之透過光觀察缺陷時陰影之大小。缺陷於輥傷之轉印或擦傷等之表面形狀變化時，以微分干涉顯微鏡之反射光觀察缺陷並確認大小。 Defects range from when the defect is a bubble or a foreign object The size of the shadow when observing a defect through the light of an interferometric microscope. When the surface shape of the transfer or scratch such as a roll injury is changed, the defect is observed by the differential interference microscope and the size is confirmed.

又，以反射光觀察時，若缺陷大小不明確，則於表面蒸鍍鋁或鉑後進行觀察。生產性良好地獲得以該缺陷頻度表示之品質優異之薄膜時，有效地是於恰在澆鑄前高精度過濾聚合物溶液，或提高澆鑄機周邊之乾淨度，且階段性設定澆鑄後之乾燥條件，效率良好且抑制發泡地進行乾燥。 Further, when observing the reflected light, if the size of the defect is not clear, aluminum or platinum is vapor-deposited on the surface and observed. When the film having excellent quality expressed by the frequency of the defect is obtained with good productivity, it is effective to filter the polymer solution with high precision just before casting, or to improve the cleanliness of the periphery of the casting machine, and to set the drying conditions after casting in stages. It is efficient and inhibits foaming and drying.

缺陷個數若多於1個/10cm見方，則於例如其後步驟之加工時等對薄膜施加張力時，會有以該缺陷作為起點使薄膜破裂而使生產性降低之情況。且，缺陷直徑若為5μm以上，則藉由偏光板觀察等可以目視進行確認，於使用作為光學構件時有產生亮點之情況。 When the number of defects is more than one /10 cm square, for example, when tension is applied to the film during processing such as the subsequent step, the film may be broken by the defect as a starting point, and the productivity may be lowered. 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 a bright spot may be generated when the optical member is used.

(全光線透過率) (total light transmittance)

本實施形態之坯片薄膜較好其全光線透過率為90%以上，更好為93%以上。且作為全光線透過率之現實上之上限為99%左右。達成以該全光線透過率表示之優異透明性時，不導入會吸收可見光之添加劑或共聚合成分，或藉由高精度過濾聚合物中之異物，可有效地減低薄膜內之光擴散或吸收。且，藉由使製膜時之薄膜接觸部(冷卻輥、軋光輥、滾筒、皮帶、溶液製膜中之塗佈基材、搬送輥等)之表面粗糙度減小而使薄膜表面的表面粗糙度減小，可有 效減低薄膜表面之光擴散或反射。 The green sheet 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 total light transmittance is about 99%. When the excellent transparency is expressed by the total light transmittance, the additive or the copolymerization component which absorbs visible light is not introduced, or the foreign matter in the polymer is filtered with high precision, and the light diffusion or absorption in the film can be effectively reduced. 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. Roughness is reduced, there may be Effectively reduce light diffusion or reflection on the surface of the film.

(坯片薄膜之製膜法) (film forming method of blank film)

包含上述樹脂之本實施形態之坯片薄膜可藉由以下所示之溶液澆鑄製膜法、熔融澆鑄製膜法之任一者製膜。又，此處針對坯片薄膜包含纖維素酯系樹脂之情況加以說明，但包含其他樹脂之情況亦相同。 The green sheet film of the present embodiment containing the above resin can be formed into a film by any of the solution casting film forming method and the melt casting film forming method shown below. Here, the case where the green sheet-form film contains the cellulose ester-based resin will be described, but the case of including other resins is also the same.

以溶液澆鑄製膜法製造坯片薄膜時，纖維素酯系樹脂之坯片薄膜之原料溶液的濃液藉由澆鑄模嘴澆鑄於由旋轉金屬製環型皮帶所成之支撐體上。藉由澆鑄而於支撐體上形成之濃液膜亦即網片(web)於支撐體上繞約一周後，藉由剝離輥剝離。剝離之網片(薄膜)接著導入由拉幅機所成之延伸裝置。 When a green sheet film is produced by a solution casting film forming method, a dope of a raw material solution of a green sheet resin of a cellulose ester resin is cast on a support made of a rotating metal toroidal belt by a casting nozzle. The concentrated liquid film formed on the support by casting, that is, the web, is wound around the support for about one week, and then peeled off by a peeling roll. The stripped web (film) is then introduced into an extension device formed by a tenter.

以熔融澆鑄製膜法製造坯片薄膜時，藉由使用T模嘴之擠出方法，將聚合物於可熔融之溫度熔融，自T模嘴以薄膜狀(薄片狀)擠出於冷卻滾筒上，冷卻固化並自冷卻滾筒剝離薄膜。剝離之薄膜接著導入由拉幅機所成之延伸裝置。 When a green sheet film is produced by a melt casting film forming method, the polymer is melted at a meltable temperature by a T-die extrusion method, and extruded from a T-die into a film roll (sheet-like) on a cooling drum. The film is cooled and solidified and the film is peeled off from the cooling drum. The peeled film is then introduced into an extension device formed by a tenter.

以下針對各製膜法細節加以說明。 The details of each film forming method will be described below.

[溶液澆鑄製膜法] [solution casting film forming method]

於利用溶液澆鑄製膜法之坯片薄膜之製造方法中，將纖維素酯溶液的濃液之固體成分濃度調製為通常10~40質量%左右，且於澆鑄步驟中之澆鑄時濃液黏度調製為 1~200泊之範圍。 In the method for producing a green sheet film by a solution casting film forming method, the solid content concentration of the dope of the cellulose ester solution is adjusted to about 10 to 40% by mass, and the viscosity of the dope is adjusted during casting in the casting step. for 1 to 200 poise range.

此處，首先，纖維素酯之溶解通常使用於溶解釜中之攪拌溶解方法、加熱溶解方法、超音波溶解方法等手段，於加壓下加熱至溶劑之常壓下之沸點以上且不使溶劑沸騰之範圍的溫度，邊攪拌邊溶解之方法，由於可防止凝膠或稱為麵疙瘩之塊狀未溶解物發生故而較佳。又，亦可使用日本特開平9-95538號公報記載之冷卻溶解方法或日本特開平11-21379號公報記載之高壓下溶解之方法等。 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 dissolution method, and the like, and is heated under pressure to a boiling point of a solvent at a normal pressure or higher without causing a solvent. The method of dissolving while stirring at a temperature in the boiling range is preferable because it prevents the occurrence of a gel or a blocky undissolved matter called a dough. Further, a method of cooling and dissolving described in JP-A-H09-95538, a method of dissolving under high pressure as described in JP-A-11-21379, and the like can be used.

亦較好使用將纖維素酯與弱溶劑混合並濕潤或膨潤後進一步與良溶劑混合並溶解之方法。此時，亦可各分為將纖維素酯與弱溶劑混合並濕潤或膨潤之裝置，及與良溶劑混合並溶解之裝置。 It is also preferred to use a method in which a cellulose ester is mixed with a weak solvent, wetted or swollen, and further mixed with a good solvent and dissolved. In this case, it may be divided into a device which mixes and wets or swells a cellulose ester with a weak solvent, and a device which mixes and dissolves with a good solvent.

纖維素酯之溶解所用之加壓容器種類並未特別限制，只要可耐特定壓力，可於加壓下加熱、攪拌即可。加壓容器可適當配設其他壓力計、溫度計等測定器類。加壓亦可藉由壓入氮氣等惰性氣體之方法或藉由加熱使溶劑蒸氣壓上升而進行。加熱較好自外部進行，例如夾套型者由於溫度控制容易故較佳。 The type of the pressurized container used for the dissolution of the cellulose ester is not particularly limited, and may be heated and stirred under pressure as long as it can withstand a specific pressure. As the pressurized container, other measuring instruments such as a pressure gauge and a thermometer can be appropriately disposed. The pressurization may be carried out by injecting an inert gas such as nitrogen or by heating to increase the vapor pressure of the solvent. The heating is preferably carried out from the outside, and for example, a jacket type is preferred because of temperature control.

添加溶劑之加熱溫度為使用之溶劑沸點以上，於2種以上之混合溶劑時，較好為加溫至沸點低者之溶劑的沸點以上之溫度且該溶劑不沸騰之範圍之溫度。加熱溫度過高時，所需之壓力變大，生產性變差。較佳之加熱溫度範圍為20~120℃，更好為30~100℃，又更好為 40~80℃之範圍。且壓力係調整為於設定溫度下不使溶劑沸騰。 The heating temperature of the solvent to be added is not less than the boiling point of the solvent to be used. When the solvent is mixed in two or more kinds, it is preferably a temperature which is heated to a temperature equal to or higher than the boiling point of the solvent having a low boiling point and which does not boil. When the heating temperature is too high, the required pressure becomes large, and productivity is deteriorated. The preferred heating temperature range is 20 to 120 ° C, more preferably 30 to 100 ° C, and even better 40~80 °C range. And the pressure is adjusted so as not to boil the solvent at the set temperature.

除了纖維素酯與溶劑以外，必要之可塑劑、紫外線吸收劑等之添加劑可預先與溶劑混合、溶解或分散後投入纖維素酯溶解前之溶劑中，亦可投入纖維素酯溶解後之濃液中。 In addition to the cellulose ester and the solvent, an additive such as a plasticizer or an ultraviolet absorber may be mixed with a solvent, dissolved or dispersed, and then introduced into a solvent before dissolution of the cellulose ester, or may be added to a concentrated solution after dissolution of the cellulose ester. in.

纖維素酯溶解後係邊冷卻邊自溶劑取出，或以泵自容器抽出並以熱交換器冷卻，將所得之纖維素酯濃液供於製膜，此時之冷卻亦可進行至常溫。 After the cellulose ester is dissolved, it is taken out from the solvent while being cooled, or pumped from the container and cooled by a heat exchanger, and the obtained cellulose ester dope is supplied to the film, and the cooling can be carried out to room temperature.

纖維素酯原料與溶劑之混合物以具有攪拌機之溶解裝置溶解時，較好使攪拌翼之周速至少0.5m/秒以上，且攪拌30分鐘以上而溶解。 When the mixture of the cellulose ester raw material and the solvent is dissolved in a dissolving device having a stirrer, the peripheral speed of the stirring blade is preferably at least 0.5 m/sec or more, and the mixture is stirred for 30 minutes or more to be dissolved.

纖維素酯濃液中所含之異物(尤其是液晶顯示裝置中誤認為圖像之異物)必須藉由過濾將其去除。作為光學薄膜之品質亦可藉由過濾而決定。 The foreign matter contained in the cellulose ester concentrate (especially a foreign matter which is mistaken for an image in a liquid crystal display device) must be removed by filtration. The quality of the optical film can also be determined by filtration.

過濾所使用之濾材之絕對過濾精度越小越好，絕對過濾精度過小時，容易發生濾材阻塞，必須頻繁進行濾材之更換，而有生產性降低之問題。因此，纖維素酯濃液中使用之濾材較好為絕對過濾精度0.008mm以下者，更好為0.001~0.008mm之範圍，又更好為0.003~0.006mm之範圍的濾材。 The absolute filtration accuracy of the filter material used for filtration is preferably as small as possible. When the absolute filtration accuracy is too small, the filter material is likely to be clogged, and the filter material must be frequently replaced, and the productivity is lowered. Therefore, the filter medium used in the cellulose ester dope preferably has an absolute filtration accuracy of 0.008 mm or less, more preferably 0.001 to 0.008 mm, and more preferably a filter material in the range of 0.003 to 0.006 mm.

濾材材質並未特別限制，可使用通常之濾材，但聚丙烯、鐵氟龍(註冊商標)等之塑膠纖維製之濾材或不鏽鋼纖維等金屬製濾材並無纖維脫落等而較佳。 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 preferably not detached from the fiber.

纖維素酯濃液之過濾可藉通常方法進行，但為在溶劑之常壓下之沸點以上且不使溶劑沸騰之範圍之溫度加壓下加熱邊過濾之方法由於濾材前後壓差(以下有時稱為濾壓)上升較小故較佳。 Filtration of the cellulose ester concentrate can be carried out by a usual method, but it is a method of filtering under heating under pressure at a temperature above the boiling point of the solvent at a normal pressure and not boiling the solvent due to the difference in pressure before and after the filter material (hereinafter sometimes It is better to refer to the filter pressure as the rise is small.

較佳之過濾溫度範圍為45~120℃，更好為45~70℃，又更好在45~55℃之範圍。 The preferred filtration temperature range is from 45 to 120 ° C, more preferably from 45 to 70 ° C, and even more preferably from 45 to 55 ° C.

濾壓較好為3500kPa以下，更好為3000kPa以下，又更好為2500kPa以下。又，濾壓可藉由適當選擇過濾流量與過濾面積而控制。 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. Further, the filtration pressure can be controlled by appropriately selecting the filtration flow rate and the filtration area.

製造纖維素酯系樹脂之坯片薄膜時，首先，將纖維素酯溶解於良溶劑與弱溶劑之混合溶劑中，於其中添加上述可塑劑或紫外線吸收劑而調製纖維素酯溶液(濃液)。 When producing a green sheet film of a cellulose ester resin, first, a cellulose ester is dissolved in a mixed solvent of a good solvent and a weak solvent, and the above plasticizer or ultraviolet absorber is added thereto to prepare a cellulose ester solution (dope). .

濃液可於支撐體之溫度一般為0℃~未達溶劑沸點之範圍澆鑄於支撐體上，進而可於5℃~溶劑沸點-5℃之溫度範圍澆鑄於支撐體上，但更好於5~30℃之溫度範圍澆鑄於支撐體上。此時，周圍氛圍濕度必須控制為露點以上。 The dope can be cast on the support at a temperature of usually from 0 ° C to the boiling point of the solvent, and can be cast on the support at a temperature ranging from 5 ° C to the boiling point of the solvent - 5 ° C, but better than 5 A temperature range of ~30 ° C is cast on the support. At this time, the ambient humidity must be controlled to be above the dew point.

又，濃液黏度調整為1~200泊之濃液自澆鑄模嘴已成為大致均一膜厚之方式澆鑄於支撐體上，於澆鑄膜中之殘留溶劑量對於固體成分重量200%以上時，使澆鑄膜溫度成為溶劑沸點以下，且於殘留溶劑量為200%以下~剝離之前，澆鑄膜溫度成為溶劑沸點+20℃以下之範圍之方式，藉由乾燥風乾燥澆鑄膜(網片)。 Further, the dope having a viscosity of the concentrated liquid adjusted to a concentration of 1 to 200 poises is cast onto the support in such a manner that the solid solution mold mouth has a substantially uniform film thickness, and when the amount of residual solvent in the cast film is 200% or more by weight of the solid component, The temperature of the cast film is not more than the boiling point of the solvent, and the cast film (mesh) is dried by dry air so that the amount of the residual solvent is 200% or less to the range of the boiling point of the solvent and the boiling point of the solvent is not more than 20 ° C.

此處，殘留溶劑量係以下述式表示。 Here, the amount of residual solvent is represented by the following formula.

殘留溶劑量(質量%)={(M-N)/N}×100 Residual solvent amount (% by mass) = {(M - N) / N} × 100

惟，式中，M為網片之任意時點之重量，N為將重量M者於110℃乾燥3小時時之重量。 However, in the formula, M is the weight of the mesh at any point in time, and N is the weight when the weight M is dried at 110 ° C for 3 hours.

於支撐體上，為了將網片乾燥固化至成為可自支撐體剝離之膜強度，較好將網片中殘留溶劑量乾燥至150質量%以下，更好為50~120%。 In order to dry and cure the web to a film strength which can be peeled off from the support, the amount of residual solvent in the web is preferably dried to 150% by mass or less, more preferably 50 to 120%.

自支撐體剝離網片時之網片溫度較好為0~30℃。又，網片剛自支撐體剝離後因自支撐體密著面側之溶劑蒸發而使溫度暫時急速下降，為了易於冷凝氛圍中之水蒸氣或溶劑蒸氣等揮發性成分，故更好剝離時之網片溫度為5~30℃。 The web temperature when the self-supporting body peels off the mesh is preferably 0 to 30 °C. Further, immediately after the web is peeled off from the support, the temperature of the self-supporting body is evaporated, and the temperature is temporarily lowered rapidly. In order to easily condense volatile components such as water vapor or solvent vapor in the atmosphere, it is better to peel off. The mesh temperature is 5~30 °C.

網片(或薄膜)之乾燥步驟一般採用輥懸掛方法，或以銷拉幅機方式或夾具拉幅機方式邊搬送網片邊乾燥之方式。 The drying step of the mesh (or film) is generally carried out by a roll hanging method, or by means of a pin tenter method or a clamp tenter method while conveying the mesh side to dry.

將剝離後之網片例如導入一次乾燥裝置。於一次乾燥裝置內，藉由自側面看配置為鋸齒狀之複數個搬送輥蛇行搬送網片，於其間之網片自乾燥裝置之頂側吹入並自乾燥裝置底部分排出之溫風而乾燥。 The peeled web is introduced, for example, into a primary drying device. In a drying apparatus, a plurality of conveying rollers arranged in a zigzag shape are arranged to be serpentinely conveyed from the side, and the web is blown in from the top side of the drying device and dried by the warm air discharged from the bottom portion of the drying device. .

其次，將所得薄膜(薄片)於單軸方向延伸。藉由延伸使分子配向。延伸方法並未特別限制，但可較好地使用習知之銷拉幅機或夾具式拉幅機等。延伸方向可為長度方向亦可為寬度方向之任意方向(斜面方向)，但藉由將延伸方向設為寬度方向，易於調整坯片薄膜之斷 裂身長度而較佳。 Next, the obtained film (sheet) was stretched in the uniaxial direction. The molecules are aligned by extension. The stretching method is not particularly limited, but a conventional pin tenter or jig tenter or the like can be preferably used. The extending direction may be either the length direction or the width direction (the bevel direction), but it is easy to adjust the blank film by setting the extending direction to the width direction. It is better to split the length.

尤其，自支撐體剝離後之乾燥步驟中，因溶劑之蒸發而使網片於寬度方向收縮。越於高溫度乾燥收縮越大。邊儘可能抑制該收縮邊乾燥時，由於使完成之薄膜平面性良好而較佳。基於此點，較好為例如日本特開昭62-46625號公報所示般之乾燥所有步驟或一部分步驟於寬度方向以夾具對網片寬度兩端進行寬度保持邊乾燥之方法(拉幅機方式)。 In particular, in the drying step after the self-supporting body is peeled off, the web is shrunk in the width direction by evaporation of the solvent. The higher the drying shrinkage at higher temperatures. When the shrinkage is dried as much as possible, it is preferable because the film properties of the finished film are good. In this regard, it is preferable to dry all the steps or a part of the steps in the width direction by the jig to maintain the width of both ends of the width of the mesh in the width direction (tenter method). ).

作為坯片薄膜之延伸條件可以獲得期望之斷裂伸長度特性之方式選擇溫度、倍率。通常，延伸倍率為1.1~2.0倍，較好為1.2~1.5倍，延伸溫度通常設定為構成薄片之樹脂的玻璃轉移溫度(Tg)-40℃~Tg+50℃，較好為Tg-40℃~Tg+40℃之溫度範圍。延伸倍率過小時，有無法獲得期望斷裂伸長度特性之情況，相反地若過大，則有斷裂之情況。延伸溫度過低時會破裂，且過高時有無法獲得期望斷裂伸長度特性之情況。 The temperature and the magnification are selected in such a manner that the elongation at break of the desired properties can be obtained as the elongation condition of the green sheet film. 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 to a glass transition temperature (Tg) of -40 ° C to Tg + 50 ° C, preferably Tg - 40 ° C. ~Tg+40°C temperature range. When the stretching ratio is too small, there is a case where the desired elongation at break property cannot be obtained, and if it is too large, there is a case where it is broken. When the elongation temperature is too low, it will rupture, and when it is too high, the desired elongation at break property cannot be obtained.

以上述方法製作之熱塑性樹脂薄膜之斷裂伸長度特性於修正為符合目的之期望特性時，薄膜亦可於長度方向或寬度方向延伸或收縮。於長度方向收縮時，有藉由例如於寬度延伸暫時釋放夾具而於長度方向鬆弛，或於橫延伸裝置之相鄰夾具之間隔緩慢變窄，而使薄膜收縮之方法。後者方法可使用一般同時雙軸延伸裝置，藉由使縱方向相鄰之夾具間隔以例如縮放方式或線性驅動方式驅動夾具部分滑順地緩慢變窄之方法進行。 When the elongation at break property of the thermoplastic resin film produced by the above method is corrected to a desired characteristic according to the purpose, the film may also extend or contract in the longitudinal direction or the width direction. When shrinking in the longitudinal direction, there is a method in which the film is shrunk in the longitudinal direction by, for example, stretching the temporary release jig, or the interval between adjacent jigs of the lateral stretching device is gradually narrowed. The latter method can be carried out by using a generally simultaneous biaxial stretching device by driving the longitudinally adjacent jig spacing to, for example, zoom or linear drive to drive the grip portion to smoothly narrow.

以拉幅機之把持/延伸亦可於自剛剝離後之膜的殘留溶劑量為50~150質量%至正要捲取前之實質殘留溶劑量為0質量%之範圍進行，但較好以殘留溶劑量為5~10%之範圍進行。 The holding/extension of the tenter may be carried out in a range from 50 to 150% by mass of the residual solvent of the film immediately after the stripping to a mass residual amount of 0% by mass before the winding, but preferably The amount of residual solvent is in the range of 5 to 10%.

拉幅機一般亦可在基底行進方向分為數個溫度區域良好地進行。延伸時之溫度係選擇為可獲得期望物性或平面性之溫度，但拉幅機前後之乾燥區域溫度因種種理由有時亦選擇與延伸時之溫度不同之溫度。例如拉幅機前之乾燥區域之氛圍溫度與拉幅機內之溫度不同時，接近拉幅機入口之區域溫度一般係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溫度而進行。拉幅機後與拉幅機內之溫度不同時亦同樣將接近拉幅機出口之區域溫度設定為拉幅機後與拉幅機內之溫度的中間溫度。拉幅機前之乾燥區域溫度一般為30~120℃，較好為50~100℃，拉幅機內延伸部之溫度為50~180℃，較好為80~170℃，拉幅機入口部或出口部之溫度係自該等中間溫度適當選擇。 The tenter can generally be carried out well in several temperature zones in the direction of travel of the substrate. The temperature at the time of extension is selected to obtain a desired physical property or flatness temperature, but the temperature of the drying zone before and after the tenter may be different from the temperature at the time of extension for various reasons. For example, when the ambient temperature in the drying area before the tenter is different from the temperature in the tenter, the temperature in the area near the entrance of the tenter is generally set to the temperature in the dry area before the tenter and the temperature in the center of the tenter. The intermediate temperature is carried out. The temperature of the region near the exit of the tenter is also set to the intermediate temperature between the tenter and the temperature inside the tenter when the tenter is different from the temperature in the tenter. The temperature in the drying zone before the tenter is generally 30~120°C, preferably 50~100°C, and the temperature in the extension part of the tenter is 50~180°C, preferably 80~170°C, the entrance of the tenter. The temperature at the outlet or the outlet is suitably selected from these intermediate temperatures.

延伸之圖型亦即把持夾具之軌跡係與溫度同樣基於膜之光學物性或平面性而選擇且有多種，但較好使用於把持開始後暫時為固定寬，隨後進行延伸，延伸結束後再以一定寬度保持之圖型。於拉幅機出口附近之夾具把持結束之附近，為了抑制因釋放把持所致之基底振動，一般進行寬度緩和。 The extended pattern, that is, the trajectory of the holding fixture and the temperature are also selected based on the optical properties or planarity of the film, and are preferably used for temporarily fixing the width after the start of the holding, and then extending, and after the extension is completed, A pattern that maintains a certain width. In the vicinity of the grip holding near the exit of the tenter, in order to suppress the vibration of the base due to the release grip, the width is generally relaxed.

延伸之圖型亦與延伸速度有關連，但延伸速 度一般為10~1000(%/min)，較好為100~500(%/min)。該延伸速度於夾具軌跡為曲線時並非固定，而是於基底行進方向緩緩變化。 The extended pattern is also related to the extension speed, but the extension speed The degree is generally 10 to 1000 (%/min), preferably 100 to 500 (%/min). The extension speed is not fixed when the jig trajectory is a curve, but changes slowly in the direction in which the substrate travels.

再者，利用上述拉幅機方式之乾燥後網片(薄膜)接著導入二次乾燥裝置。於二次乾燥裝置內，藉由自側面來看配置為鋸齒狀之複數搬送輥使網片蛇行搬送，於其間之網片藉由自二次乾燥裝置頂板吹入且自二次乾燥裝置底部分排出之溫風而乾燥，並作為纖維素酯系樹脂之坯片薄膜捲取於捲取機上。 Further, the dried web (film) by the above tenter method is then introduced into a secondary drying apparatus. In the secondary drying device, the mesh is meandered by a plurality of conveying rollers arranged in a zigzag shape from the side, wherein the mesh is blown in from the top plate of the secondary drying device and from the bottom portion of the secondary drying device The discharged warm air was dried, and the green film as a cellulose ester resin was taken up on a coiler.

使網片乾燥之手段並未特別限制，一般使用熱風、紅外線、加熱輥、微波等。基於簡便之方面，較好以熱風乾燥。乾燥溫度較好為40~150℃，於80~130℃時由於平面性、尺寸安定性良好故進而更佳。 The means for drying the web is not particularly limited, and hot air, infrared rays, heating rolls, microwaves, and the like are generally used. Based on the simple aspect, it is preferably dried by hot air. The drying temperature is preferably from 40 to 150 ° C, and is better at 80 to 130 ° C due to good planarity and dimensional stability.

因此，於網片乾燥步驟中，自支撐體剝離之網片進一步乾燥，最終使殘留溶劑量為3質量%以下，較好1質量%以下，更好0.5質量%以下時，可獲得尺寸安定性良好之薄膜故而較佳。 Therefore, in the web drying step, the web which has been peeled off from the support is further dried, and finally, the amount of residual solvent is 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and dimensional stability can be obtained. A good film is preferred.

自該等澆鑄至後乾燥之前之步驟可在空氣氛圍下進行，亦可在氮氣等惰性氣體氛圍下進行。該情況下，當然係考慮溶劑之***界限濃度而實施乾燥氛圍。 The steps from the casting to the post-drying may be carried out under an air atmosphere or under an inert gas atmosphere such as nitrogen. In this case, of course, the dry atmosphere is carried out in consideration of the explosion limit concentration of the solvent.

又，對於完成搬送乾燥步驟之纖維素酯系樹脂之坯片薄膜，於導入捲取步驟之前段中，較好藉由壓花加工裝置，於纖維素酯系樹脂之坯片薄膜兩側緣部進行形成壓花之加工。作為壓花加工裝置可利用例如日本特開昭 63-74850號公報中記載之裝置。 Further, the green sheet film of the cellulose ester resin which has been subjected to the transport drying step is preferably subjected to an embossing apparatus in the preceding stage of the winding step, and is formed on both sides of the film of the cellulose ester resin. The processing for forming embossing is performed. As an embossing processing device, for example, Japanese special opening can be utilized. The device described in the publication No. 63-74850.

纖維素酯系樹脂之坯片薄膜製造中之捲取機若為一般使用者即可，可藉固定張力法、固定轉矩法、漸變張力法、內部應力固定之程式張力控制法等之捲取方法進行捲取。 The coiler for the production of the cellulose film of the cellulose ester resin may be a general user, and may be wound by a fixed tension method, a fixed torque method, a gradient tension method, a program tension control method in which internal stress is fixed, or the like. Method for volume retrieval.

捲取後之坯片薄膜膜厚係根據使用目的而異，但膜厚範圍可為20~200μm，基於最近薄片傾向較好為30~120μm之範圍，特佳為40~100μm之範圍。 The thickness of the green film after winding is different depending on the purpose of use, but the film thickness may range from 20 to 200 μm, preferably from 30 to 120 μm, and particularly preferably from 40 to 100 μm.

[熔融澆鑄製膜法] [Melting casting film forming method]

作為熔融澆鑄製膜法有使用T模嘴之方法或吹塑法等之熔融擠出法、軋光法、熱加壓法、射出成形法等。其中，使用T模嘴之方法可使厚度不均較小，易加工為50~500μm左右之厚度、且膜厚不均或延遲偏差較小故而較佳。使用T模嘴之擠出方法係使聚合物在可熔融之溫度熔融，自T模嘴以薄膜狀(薄片狀)擠出於冷卻滾筒上，冷卻固化並自冷卻滾筒剝離之方法，且所得薄膜厚度精度優異故可較好地使用。 As the melt casting film forming method, there are a method using a T die nozzle, a melt extrusion method such as a blow molding method, a calendering method, a hot press method, and an injection molding method. Among them, the method of using the T-die can make the thickness unevenness small, and it is easy to process to a thickness of about 50 to 500 μm, and the film thickness is uneven or the retardation deviation is small, so that it is preferable. The extrusion method using a T-die is a method in which a polymer is melted at a meltable temperature, extruded from a T-die in a film form (flaky form) onto a cooling drum, cooled and solidified, and peeled off from the cooling drum, and the obtained film is obtained. Excellent in thickness accuracy, so it can be used well.

熔融擠出可在與其他聚酯等之熱塑性樹脂所用之條件相同條件下進行。例如於熱風或真空或減壓下乾燥之纖維素酯使用單軸或雙軸型擠出機，於擠出溫度200~300℃左右熔融，以葉盤型之過濾器等過濾去除異物後，自T模嘴澆鑄為薄膜狀(薄片狀)，於冷卻滾筒上固化。較好自供給漏斗導入擠出機時設為減壓下或惰性氛圍 下而防止氧化分解。 The melt extrusion can be carried out under the same conditions as those used for other thermoplastic resins such as polyester. For example, the cellulose ester dried under hot air or under vacuum or under reduced pressure is melted at a temperature of about 200 to 300 ° C using a uniaxial or biaxial extruder, and is filtered by a filter of a leaf disc type to remove foreign matter. The T nozzle was cast into a film shape (flaky shape) and solidified on a cooling drum. It is better to use the supply funnel as a decompression or inert atmosphere when it is introduced into the extruder. Underneath to prevent oxidative decomposition.

擠出流量較好導入齒輪泵等而穩定地進行。又，作為異物去除所用之過濾器較好使用不鏽鋼纖維燒結過濾器。不鏽鋼纖維燒結過濾器由於藉由作成使不鏽鋼纖維體複雜絡合之狀態而使壓縮接觸部位燒結而一體化者，故藉由其纖維粗細與壓縮量可改變密度並調整過濾精度。較好作成過濾精度以粗、密連續重複複數次而成之多層體者。又，藉由依序增大過濾精度而構成，成為使過濾精度之粗、密反覆之方法，可延長過濾器之過濾壽命且亦提高異物或凝膠等之捕捉精度故而較佳。 The extrusion flow rate is preferably carried out stably by introducing a gear pump or the like. Further, as the filter for removing foreign matter, a stainless steel fiber sintered filter is preferably used. In the stainless steel fiber sintered filter, since the compressed contact portion is sintered and integrated by the state in which the stainless steel fiber body is complicatedly complexed, the density can be changed and the filtration precision can be adjusted by the fiber thickness and the amount of compression. It is better to form a multilayer body in which the filtration precision is repeated in a plurality of coarse and dense steps. Further, by increasing the filtration accuracy in order, it is preferable to increase the filtration accuracy in a thick and dense manner, thereby prolonging the filtration life of the filter and also improving the capturing accuracy of foreign matter or gel.

若對模嘴造成損傷或附著異物則有發生條文狀缺陷之情況。此種缺陷稱為模嘴線，為了減少模嘴線等之表面缺陷，較好自擠出機至模嘴之配管構成為使樹脂之滯留部極力減少。又，較好使用模嘴內部或模唇極力無傷痕者。由於有自模嘴周邊之樹脂析出揮發成分而成為模嘴線之原因之情況，故較好對含揮發成分之氛圍進行抽吸。且由於亦有於靜電施加等裝置析出之情況，故較好藉施加交流之其他加熱手段防止析出。 If a damage is caused to the nozzle or foreign matter is attached, a strip-like defect may occur. Such a defect is called a die line. In order to reduce the surface defects of the die line or the like, it is preferable that the pipe from the extruder to the die is configured to minimize the retention of the resin. Moreover, it is preferred to use the inside of the die mouth or the lip of the die without any scars. Since the resin is precipitated from the resin around the die and becomes a cause of the nozzle line, it is preferable to suction the atmosphere containing the volatile component. Further, since it is also precipitated in a device such as electrostatic application, it is preferable to prevent precipitation by other heating means for applying an alternating current.

可塑劑等之添加劑可預先與樹脂混合，亦可於擠出機中途混練。為了均一添加，較好使用靜態混合機等之混合裝置。 The additive such as a plasticizer may be mixed with the resin in advance or may be kneaded in the middle of the extruder. For uniform addition, it is preferred to use a mixing device such as a static mixer.

冷卻滾筒之溫度較好為熱塑性樹脂之玻璃轉移溫度以下。為了使樹脂密著於冷卻滾筒，較好使用藉由靜電施加而密著之方法、藉由風壓而密著之方法、夾捏全 寬或端部而密著之方法、藉減壓而密著之方法等。 The temperature of the cooling drum is preferably below the glass transition temperature of the thermoplastic resin. In order to adhere the resin to the cooling drum, it is preferable to use a method in which it is adhered by electrostatic application, a method in which it is adhered by wind pressure, and a pinch. A method of wide or end and close, and a method of tightness by decompression.

藉此等熔融澆鑄製膜法成形之熱塑性樹脂之坯片薄膜與藉溶液澆鑄製膜法成形之坯片薄膜不同，具有於厚度方向延遲(Rt)較小之特徵，有時需要與溶液澆鑄製膜法不同之延伸條件。為了獲得期望之光學物性，依據情況，亦有同時或逐次進行薄膜行進方向之延伸與薄膜寬度方向之延伸兩者。且，根據情況，亦有僅於薄膜寬度方向延伸之情況。因該延伸操作使分子配向，而將薄膜調整至必要之延遲值。 The green sheet film formed by the melt casting film forming method is different from the green sheet film formed by the solution casting film forming method, and has a small retardation (Rt) in the thickness direction, and sometimes needs to be cast with a solution. Different extension conditions of the membrane method. In order to obtain the desired optical properties, depending on the case, both the extension of the film traveling direction and the extension of the film width direction may be performed simultaneously or sequentially. Further, depending on the case, there is a case where it extends only in the width direction of the film. The film is adjusted to the necessary retardation value because the stretching operation causes the molecules to align.

本實施形態之坯片薄膜藉由熔融澆鑄製膜法製造時，作為可使用之紫外線吸收劑可使用與前述利用溶液澆鑄製膜法之坯片薄膜製造方法中所用者大致同樣者。 When the green sheet film of the present embodiment is produced by a melt casting film forming method, the ultraviolet absorber which can be used can be used in substantially the same manner as those used in the above-described method for producing a green sheet film by a solution casting film forming method.

該等紫外線吸收劑之調配量對於熱塑性樹脂較好於0.01~10質量%之範圍，更好為0.1~5質量%。使用量過少時，有紫外線吸收效果不充分之情況，反之若過多，則有薄膜透明性劣化之情況。紫外線吸收劑較好為熱安定性高者。 The blending amount of the ultraviolet absorber is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the thermoplastic resin. When the amount used is too small, the ultraviolet absorbing effect may be insufficient, and if it is too large, the film transparency may be deteriorated. The ultraviolet absorber is preferably one having high heat stability.

較好於坯片薄膜中添加用以賦予薄膜平滑性之微粒子。作為所用微粒子，若具有熔融時之耐熱性則為無機化合物或有機化合物之任一者均可，例如作為無機化合物較好為含矽之化合物、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，更好為含矽之無機化合物或氧化鋯。其中，二氧化矽由於可將濁度抑制為較小 故可特佳地使用。以熔融澆鑄製膜法製造坯片薄膜時，作為所使用之霧化劑可使用與前述利用溶液澆鑄製膜法之坯片薄膜製造方法中所用者大致同樣者。 It is preferred to add fine particles for imparting smoothness to the film. The fine particles to be used may be either an inorganic compound or an organic compound if they have heat resistance at the time of melting. For example, the inorganic compound is preferably a cerium-containing compound, cerium oxide, aluminum oxide, zirconium oxide or calcium carbonate. Talc, clay, calcined kaolin, calcined calcium citrate, hydrated calcium citrate, aluminum citrate, magnesium citrate and calcium phosphate, etc., more preferably an inorganic compound containing cerium or zirconia. Among them, cerium oxide can suppress turbidity to a small Therefore, it can be used particularly well. When a green sheet film is produced by a melt casting film forming method, the atomizing agent to be used can be substantially the same as those used in the above-described method for producing a green sheet film by a solution casting film forming method.

<坯片薄膜之規格> <Specification of Blank Film>

本實施形態之坯片薄膜厚度為1~400μm，較好為20~200μm，更好為30~120μm，特佳為40~100μm之範圍。 The thickness of the green sheet film of the present embodiment is from 1 to 400 μm, preferably from 20 to 200 μm, more preferably from 30 to 120 μm, particularly preferably from 40 to 100 μm.

坯片薄膜寬度並未特別限定，但可為500~4000mm，較好為1000~2000mm。 The width of the green sheet film is not particularly limited, but may be 500 to 4000 mm, preferably 1000 to 2000 mm.

坯片薄膜於斜面延伸時之延伸溫度之較佳彈性率以楊氏模數表示為0.01MPa以上5000MPa以下，更好為0.1MPa以上500MPa以下。彈性率過低時，延伸時/延伸後之收縮率變低，皺褶不易消失。又，彈性率過高時，延伸時施加之張力增大，而必須提高保持薄膜兩側緣部之部分強度，對於後續步驟之拉幅機之負荷變大。 The preferred elastic modulus of the elongation temperature of the green sheet film when extending on the inclined surface is 0.01 MPa to 5000 MPa, and more preferably 0.1 MPa to 500 MPa, in terms of Young's modulus. When the modulus of elasticity is too low, the shrinkage ratio at the time of extension/extension becomes low, and wrinkles are not easily lost. Further, when the modulus of elasticity is too high, the tension applied during stretching increases, and it is necessary to increase the strength of the portions on both side edges of the film, and the load on the tenter in the subsequent step becomes large.

作為坯片薄膜可使用無配向者，亦可供給預先具有配向之薄膜。又，若需要亦可作成坯片薄膜之配向於寬度方向之分佈為弓狀之所謂弓形。總之，坯片薄膜之配向狀態可調整為於完成後續步驟之延伸之位置之薄膜配向成為期望者。 As the green sheet film, an unaligned one can be used, and a film having an alignment in advance can also be supplied. Further, if necessary, a so-called bow shape in which the alignment of the green sheet film is bowed in the width direction can be obtained. In summary, the alignment of the green sheet film can be adjusted to achieve the desired film alignment at the location where the subsequent steps are extended.

<斜面延伸薄膜之製造方法及製造裝置> <Method and apparatus for manufacturing beveled stretched film>

其次，針對使上述長條薄膜對於寬度方向斜面方向延 伸而製造長條狀斜面延伸薄膜之斜面延伸薄膜之製造方法及製造裝置加以說明。 Secondly, the above-mentioned long film is extended in the direction of the width direction A method and a manufacturing apparatus for manufacturing a beveled stretched film of a long beveled stretched film are described.

(裝置概要) (device summary)

圖1為示意性顯示斜面延伸薄膜之製造裝置1之概略構成之俯視圖。製造裝置1自長條薄膜之搬送方向上游側起依序具備薄膜捲出部2、搬送方向變更部3、導輥4、延伸部5、導輥6、搬送方向變更部7與薄膜捲取部8。又，亦可於搬送方向變更部7與薄膜捲取部8之間設置薄膜切斷裝置，將斜面延伸後之薄膜以期望長度切斷，並以薄膜捲取部8進行捲取。又，關於延伸部5之細節將於後述。 Fig. 1 is a plan view schematically showing a schematic configuration of a manufacturing apparatus 1 for a beveled stretch film. The manufacturing apparatus 1 is provided with a film take-up portion 2, a conveyance direction changing portion 3, a guide roller 4, an extending portion 5, a guide roller 6, a conveyance direction changing portion 7, and a film winding portion in this order from the upstream side in the conveyance direction of the long film. 8. Further, a film cutting device may be provided between the conveying direction changing portion 7 and the film winding portion 8, and the film having the inclined surface extending may be cut to a desired length and wound by the film winding portion 8. Further, details of the extension portion 5 will be described later.

薄膜捲出部2係捲出上述長條薄膜而供給至延伸部5者。該薄膜捲出部2可構成為與長條薄膜之製膜裝置不同構件，亦可一體構成。前者之情況，將長條薄膜於製膜後暫時捲取於捲芯成為捲繞體(長條薄膜坯片)者裝填於薄膜捲出部2，而自薄膜捲出部2捲出長條薄膜。另一方面，後者之情況，薄膜捲出部2於長條薄膜製膜後，不捲取其長條薄膜，而對於延伸部5捲出。 The film take-up portion 2 winds up the long film and supplies it to the extension portion 5. The film take-up portion 2 may be configured as a separate member from the film forming device of the long film, or may be integrally formed. In the former case, the long film is temporarily wound up on the winding core after the film formation, and the wound body (long film blank) is loaded into the film take-up portion 2, and the long film is taken out from the film take-up portion 2. . On the other hand, in the latter case, after the film winding portion 2 is formed into a film of a long film, the film is not taken up, but is unwound for the extending portion 5.

搬送方向變更部3係將自薄膜捲出部2捲出之長條薄膜之搬送方向變更為朝向作為斜面延伸拉幅機之延伸部5之入口之方向者。此搬送方向變更部3係以包含藉由例如邊搬送薄膜邊折返而變更方向之轉向桿或於該轉向桿以對薄膜平行之面內旋轉之旋轉台而構成。 The conveyance direction changing unit 3 changes the conveyance direction of the long film wound from the film take-up unit 2 to the direction toward the entrance of the extension portion 5 of the tenter extending the tenter. The conveyance direction changing unit 3 includes a steering column that changes direction by, for example, folding a film while transferring the film, or a rotating table that rotates in a plane parallel to the film.

藉由以搬送方向變更部3將長條薄膜之搬送方向如上述般變更，可使製造裝置1整體寬度更狹窄以外，亦可較細地控制薄膜捲出位置及角度，而可獲得膜厚、光學值之偏差小的斜面延伸薄膜。又，若可移動薄膜捲出部2及搬送方向變更部3(可滑動、可旋轉)，則可有效防止延伸部5中夾住長條薄膜之寬度方向兩端部之左右夾具(把持具)對薄膜之咬入不良。 By changing the conveyance direction of the long film by the conveyance direction changing unit 3 as described above, the entire width of the manufacturing apparatus 1 can be made narrower, and the film winding position and angle can be controlled finely, and the film thickness can be obtained. A bevel extending film having a small deviation in optical value. Further, when the movable film take-up portion 2 and the conveyance direction changing portion 3 (slidable and rotatable) are used, it is possible to effectively prevent the left and right jigs (handles) of the extending portions 5 from sandwiching the both end portions in the width direction of the long film. Poor biting on the film.

又，上述之薄膜捲出部2亦可為可滑動及可旋轉以對於延伸部5之入口以特定角度送出長條薄膜。該情況下，亦可設為省略搬送方向變更部3之設置之構成。 Further, the film take-up portion 2 described above may be slidable and rotatable to feed the long film at a specific angle to the entrance of the extending portion 5. In this case, the configuration in which the transport direction changing unit 3 is omitted may be omitted.

導輥4為了使長條薄膜行進時於軌道上安定而於延伸部5之上游側至少設置1根。又，導輥4亦可以挾住薄膜之上下一對輥對構成，亦可以複數輥對構成。最靠近延伸部5之入口之導輥4係導引薄膜行進之從動輥，分別透過未圖示之軸承部旋轉自如地軸支撐。作為導輥4之材質可使用習知者。又，為了防止薄膜損傷，較好於導輥4表面施以陶瓷塗佈，藉由對鋁等之輕金屬施以鉻鍍敷等而使導輥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 long film on the rail. Further, the guide roller 4 may be formed by sandwiching a pair of the pair of rollers above the film, or may be constituted by a plurality of pairs of rollers. The guide roller 4 closest to the entrance of the extending portion 5 guides the driven roller that travels the film, and is rotatably supported by a bearing portion (not shown). As the material of the guide roller 4, a conventional one can be used. Moreover, in order to prevent damage of the film, it is preferable to apply ceramic coating to the surface of the guide roller 4, and to lighten the guide roller 4 by applying chromium plating or the like to a light metal such as aluminum.

又，於比最靠近延伸部5之入口之導輥4更上游測之輥中之1根較好壓抵橡膠輥並捏挾。藉由成為此捏挾輥，可抑制薄膜移動方向之捲出張力變動。 Further, one of the rolls measured upstream of the guide rolls 4 closest to the entrance of the extending portion 5 is preferably pressed against the rubber roll and kneaded. By this kneading roll, it is possible to suppress the fluctuation in the winding tension in the moving direction of the film.

於最靠近延伸部5之入口之導輥4兩端(左右)之一對軸承部分別設有作為用以檢測該輥中對於薄膜產生之張力之薄膜張力檢測裝置之第1張力檢測裝置、第 2張力檢測裝置。作為薄膜張力檢測裝置可使用例如荷重單元。作為荷重單元可使用拉伸或壓縮型之習知者。荷重單元係將作用於著力點之荷重藉由安裝於易曲元件之變形量規而轉換為電信號並檢測之裝置。 The first tension detecting device, which is a film tension detecting device for detecting the tension generated in the film in the roller, is provided at one of the both ends (left and right) of the guide roller 4 closest to the entrance of the extending portion 5 2 tension detecting device. As the film tension detecting device, for example, a load cell can be used. As the load cell, a conventional one of a stretched or compressed type can be used. The load cell is a device that converts the load acting on the force point into an electrical signal and detects it by a deformation gauge attached to the flexible component.

荷重單元藉由設置於最靠近延伸部5之入口之導輥4左右之軸承部，而可左右獨立地檢測行進中之薄膜對於輥造成之力亦即於薄膜兩側緣附近產生之薄膜行進方向上之張力。又亦可於構成輥之軸承部之支撐體上直接安裝變形量規，基於該支撐體所產生之變形而檢測出荷重亦即薄膜張力。所發生之變形與薄膜張力之關係係預先測量而設為已知者。 The load cell can independently and independently detect the force exerted by the film in progress on the roller, that is, the film traveling direction near the two side edges of the film, by the bearing portion disposed at the left and right of the guide roller 4 closest to the entrance of the extension portion 5. The tension on the top. Further, a deformation gauge may be directly attached to the support body constituting the bearing portion of the roller, and the load, that is, the film tension, may be detected based on the deformation generated by the support. The relationship between the deformation occurring and the film tension is measured in advance and is known.

自薄膜捲出部2或搬送方向變更部3供給至延伸部5之薄膜位置及搬送方向自朝向延伸部5之入口之位置及搬送方向偏移時，對應於偏移量，於最靠近延伸部5之入口之導輥4中薄膜兩端緣附近產生張力差異。因此，藉由如上述設置薄膜張力檢測裝置檢測上述張力差，可判別該偏移程度。亦即，若薄膜搬送位置及搬送方向適當(若為朝向延伸部5之入口之位置及方向)，則作用於上述導輥4之荷重於軸方向兩端成為大致均等，若不適當，則於左右產生薄膜張力差。 When the film position and the conveyance direction supplied from the film take-up portion 2 or the conveyance direction changing portion 3 to the extension portion 5 are shifted from the position toward the entrance of the extension portion 5 and the conveyance direction, the offset is the closest to the extension portion. A difference in tension is generated near the both end edges of the film in the guide roller 4 at the entrance of 5. Therefore, the degree of the offset can be discriminated by detecting the tension difference by providing the film tension detecting means as described above. In other words, if the film transport position and the transport direction 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 in the axial direction, and if not, the The film tension difference is generated on the left and right.

因此，若以使最靠近延伸部5之入口之導輥4之左右薄膜張力差相等之方式，藉由例如上述之搬送方向變更部3而適當調整薄膜位置及搬送方向(對於延伸部5之入口之角度)，則由延伸部5之入口部之把持具對薄膜 之把持安定，可減少偏離把持具等之障礙發生。再者，可使利用延伸部5斜面延伸後之薄膜寬度方向之物性安定。 Therefore, the film position and the conveyance direction are appropriately adjusted by, for example, the above-described conveyance direction changing unit 3 so that the left and right film tension differences of the guide rolls 4 closest to the entrance of the extension portion 5 are equal (the entrance to the extension portion 5) Angle), the handle of the extension portion 5 is held by the pair of films The stability of the control can reduce the obstacles such as deviation from the holding device. Further, the physical properties in the width direction of the film which are extended by the inclined surface of the extending portion 5 can be stabilized.

導輥6為了使由延伸部5斜面延伸之薄膜之行進時於軌道上穩定，於延伸部5下游側至少設置1根。 The guide roller 6 is provided on the downstream side of the extending portion 5 at least one side in order to stabilize the film on the slope of the film extending from the inclined surface of the extending portion 5.

搬送方向變更部7係將自延伸部5搬送之延伸後薄膜之搬送方向變更為朝向薄膜捲取部8之方向者。 The conveyance direction changing unit 7 changes the conveyance direction of the film after the extension from the extension unit 5 to the direction toward the film winding unit 8.

此處，為了對應於配向角(薄膜之面內慢軸方向)之微調整或製品變化，有必要調整延伸部5之入口之薄膜行進方向與延伸部5出口之薄膜行進方向所成之角度。為了該角度調整，必須藉由搬送方向變更部3變更製膜之薄膜行進方向並將薄膜導入延伸部5之入口，及/或藉由搬送方向變更部7變更自延伸部5出口導出之薄膜行進方向而將薄膜恢復至薄膜捲取部8之方向。 Here, in order to correspond to the fine adjustment or the product change of the alignment angle (the in-plane slow axis direction of the film), it is necessary to adjust the angle between the film traveling direction of the entrance of the extending portion 5 and the film traveling direction of the exit of the extending portion 5. In order to adjust the angle, it is necessary to change the film traveling direction of the film formation by the conveyance direction changing unit 3 and to introduce the film into the entrance of the extending portion 5, and/or change the film traveling from the outlet of the extending portion 5 by the conveying direction changing unit 7. The film is returned to the direction of the film take-up portion 8 in the direction.

又，連續進行製膜及斜面延伸就生產性或收率之方面較佳。連續進行製膜步驟、斜面延伸步驟、捲取步驟時，藉由搬送方向變更部3及/或搬送方向變更部7變更薄膜行進方向，可使製膜步驟及捲取步驟中薄膜行進方向一致，亦即如圖1所示，藉由自薄膜捲出部2捲出之薄膜之行進方向(捲出方向)與捲取於薄膜捲取部8之前之薄膜行進方向(捲取方向)一致，可使對於薄膜行進方向之裝置全體寬度減小。 Further, continuous film formation and bevel stretching are preferred in terms of productivity or yield. When the film forming step, the slope extending step, and the winding step are continuously performed, the conveying direction changing unit 3 and/or the conveying direction changing unit 7 change the film traveling direction, so that the film forming direction and the film running direction in the winding step can be made uniform. That is, as shown in FIG. 1, the traveling direction (winding direction) of the film unwound from the film unwinding portion 2 coincides with the film traveling direction (winding direction) before being taken up by the film winding portion 8, The overall width of the device for the direction of travel of the film is reduced.

又，製膜步驟與捲取步驟中薄膜行進方向並無必要需一致，但較好以使薄膜捲出部2與薄膜捲取部8不產生干涉之佈局之方式，藉由搬送方向變更部3及/或 搬送方向變更部7變更薄膜之行進方向。 Moreover, it is not necessary to match the film traveling direction in the film forming step and the winding step, but it is preferable that the film winding portion 2 and the film winding portion 8 do not interfere with each other, and the conveying direction changing portion 3 is provided. And/or The conveyance direction changing unit 7 changes the traveling direction of the film.

作為如上述之搬送方向變更部3、7可藉由使用氣流輥或空氣轉向桿等之習知方法實現。 The conveyance direction changing sections 3 and 7 as described above can be realized by a known method using an air flow roller or an air steering lever.

薄膜捲取部8係將來自延伸部5通過搬送方向變更部7搬送之薄膜進行捲取者，可以例如捲繞裝置、儲能裝置、驅動裝置等構成。薄膜捲取部8欲調整薄膜捲取位置，較好為可於橫方向滑動之構造。 The film winding unit 8 is configured to wind up a film conveyed from the extending unit 5 by the conveying direction changing unit 7, and may be configured by, for example, a winding device, an energy storage device, a driving device, or the like. The film take-up portion 8 is intended to adjust the film take-up position, and is preferably configured to be slidable in the lateral direction.

薄膜捲取部8可以對於延伸部5出口以特定角度拉取薄膜之方式，較細地控制薄膜拉取位置及角度。藉此，可獲得膜厚、光學值之偏差小的長條斜面延伸薄膜。且，為了可有效防止薄膜皺褶發生並且提高薄膜捲取性，薄膜亦可以長條狀捲取。 The film take-up portion 8 can finely control the film take-up position and angle by pulling the film at a specific angle to the exit of the extension portion 5. Thereby, a long beveled stretched film having a small film thickness and a small variation in optical value can be obtained. Moreover, in order to effectively prevent film wrinkles from occurring and to improve film take-up, the film can also be wound up in a long strip.

該薄膜捲取部8構成以固定張力拉取於延伸部5延伸並搬送之薄膜之拉取部。又，於延伸部5與薄膜捲取部8之間，亦可設置用以以固定張力拉取薄膜之拉取輥。又上述導輥6亦可具有作為上述拉取輥之功能。 The film take-up portion 8 constitutes a drawing portion that pulls a film that extends and is conveyed by the extending portion 5 with a fixed tension. Further, between the extending portion 5 and the film winding portion 8, a pulling roller for pulling the film at a fixed tension may be provided. Further, the guide roller 6 may have a function as the above-described pull roller.

本實施形態中，延伸後之薄膜拉取張力T(N/m)較好於100N/m<T<300N/m，更好150N/m<T<250N/m之間調整。上述拉取張力為100N/m以下時，易發生薄膜鬆弛或起皺，延遲、配向角之薄膜寬度方向之分佈亦惡化。相反地，拉取張力若為300N/m以上，則配向角之薄膜寬度方向偏差惡化，寬度收率(寬度方向處理效率)惡化。 In the present embodiment, the film drawing tension T (N/m) after stretching is preferably adjusted to be 100 N/m < T < 300 N/m, more preferably 150 N/m < T < 250 N/m. When the pulling tension is 100 N/m or less, the film is liable to be slack or wrinkled, and the distribution of the retardation and the alignment angle in the film width direction is also deteriorated. On the other hand, when the pulling tension is 300 N/m or more, the film width direction deviation of the alignment angle is deteriorated, and the width yield (width direction processing efficiency) is deteriorated.

又，本實施形態中，較好以上述拉取張力T 之變動未達±5%，更好未達±3%之精度控制。上述拉取張力T之變動若為±5%以上，則寬度方向及移動方向(搬送方向)之光學特性偏差變大。作為將上述拉取張力T之變動控制於上述範圍內之方法，舉例為測定施加於延伸部5出口側之最初輥(導輥6)之荷重亦即薄膜張力，以使其值成為固定之方式，藉由一般PID控制方式控制捲取輥或薄膜捲取部8之捲取輥之旋轉速度之方法。作為測定上述荷重之方法舉例為對導輥6之軸承部安裝荷重單元，測定施加於導輥6之荷重亦即薄膜張力之方法。作為荷重單元可使用拉伸型或壓縮型之習知者。 Further, in the present embodiment, it is preferable to use the above-described pulling tension T The change is less than ±5%, and better than ±3% accuracy control. When the fluctuation of the pulling tension T is ±5% or more, the variation in optical characteristics in the width direction and the moving direction (transport direction) becomes large. The method of controlling the fluctuation of the pulling tension T within the above range is, for example, measuring the load of the first roller (guide roller 6) applied to the outlet side of the extending portion 5, that is, the film tension so that the value thereof is fixed. A method of controlling the rotational speed of the take-up roll of the take-up roll or film take-up portion 8 by a general PID control method. As a method of measuring the above-described load, a load cell is attached to the bearing portion of the guide roller 6, and a method of measuring the load applied to the guide roller 6, that is, the film tension is measured. As the load cell, a conventional one of a stretch type or a compression type can be used.

延伸後之薄膜放開由延伸部5之把持具之把持，自延伸部5之出口排出，並將以把持具把持之薄膜兩端(兩側)修整後，依序捲取於捲芯(捲取輥)上成為長條斜面延伸薄膜之捲繞體。又，上述修整只要根據需要進行即可。 The extended film is released by the holding device of the extending portion 5, is discharged from the outlet of the extending portion 5, and is trimmed at both ends (both sides) of the film held by the holding device, and then sequentially taken up to the core (volume) The take-up roll is formed into a wound body of a long beveled stretch film. Further, the above trimming may be performed as needed.

又，長條斜面延伸薄膜捲取前，為了防止薄膜彼此黏連，亦可對長條斜面延伸薄膜重疊遮蔽薄膜同時捲取，亦可邊對因捲取而重疊之長條斜面延伸薄膜之至少一(較好兩)端貼合膠帶等邊捲取。作為遮蔽薄膜若為可保護長條斜面延伸薄膜者則無特別限制，舉例為例如聚對苯二甲酸乙二酯薄膜、聚乙烯薄膜、聚丙烯薄膜等。 Moreover, before the long beveled stretch film is taken up, in order to prevent the films from sticking to each other, the long beveled stretch film may be overlapped and the film may be wound at the same time, or at least the long beveled film which is overlapped by the winding may be overlapped. One (better two) end-fitting tape is taken up side by side. The masking film is not particularly limited as long as it can protect the long bevel stretch film, and examples thereof include a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and the like.

又，長條斜面延伸薄膜捲取前，藉由於該薄膜之至少一面(較好兩面)之寬度方向之兩端部形成稱為滾花部或壓花部之比薄膜面更蓬鬆之部分(凸部)，亦可 防止捲取薄膜時之薄膜彼此黏連。又，滾花部之高度及形狀於寬度方向兩端部亦可不同(亦可非對稱)。 Further, before the long beveled stretched film is taken up, a portion which is called a knurled portion or an embossed portion is more fluffy than the film portion due to the width direction of at least one side (preferably both sides) of the film (convex) Department) The film is prevented from sticking to each other 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.

(延伸部細節) (extension details)

其次針對上述延伸部5之細節加以說明。圖2係示意性顯示延伸部5之鐵道圖型之一例之俯視圖。但，此為一例，延伸部5之構成並非限定於此。 Next, the details of the above-described extension portion 5 will be described. Fig. 2 is a plan view schematically showing an example of a railway pattern of the extension portion 5. However, this is an example, and the configuration of the extension portion 5 is not limited thereto.

本實施形態之長條斜面延伸薄膜之製造係使用可斜面延伸之拉幅機(斜面延伸機)作為延伸部5而進行，。該拉幅機係將長條薄膜加熱至可延伸之任意溫度並斜面延伸之裝置。該拉幅機具備加熱區域Z、於左右一對之鐵道Ri、Ro及搬送沿著鐵道Ri、Ro行走之薄膜之多數把持具Ci、Co(圖2僅圖示1組把持具)。又，關於加熱區域Z之細節於後述。鐵道Ri、Ro分別以連結部連結複數鐵道部而構成(圖2中之空心圓為連結部之一例)。把持具Ci、Co係以把持薄膜寬度方向兩端之夾具構成。 The manufacture of the long beveled stretch film of the present embodiment is carried out using a tenter (bevel expander) which can be inclined to extend as the extending portion 5. The tenter is a device that heats a long strip of film to any temperature that can be extended and extends obliquely. The tenter includes a heating zone Z, a pair of left and right railways Ri, Ro, and a plurality of grippers Ci and Co that transport a film that travels along the railways Ri and Ro (only one set of grippers is shown in Fig. 2). Further, details of the heating zone Z will be described later. Each of the railways Ri and Ro is connected to the plurality of railway portions by a connecting portion (the hollow circle in Fig. 2 is an example of a connecting portion). The grippers Ci and Co are configured to hold the clamps at both ends in the width direction of the film.

圖2中，長條薄膜之捲出方向D1與延伸後長條斜面延伸薄膜之捲取方向D2不同，於與捲取方向D2之間成為捲出角度θi。捲出角度θi可於超過0°且未達90°之範圍，以期望角度任意設定。 In Fig. 2, the unwinding direction D1 of the long film is different from the winding direction D2 of the extended long bevel extending film, and becomes a winding angle θi between the winding direction D2 and the winding direction D2. The unwinding angle θi can be arbitrarily set at a desired angle over a range of more than 0° and less than 90°.

如此，由於捲出方向D1與捲取方向D2不同，故拉幅機之鐵道圖型成為於左右非對稱形狀，使薄膜搬送路徑於中途彎曲。因此，可根據對於欲製造之長條斜面延伸薄膜賦予之配向角θ、延伸倍率等，手動或自動地 調整鐵道圖型。本實施形態之製造方法所用之斜面延伸機較好可自由設定構成鐵道Ri、Ro之各鐵道部及鐵道連結部之位置，且可任意變更鐵道圖型。 As described above, since the winding direction D1 is different from the winding direction D2, the railway pattern of the tenter is formed in a left-right asymmetric shape, and the film conveying path is curved in the middle. Therefore, it can be manually or automatically determined according to the alignment angle θ, the stretching ratio, and the like imparted to the long bevel extending film to be manufactured. Adjust the railway pattern. It is preferable that the beveling machine used in the manufacturing method of the present embodiment can freely set the positions of the respective railway portions and the railway connecting portions constituting the railways Ri and Ro, and the railway pattern can be arbitrarily changed.

本實施形態中，拉幅機之複數把持具Ci、Co與前後之把持具Ci、Co保持固定間隔，並以固定速度行走。把持具Ci、Co之行走速度可適當選擇，但通常為1~150m/分鐘。本實施形態中，考慮薄膜之生產性，較好為20~100m/分鐘。左右一對之把持具Ci、Co之行走速度差通常係行走速度之1%以下，較好為0.5%以下，更好為0.1%以下。此係因為於延伸步驟出口若薄膜左右有行進速度差，則延伸步驟出口發生皺褶、聚集，故要求將左右把持具Ci、Co之速度差為實質上同速度。於一般之拉幅機裝置等，對應於驅動鍊條之鏈輪齒之齒週期、驅動馬達之頻率等，而有以秒以下之等級發生之速度不均之情況，經常產生數%之不均，但該等不相當於本實施形態所述之速度差。 In the present embodiment, the plurality of grippers Ci and Co of the tenter are held at regular intervals with the front and rear grippers Ci and Co, and travel at a fixed speed. 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 from 20 to 100 m/min. The difference in travel speed between the pair of left and right grippers Ci and Co is usually 1% or less, preferably 0.5% or less, more preferably 0.1% or less. This is because if there is a difference in the traveling speed between the left and right sides of the film at the exit of the stretching step, wrinkles and aggregation occur at the exit of the stretching step. Therefore, it is required that the speed difference between the left and right grippers Ci and Co be substantially the same speed. In the case of a general tenter device or the like, the tooth period of the sprocket of the drive chain, the frequency of the drive motor, and the like, and the speed unevenness occurring in the order of seconds or less often causes unevenness of several %. However, these are not equivalent to the speed difference described in the embodiment.

本實施形態之製造方法所用之斜面延伸機中，尤其於薄膜搬送傾斜之部位，對於限制把持具之軌跡之鐵道經常要求較大之彎曲率。基於避免因急遽彎曲所致之把持具彼此之干涉或局部應力集中之目的，期望於彎曲部以把持具之軌跡描繪曲線。 In the bevel stretching machine used in the manufacturing method of the present embodiment, particularly in the portion where the film conveyance is inclined, a large bending rate is often required for the rail which restricts the trajectory of the gripper. For the purpose of avoiding interference or partial stress concentration of the grippers due to rapid bending, it is desirable to draw a curve with the trajectory of the gripper at the bend.

如此，用以對長條薄膜賦予斜面配向所用之斜面延伸拉幅機較好為藉由使鐵道圖型有各種變化，而可自如設定薄膜之配向角，進而可遍及薄膜寬度方向左右均 等地高精度使薄膜配向軸(慢軸)配向，且可高精度地控制薄膜厚度或延遲之拉幅機。 Therefore, the bevel extending tenter used for imparting the oblique alignment to the long film preferably sets the alignment angle of the film by various changes of the railway pattern, and can be applied to the left and right of the film width direction. A tenter that precisely aligns the film alignment axis (slow axis) with high precision and can control film thickness or delay with high precision.

其次，針對延伸部5之延伸動作加以說明。長條薄膜其兩端藉由左右之把持具Ci、Co把持，隨著把持具Ci、Co於加熱區域Z內行走而搬送。左右之把持具Ci、Co於延伸部5之入口部(圖中A之位置)中，於相對於對於薄膜行進方向(捲出方向D1)略垂直方向呈左右非對稱之鐵道Ri、Ro上分別行走，於延伸結束時之出口部(圖中B之位置)放開被把持之薄膜。自把持具Ci、Co放開之薄膜以前述薄膜捲取部8捲取於捲芯上。一對鐵道Ri、Ro分別具有環狀之連續軌道，於拉幅機之出口部放開薄膜把持之把持具Ci、Co於外側鐵道上行走並依序返回入口部。 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 carried as the grippers Ci and Co travel in the heating zone Z. The left and right grippers Ci and Co are respectively located at the entrance portion (the position of A in the figure) of the extension portion 5, respectively, on the railways Ri and Ro which are asymmetric with respect to the direction perpendicular to the film traveling direction (winding direction D1). Walk and release the held film at the exit (at the position of B in the figure) at the end of the extension. The film which is released from the holding device Ci and Co is taken up on the winding core by the film winding portion 8. Each of the pair of railways Ri and Ro has a continuous continuous track, and the grippers Ci and Co which are held by the film at the exit portion of the tenter are traveled on the outer rail and sequentially return to the entrance.

此時，由於鐵道Ri、Ro為左右非對稱，故於圖2之例中，於圖中A之位置左右對稱之把持具Ci、Co隨著於鐵道Ri、Ro上行走，成為於鐵道Ri側(內車道側)行走之把持具Ci相對於於鐵道Ro側(外車道側)行走之把持具Co先行之位置關係。 At this time, since the railways Ri and Ro are asymmetrical to the left and right, in the example of Fig. 2, the grippers Ci and Co which are bilaterally symmetrical in the position of A in the figure travel along the railways Ri and Ro, and become the side of the railway Ri. (Inside lane side) The grip position of the walking gripper Ci with respect to the rail Ro side (outer lane side) is preceded by Co.

亦即，於圖中A位置相對於對於薄膜之捲出方向D1略垂直之方向之把持具Ci、Co中，一把持具Ci先到達薄膜延伸結束時之位置B時，連結把持具Ci、Co之直線對於與薄膜捲取方向D2略垂直之方向僅以角度θL傾斜。進行以上作為，使長條薄膜對於寬度方向以θL之角度斜面延伸。此處，所謂略垂直表示處於90±1°之範 圍。 That is, in the holders Ci and Co in the direction A of the drawing with respect to the direction perpendicular to the winding direction D1 of the film, when the holder Ci first reaches the position B at the end of the film extension, the holders Ci, Co are connected. The straight line is inclined only at an angle θL with respect to a direction slightly perpendicular to the film winding direction D2. In the above manner, the long film is extended obliquely at an angle of θL with respect to the width direction. Here, the so-called slightly vertical means that it is at 90±1° Wai.

其次，針對上述加熱區域Z之細節加以說明。延伸部5之加熱區域Z係以預熱區域Z1、延伸區域Z2及緩和區域Z3構成。延伸部5中，由把持具Ci、Co把持之薄膜依序通過預熱區域Z1、延伸區域Z2及緩和區域Z3。本實施形態中，預熱區域Z1與延伸區域Z2以隔離壁區分，延伸區域Z2與緩和區域Z3以隔離壁隔開。又，預熱區域Z1、延伸區域Z2及緩和區域Z3各區域內，亦可設置適宜隔離壁(各區域內部亦可進而以隔離壁分割)。 Next, the details of the above-described heating zone Z will be described. The heating zone Z of the extension portion 5 is composed of a preheating zone Z1, an extension zone Z2, and a relaxation zone Z3. In the extension portion 5, the film held by the grippers Ci and Co sequentially passes through the preheating zone Z1, the extension zone Z2, and the relaxation zone Z3. In the present embodiment, the preheating zone Z1 and the extension zone Z2 are separated by a partition wall, and the extension zone Z2 and the mitigation zone Z3 are separated by a partition wall. Further, in each of the preheating zone Z1, the extension zone Z2, and the relaxation zone Z3, a suitable partition wall may be provided (the inside of each zone may be further divided by a partition wall).

預熱區域Z1係於加熱區域Z之入口部，使把持薄膜兩端之把持具Ci、Co於左右(薄膜寬度方向)保持固定間隔之狀態行走之區域。 The preheating zone Z1 is attached to the entrance of the heating zone Z, and the gripper Ci and Co at both ends of the holding film are moved in a state where the left and right (film width direction) are kept at a fixed interval.

延伸區域Z2係使把持薄膜兩端之把持具Ci、Co空出間隔直至成為特定間隔之區域。此時，進行如上述之斜面延伸，但亦可根據需要於斜面延伸前後於縱方向或橫方向延伸。圖2中顯示延伸區域Z2於沿著薄膜搬送方向包含橫延伸區域Z2-1與斜面延伸區域Z2-2之例。於橫延伸區域Z2-1，藉由於薄膜搬送之同時，擴大一對把持具Ci、Co之間隔，使薄膜於寬度方向(橫方向)延伸。於斜面延伸區域Z2-2，使薄膜搬送方向於中途改變，使一把持具Ci相對先行，另一把持具Co相對延遲，而進行使薄膜於相對於寬度方向斜面方向延伸之斜面延伸步驟。 The extended region Z2 is a region in which the grippers Ci and Co at both ends of the grip film are spaced apart until they are at a specific interval. At this time, the slope is extended as described above, but it may extend in the longitudinal direction or the lateral direction before and after the slope extends as needed. 2 shows an example in which the extended region Z2 includes a laterally extending region Z2-1 and a sloped extending region Z2-2 along the film transporting direction. In the laterally extending region Z2-1, the film is stretched at the same time, and the distance between the pair of grippers Ci and Co is increased to extend the film in the width direction (lateral direction). In the inclined surface extending region Z2-2, the film conveying direction is changed midway, so that one holding device Ci is advanced and the other holding member Co is relatively delayed, and a step of extending the film in a slope direction with respect to the width direction is performed.

緩和區域Z3係於延伸區域Z2之斜面延伸步驟結束後，進行使因斜面延伸而殘留於薄膜之應力(殘留應力)藉由後述之溫度設定而緩和之緩和步驟之區域。緩和區域Z3由於使斜面延伸之薄膜之光學軸(慢軸)固定故緩和區域Z3亦稱為熱固定區域。於緩和區域Z3，兩端之保持具Ci、Co可保持平行之狀態行走，亦可使薄膜於寬度方向收縮後，保持平行之方式行走，任一情況下，緩和區域Z3中，薄膜搬送路徑並未如斜面延伸區域Z2-2般彎曲，而使薄膜搬送方向固定。 After the step of extending the slope of the extension region Z2, the relaxation region Z3 is subjected to a relaxation step in which the stress (residual stress) remaining on the film due to the slope is relaxed by the temperature setting described later. The relaxation zone Z3 is also referred to as a heat fixation zone because the optical axis (slow axis) of the film on which the slope extends is fixed. In the relaxation zone Z3, the holders Ci and Co at both ends can be kept in a parallel state, and the film can be moved in the width direction and then kept parallel. In either case, in the relaxation zone Z3, the film conveyance path is It is not bent like the slope extending region Z2-2, and the film conveying direction is fixed.

又，延伸後之薄膜通過緩和區域Z3後，亦可通過區域內溫度設定於構成薄膜之熱塑性樹脂之玻璃轉移溫度Tg(℃)以下之區間(冷卻區域)。 Further, after the stretched film passes through the relaxation region Z3, the temperature in the region may be set in a region (cooling region) equal to or lower than the glass transition temperature Tg (°C) of the thermoplastic resin constituting the film.

對於熱塑性樹脂之玻璃轉移溫度Tg，較好預熱區域Z1之溫度設定為Tg~Tg+60℃，延伸區域Z2之溫度設定為Tg~Tg+50℃，緩和區域Z3及冷卻區域之溫度設定為Tg-40~Tg+30℃。 For the glass transition temperature Tg of the thermoplastic resin, the temperature of the preheating zone Z1 is preferably set to Tg~Tg+60°C, the temperature of the extension zone Z2 is set to Tg~Tg+50°C, and the temperature of the relaxation zone Z3 and the cooling zone is set to Tg-40~Tg+30°C.

又，預熱區域Z1、延伸區域Z2及緩和區域Z3之長度可適當選擇，對於延伸區域Z2之長度，預熱區域Z1之長度通常為50~200%，緩和區域Z3長度通常為50~150%。 Moreover, the lengths of the preheating zone Z1, the extension zone Z2, and the relaxation zone Z3 can be appropriately selected. For the length of the extension zone Z2, the length of the preheating zone Z1 is usually 50 to 200%, and the length of the relaxation zone Z3 is usually 50 to 150%. .

又，若延伸前之薄膜寬度設為Wo(mm)，延伸後之薄膜寬度設為W(mm)，則延伸步驟之延伸倍率R(W/Wo)較好為1.1~3.0，更好為1.3~2.0。延伸倍率若為該範圍，則薄膜寬度方向之厚度偏差較小故較佳。 Further, if the width of the film before stretching is Wo (mm) and the width of the film after stretching is W (mm), the stretching ratio R (W/Wo) of the stretching step is preferably from 1.1 to 3.0, more preferably 1.3. ~2.0. When the stretching ratio is in this range, the thickness variation in the film width direction is small, which is preferable.

[關於斜面延伸區域、緩和區域之溫度控制] [About the temperature control of the slope extension area and the relaxation area]

其次，針對斜面延伸區域Z2-2及緩和區域Z3之溫度控制加以說明。又，以下，於薄膜寬度方向，斜面延伸時一對把持具Ci、Co之一先行之行走側(把持具Ci行走之側)稱為先行側，另一者延遲之行走側(把持具Co行走之側)稱為延遲側。 Next, the temperature control of the slope extending region Z2-2 and the relaxation region Z3 will be described. Further, in the film width direction, when the slope is extended, the traveling side on which one of the pair of grippers Ci and Co is advanced (the side on which the gripper Ci travels) is referred to as the preceding side, and the other is delayed on the traveling side (the gripper Co is traveling) The side) is called the delay side.

圖3係示意性顯示斜面延伸區域Z2-2及緩和區域Z3之自延遲側至先行側之溫度分佈。本實施形態中，斜面延伸區域Z2-2中，於先行側與延遲側之間，以先行側溫度比延遲側溫度低1~15℃之方式形成第1溫度分佈。亦即，斜面延伸區域Z2-2之延遲側溫度設為T1(℃)，先行側之溫度設為T2(℃)時，1℃≦(T1-T2)≦15℃…(1) Fig. 3 is a view schematically showing the temperature distribution from the retard side to the leading side of the slope extending region Z2-2 and the mitigating region Z3. In the present embodiment, in the slope extending region Z2-2, the first temperature distribution is formed between the leading side and the retard side so that the leading side temperature is lower by 1 to 15 ° C than the retard side temperature. That is, the temperature on the retard side of the slope extending region Z2-2 is T1 (°C), and the temperature on the leading side is T2 (°C), 1°C≦(T1-T2)≦15°C...(1)

尤其，斜面延伸區域Z2-2中，斜面延伸前把持薄膜兩端之一對把持具Ci、Co分別到達斜面延伸結束位置P、Q時之連結上述一對把持具Ci、Co之方向(以下亦稱為PQ方向)中，形成上述第1溫度分佈。此時，斜面延伸結束位置P、Q成為位於分隔斜面延伸區域Z2-2與緩和區域Z3之隔離壁之正前方，亦即對於上述隔離壁位於薄膜搬送方向之上游側。又，形成上述第1溫度分佈之位置只要在斜面延伸區域Z2-2內即可，不限於上述位置(連結斜面延伸結束位置P、Q之位置)。 In particular, in the inclined surface extending region Z2-2, before the inclined surface extends, one of the two ends of the holding film is in the direction of connecting the pair of holding devices Ci and Co when the holding members Ci and Co respectively reach the inclined end positions P and Q (hereinafter also In the PQ direction, the first temperature distribution is formed. At this time, the inclined surface extending end positions P and Q are located directly in front of the partition wall separating the inclined surface extending region Z2-2 and the alleviating region Z3, that is, the partition wall is located on the upstream side in the film transporting direction. Further, the position at which the first temperature distribution is formed may be in the inclined surface extending region Z2-2, and is not limited to the above position (the position at which the inclined surface extending end positions P and Q are connected).

圖4顯示斜面延伸區域Z2-2之上述第1溫度 分佈之例。第1溫度分佈係自延遲側至先行側之溫度單調減少之分佈。例如第1溫度分佈可為如直線a1所示，自延遲側至先行側溫度以固定比例減少之分佈(溫度梯度為固定之分佈)，亦可為如曲線a2所示，自延遲側起越向先行側溫度降低量對於寬度方向位置之變化量變大之分佈，亦可如曲線a3所示，自延遲側起越向先行側溫度降低量對於寬度方向位置之變化量變小之分佈。 Figure 4 shows the above first temperature of the bevel extension zone Z2-2 An example of distribution. The first temperature distribution is a monotonously decreasing distribution of temperature from the retard side to the leading side. For example, the first temperature distribution may be a distribution such that the temperature from the retard side to the leading side decreases at a fixed ratio (the temperature gradient is a fixed distribution) as shown by a straight line a1, or may be as shown by a curve a2, from the retard side The distribution in which the amount of change in the width direction of the leading side becomes larger as the amount of change in the width direction position may be as shown by the curve a3, and the amount of change in the amount of decrease in the temperature toward the leading side from the retard side becomes smaller.

另一方面，如圖3所示，於緩和區域Z3，於先行側與延遲側之間，以先行側溫度比延遲側溫度高5~30℃之方式形成第2溫度分佈。亦即，將緩和區域Z3之先行側之溫度設為T3(℃)，將延遲側溫度設為T4(℃)時，為5℃≦(T3-T4)≦30℃...(2) On the other hand, as shown in FIG. 3, in the relaxation zone Z3, the second temperature distribution is formed between the leading side and the retard side so that the preceding side temperature is higher than the retard side temperature by 5 to 30 °C. That is, the temperature on the leading side of the relaxation zone Z3 is T3 (° C.), and when the temperature on the retard side is T4 (° C.), it is 5° C. (T3-T4) ≦ 30° C. (2)

尤其，於緩和區域Z3，於通過緩和區域Z3之中間點M3，於垂直於薄膜搬送方向之寬度方向上形成第2溫度分佈。此處，上述之中間點M3係將第1位置M1與第2位置M2連結之區間之中間位置(第3位置)，該第1位置係於斜面延伸區域Z2-2中一對把持具Ci、Co分別到達斜面延伸結束位置P、Q時之連結一對把持具Ci、Co之區間的中間，第2位置M2係於緩和區域Z3之出口(區間ST)之寬度方向中間。又，形成上述第2溫度分佈之位置只要於緩和區域Z3內即可，不限定於上述位置。 In particular, in the relaxation zone Z3, a second temperature distribution is formed in the width direction perpendicular to the film conveyance direction through the intermediate point M3 of the relaxation zone Z3. Here, the intermediate point M3 is an intermediate position (third position) of a section connecting the first position M1 and the second position M2, and the first position is a pair of grippers Ci in the slope extending region Z2-2. When Co reaches the slope extending end positions P and Q, respectively, the middle of the section connecting the pair of grippers Ci and Co, and the second position M2 is in the middle of the width direction of the exit (section ST) of the relaxation zone Z3. Further, the position at which the second temperature distribution is formed may be in the relaxation region Z3, and is not limited to the above position.

圖5顯示緩和區域Z3之上述第2溫度分佈之例。第2溫度分佈係自延遲側至先行側之溫度單調增加之 分佈。例如第2溫度分佈可為如直線b1所示，自延遲側至先行側溫度以固定比例增加之分佈(溫度梯度為固定之分佈)，亦可為如曲線b2所示，溫度增加量對於寬度方向位置之變化量減小之分佈，亦可如曲線b3所示，自延遲側起越向先行側溫度降低量對於寬度方向位置之變化量變大之分佈。 Fig. 5 shows an example of the second temperature distribution of the relaxation zone Z3. The second temperature distribution monotonically increases the temperature from the retard side to the leading side. distributed. For example, the second temperature distribution may be a distribution in which the temperature from the retard side to the leading side is increased by a fixed ratio (the temperature gradient is a fixed distribution) as shown by the straight line b1, or may be as shown by the curve b2, and the temperature increase amount is for the width direction. The distribution in which the amount of change in the position is reduced may be a distribution in which the amount of change in the amount of decrease in the width direction toward the width direction is increased from the retard side as shown by the curve b3.

且，斜面延伸區域Z2-2之溫度比緩和區域Z3高5~40℃。更具體而言，斜面延伸區域Z2-2之第1位置M1之溫度比緩和區域Z3之中間點M3(第3位置)之溫度高5~40℃。亦即，將斜面延伸區域Z2-2之第1位置M1之溫度設為T5(℃)，將緩和區域Z3之中間點M3溫度設為T6(℃)時，為5℃≦(T5-T6)≦40℃...(3) Further, the temperature of the slope extending region Z2-2 is 5 to 40 ° C higher than the relaxation region Z3. More specifically, the temperature of the first position M1 of the slope extending region Z2-2 is 5 to 40 ° C higher than the temperature of the intermediate point M3 (third position) of the relaxation region Z3. In other words, when the temperature of the first position M1 of the slope extending region Z2-2 is T5 (° C.) and the temperature of the intermediate point M3 of the relaxation region Z3 is T6 (° C.), it is 5° C. (T5-T6). ≦40°C...(3)

又，斜面延伸區域Z2-2之上述溫度亦可為斜面延伸區域Z2-2內上述第1位置M1以外之位置溫度。且緩和區域Z3之上述溫度亦可為緩和區域Z3內上述中間點M3以外之位置溫度。 Further, the temperature of the slope extending region Z2-2 may be a temperature other than the first position M1 in the slope extending region Z2-2. Further, the temperature of the relaxation zone Z3 may be a temperature other than the intermediate point M3 in the relaxation zone Z3.

滿足上述條件(1)~(3)之溫度控制可藉由如圖6所示，於斜面延伸區域Z2-2及緩和區域Z3中分別配置加熱部11、12而實現。加熱部11、12具有例如吹出熱風之吹出口，且係由藉由上述熱風加熱薄膜而自先行側至延遲側之長條狀噴嘴所形成。其中，加熱部11係形成為吹出口寬度(垂直於長條方向之開口寬度)隨著自先行側向延遲側變寬之形狀。另一方面，加熱部12係形成為 吹出口寬度(垂直於長條方向之開口寬度)隨著自延遲側向先行側變寬之形狀。藉此，斜面延伸區域Z2-2可實現延遲側溫度比先行側更高之上述第1溫度分佈，緩和區域Z3可實現先行側溫度比延遲側高之上述第2溫度分佈。且藉由使自加熱部11吹出之熱風溫度比自加熱部12吹出之熱風溫度高，可使斜面延伸區域Z2-2之溫度高於緩和區域Z3之溫度。 The temperature control satisfying the above conditions (1) to (3) can be realized by arranging the heating portions 11 and 12 in the slope extending region Z2-2 and the tempered region Z3 as shown in Fig. 6, respectively. The heating units 11 and 12 have, for example, an air outlet for blowing hot air, and are formed by a long nozzle from the leading side to the retard side by heating the film by the hot air. Among these, the heating portion 11 is formed in a shape in which the outlet width (the opening width perpendicular to the longitudinal direction) is widened from the preceding side to the retard side. On the other hand, the heating portion 12 is formed as The width of the air outlet (the width of the opening perpendicular to the longitudinal direction) becomes wider as it extends from the retarded side to the leading side. Thereby, the slope extending region Z2-2 can realize the first temperature distribution in which the retard side temperature is higher than the preceding side, and the relaxation region Z3 can realize the second temperature distribution in which the leading side temperature is higher than the retard side. Further, by setting the hot air temperature blown from the heating portion 11 to be higher than the hot air temperature blown from the heating portion 12, the temperature of the slope extending region Z2-2 can be higher than the temperature of the relaxation region Z3.

又，加熱部11、12亦可以吹出口之開口寬度固定之噴嘴構成。該情況下，藉由使吹出之熱風溫度於先行側及延遲側變化，可形成上述第1溫度分佈及第2溫度分佈。而且，藉由使自加熱部11吹出之熱風溫度比自加熱部12吹出之熱風溫度高，可使斜面延伸區域Z2-2之溫度高於緩和區域Z3之溫度。 Further, the heating portions 11 and 12 may be formed by nozzles having a wide opening width of the air outlet. In this case, the first temperature distribution and the second temperature distribution can be formed by changing the temperature of the blown hot air on the leading side and the retard side. Further, by setting the hot air temperature blown from the heating portion 11 to be higher than the hot air temperature blown from the heating portion 12, the temperature of the slope extending region Z2-2 can be made higher than the temperature of the relaxation region Z3.

又，加熱部11、12亦可由紅外線加熱器構成而取代吹出熱風之噴嘴。紅外線加熱器於先行側與延遲側之間配置複數個，藉由調整各紅外線加熱器之輸出(瓦數)，可形成上述第1溫度分佈及第2溫度分佈。而且，藉由對加熱部11及加熱部12改變紅外線加熱器之輸出，可使斜面延伸區域Z2-2之溫度高於緩和區域Z3之溫度。 Further, the heating portions 11 and 12 may be constituted by an infrared heater instead of the nozzle for blowing hot air. The infrared heater is disposed between the leading side and the retard side, and the first temperature distribution and the second temperature distribution can be formed by adjusting the output (wattage) of each infrared heater. Further, by changing the output of the infrared heater to the heating portion 11 and the heating portion 12, the temperature of the slope extending region Z2-2 can be made higher than the temperature of the relaxation region Z3.

且圖7係示意性顯示形成第2溫度分佈之手段之其他例。於延伸部5之爐內，尤其於搬送路徑為彎曲之斜面延伸區域中，於彎曲部之延遲側更易充滿爐內之熱。因此，如圖7所示，於緩和區域Z3中，先前側之排氣部E1之排氣能力(每單位時間之排氣量)高於延遲側 之排氣部E2之排氣能力，藉此於延遲側充滿爐內之熱移動至先行側，藉此亦可形成上述第2溫度分佈。具體而言，可考慮使先行側之排氣口位置比延遲側之排氣口位置更靠近鐵道側，先行側之排氣口面積比延遲側之排氣口面積廣等之方法。又，於排氣部E1、E2排氣之空氣亦可再度返回至延伸部5之爐內並於爐內循環，亦可不循環。且，進行斜面延伸之延伸區域Z2之體積若延遲側大於先行側，則由於於延遲側熱更不易充滿而更好。 FIG. 7 is a view schematically showing another example of the means for forming the second temperature distribution. In the furnace of the extension portion 5, particularly in the region where the conveying path is a curved slope, the heat in the furnace is more easily filled on the retard side of the curved portion. Therefore, as shown in FIG. 7, in the relaxation zone Z3, the exhaust capability (the amount of exhaust per unit time) of the exhaust portion E1 on the front side is higher than that on the retard side The exhaust capability of the exhaust portion E2 is such that the heat remaining in the furnace on the retard side moves to the leading side, whereby the second temperature distribution can be formed. Specifically, a method in which the position of the exhaust port on the preceding side is closer to the railway side than the position of the exhaust port on the retard side, and the area of the exhaust port on the preceding side is wider than that on the retard side. Further, the air exhausted to the exhaust portions E1 and E2 may be returned to the furnace of the extending portion 5 again and circulated in the furnace, or may not be circulated. Further, if the volume of the extended region Z2 in which the slope extends is larger than the leading side, the heat on the retard side is more difficult to be filled.

藉由滿足條件式(1)~(3)，於斜面延伸步驟產生之薄膜寬度方向之膜厚差因緩和步驟之殘留應力緩和而減小，可獲得於寬度方向膜厚大致均一之斜面延伸薄膜。藉此，可減低皺褶發生且提高斜面延伸薄膜之生產性。以下針對該點更詳細說明。 By satisfying the conditional expressions (1) to (3), the film thickness difference in the film width direction which is generated in the step of extending the slope is reduced by the relaxation of the residual stress in the relaxation step, and the beveled film having a substantially uniform film thickness in the width direction can be obtained. . Thereby, the occurrence of wrinkles can be reduced and the productivity of the bevel stretch film can be improved. This point is explained in more detail below.

以薄膜搬送方向於中途彎曲之彎曲型斜面延伸方式，一對把持具Ci、Co於薄膜寬度方向非對稱地行走，施加於薄膜之張力於寬度方向變不均一，故如上述於斜面延伸後之薄膜，先行側之膜厚較厚，延遲側之膜厚較薄。此時之薄膜表面形狀如例如圖8之虛線所示。 The pair of grippers Ci and Co travel asymmetrically in the width direction of the film in a curved bevel extending manner in which the film transport direction is bent in the middle, and the tension applied to the film becomes uneven in the width direction, so that the above-described slope extends The film has a thick film thickness on the leading side and a thin film thickness on the retard side. The surface shape of the film at this time is as shown, for example, by the dotted line in FIG.

藉由滿足條件式(1)亦即於斜面延伸區域Z2-2中，使延遲側溫度高於先行側，可使因斜面延伸而施加於薄膜之應力(張力)與殘留之應力(殘留應力)於延遲側減少，於先行側維持最小限度。而且，藉由滿足條件式(2)亦即於緩和區域Z3中，使先行側溫度高於延遲側，可使延遲側之殘留應力緩和並且抑制其緩和，且於先 行側可促進於斜面延伸步驟中維持之殘留應力之緩和。由以上可減少先行側之薄膜膜厚，可減低薄膜寬度方向之膜厚偏差。緩和步驟後之薄膜表面形狀如圖8之實線所示。 By satisfying the conditional expression (1), that is, in the slope extending region Z2-2, the temperature on the retard side is higher than the leading side, and stress (tension) and residual stress (residual stress) applied to the film due to the extending of the slope can be made. The delay side is reduced, and the leading side is kept to a minimum. Further, by satisfying the conditional expression (2), that is, in the relaxation region Z3, the front side temperature is higher than the retard side, the residual stress on the retard side can be relaxed and the relaxation can be suppressed, and the The row side promotes the relaxation of the residual stress maintained during the ramp extension step. From the above, the film thickness of the film side on the leading side can be reduced, and the film thickness deviation in the film width direction can be reduced. The surface shape of the film after the relaxation step is shown by the solid line in FIG.

又，藉由滿足條件式(3)亦即使斜面延伸區域Z2-2與緩和區域Z3產生5℃以上40℃以下之溫度差，可藉由緩和區域Z3確實地使因斜面延伸於薄膜產生之殘留應力緩和，更易於獲得薄膜寬度方向膜厚偏差減低效果。 Further, by satisfying the conditional expression (3), even if the temperature difference between 5 ° C and 40 ° C is generated in the slope extending region Z2-2 and the relaxation region Z3, the residual region Z3 can be surely caused by the slope extending to the film. The stress is alleviated, and it is easier to obtain a film thickness deviation reduction effect in the film width direction.

因此，製造膜厚大致均一之斜面延伸薄膜時，並無必要製造且事先準備於寬度方向使膜厚變化之特殊薄膜。其結果，可提高斜面延伸薄膜之生產性。又，因斜面延伸區域2-2之斜面延伸而賦予至薄膜之殘留應力由於於緩和區域Z3被適當緩和，故亦可減低起因於該殘留應力而使薄膜發生條狀皺褶(表面凹凸不平)。亦即，藉由滿足條件式(1)~(3)，可減低皺褶發生並且提高斜面延伸薄膜之生產性。 Therefore, when a bevel-stretched film having a substantially uniform film thickness is produced, it is not necessary to manufacture a special film which is prepared in advance in the width direction to change the film thickness. As a result, the productivity of the bevel stretch film can be improved. Further, since the residual stress applied to the film due to the slope of the inclined surface extending region 2-2 is appropriately moderated in the relaxation region Z3, the film may be reduced in wrinkles (surface irregularities) due to the residual stress. . That is, by satisfying the conditional expressions (1) to (3), the occurrence of wrinkles can be reduced and the productivity of the bevel stretched film can be improved.

又，於斜面延伸區域Z2-2，藉由使T1-T2為1℃以上，可確實減低延遲側之張力及殘留應力，且確實維持先行側之殘留應力。藉此，於緩和區域Z3形成第2溫度分佈時，可避免先行側應力過於緩和，避免先行側膜厚小於延遲側，避免膜厚於寬度方向不均一。另一方面，藉由使T1-T2為15℃以下，可避免延遲側殘留應力過度減低。藉此，於緩和區域Z3形成第2溫度分佈時，亦可藉由先行側之應力緩和避免先行側之膜厚變得不接近延遲 側膜厚之情況，藉此，可避免膜厚於寬度方向不均一。 Further, in the slope extending region Z2-2, by setting T1-T2 to 1 °C or more, the tension on the retard side and the residual stress can be surely reduced, and the residual stress on the leading side can be surely maintained. Thereby, when the second temperature distribution is formed in the relaxation region Z3, the stress on the leading side can be prevented from being excessively relaxed, and the film thickness on the leading side can be prevented from being smaller than the retard side, and the film thickness can be prevented from being uneven in the width direction. On the other hand, by setting T1-T2 to 15 ° C or lower, excessive reduction of the residual stress on the retard side can be avoided. Therefore, when the second temperature distribution is formed in the relaxation region Z3, the film thickness on the leading side can be prevented from becoming close to the retardation by the stress relaxation on the leading side. In the case of the side film thickness, the film thickness can be prevented from being uneven in the width direction.

又，於緩和區域Z3，藉由使T3-T4為5℃以上，可避免緩和區域Z3之先行側之應力緩和過小，可避免先行側之膜厚減少量降低。另一方面，藉由使使T3-T4為30℃以下，可避免緩和區域Z3之先行側之應力緩和過大，可避免先行側之膜厚減少量增大。任一情況均可避免膜厚於寬度方向之不均一。 Further, in the relaxation region Z3, by setting T3-T4 to 5 °C or higher, it is possible to prevent the stress relaxation on the leading side of the relaxation region Z3 from being excessively small, and it is possible to avoid a decrease in the film thickness reduction amount on the leading side. On the other hand, by setting T3-T4 to 30 ° C or lower, it is possible to prevent the stress relaxation on the leading side of the relaxation region Z3 from being excessively large, and it is possible to avoid an increase in the film thickness reduction amount on the leading side. In either case, the film thickness is not uniform in the width direction.

又，於斜面延伸區域Z2-2，於連結斜面延伸結束位置P、Q之方向(連結到達斜面延伸結束位置之P、Q之把持具Ci、Co之方向)，形成上述第1溫度分佈。於斜面延伸區域Z2-2中，連結斜面延伸結束位置P、Q之線上係斜面延伸中之張力(tension)最大之位置。因此，藉由於此位置形成上述第1溫度分佈，而於緩和區域Z3形成第2溫度分佈並減低薄膜寬度方向之膜厚偏差而言，利用本實施形態之製法非常有效。 Further, in the inclined surface extending region Z2-2, the first temperature distribution is formed in the direction connecting the inclined surface extending end positions P and Q (the directions connecting the grippers Ci and Co which reach the end of the inclined surface extending end P and Q). In the inclined surface extending region Z2-2, the line connecting the inclined surface extending end positions P and Q is the position where the tension in the inclined surface is the largest. Therefore, by forming the first temperature distribution at this position and forming the second temperature distribution in the relaxation region Z3 and reducing the film thickness variation in the film width direction, the production method of the present embodiment is very effective.

又，於緩和區域Z3中，於通過上述中間點M3、垂直於搬送方向之寬度方向中形成上述第2溫度分佈。於緩和區域Z3全體之平均位置形成第2溫度分佈，而可減少先行側之薄膜膜厚，可確實獲得減低薄膜寬度方向之膜厚偏差之效果。 Further, in the relaxation zone Z3, the second temperature distribution is formed in the width direction perpendicular to the conveyance direction through the intermediate point M3. The second temperature distribution is formed at the average position of the entire relaxation zone Z3, and the thickness of the film on the leading side can be reduced, and the effect of reducing the film thickness deviation in the film width direction can be surely obtained.

又，斜面延伸區域Z2-2之上述第1位置M1之溫度比緩和區域Z3之上述中間點M3之溫度高5~40℃。藉由使第1位置M1及中間點M3中之溫度差如上述規定，可使條件式(3)之設定更有效。 Further, the temperature of the first position M1 of the slope extending region Z2-2 is higher than the temperature of the intermediate point M3 of the relaxation region Z3 by 5 to 40 °C. By setting the temperature difference between the first position M1 and the intermediate point M3 as described above, the setting of the conditional expression (3) can be made more effective.

又，由於上述第1溫度分佈自延遲側至先行側溫度單調地減少而分佈，故可確實實現先行側溫度低於延遲側溫度之溫度分佈(第1溫度分佈)。 In addition, since the temperature of the first temperature distribution is monotonously decreased from the retard side to the leading side, the temperature distribution (first temperature distribution) at which the front side temperature is lower than the retard side temperature can be surely achieved.

同樣，由於上述第2溫度分佈自延遲側至先行側溫度單調地增加而分佈，故可確實實現先行側溫度高於延遲側溫度之溫度分佈(第2溫度分佈)。 In the same manner, since the temperature of the second temperature distribution is monotonously increased from the retard side to the leading side, the temperature distribution (second temperature distribution) of the preceding side temperature higher than the retard side temperature can be surely achieved.

不過，於斜面延伸區域Z2-2，亦可以使薄膜之慢軸相對於寬度方向成為30°~60°之角度之方式，使薄膜於斜面方向延伸。尤其，以輥對輥方式製造使長條狀斜面延伸薄膜與長條狀偏光器(長條偏光薄膜)貼合之長條狀偏光板時，基於可飛躍地提高圓偏光板之生產性之觀點，期望以使薄膜之慢軸相對於寬度方向成為約45°之角度之方式，使薄膜於斜面方向延伸，製造長條狀斜面延伸薄膜。又，所謂約45°包含45°±3°之範圍。 However, in the inclined surface extending region Z2-2, the slow axis of the film may be inclined at an angle of 30 to 60 with respect to the width direction to extend the film in the oblique direction. In particular, when a long polarizing plate in which a long beveled stretch film and a long strip polarizer (long polarizing film) are bonded together by a roll-to-roll method is used, the viewpoint of the productivity of the circular polarizer can be greatly improved. It is desirable to form the elongated beveled stretched film by extending the film in the direction of the slope so that the slow axis of the film is at an angle of about 45° with respect to the width direction. Further, the term "about 45" includes a range of 45 ° ± 3 °.

(其他) (other)

斜面延伸步驟中，薄膜之搬送速度可為1~150m/分鐘。以提高薄膜生產性之觀點而言，薄膜之搬送速度期望為10~120m/分鐘，更期望為20~100m/分鐘。 In the step of extending the bevel, the transport speed of the film may be from 1 to 150 m/min. From the viewpoint of improving film productivity, the film transport speed is desirably 10 to 120 m/min, and more desirably 20 to 100 m/min.

<長條斜面延伸薄膜之品質> <Quality of long beveled stretch film>

藉由本實施形態之製造方法所得之長條斜面延伸薄膜中，較好配向角θ以對於捲取方向以例如大於0°且未達90°之範圍傾斜，至少於1300mm之寬度中，寬度方向之 面內延遲Ro之偏差為2nm以下，配向角θ之偏差未達0.6°。又，前述長條斜面延伸薄膜之於波長550nm測定之面內延遲值Ro(550)較好於80nm以上160nm以下之範圍，更好於90nm以上150nm以下之範圍。 In the long bevel extending film obtained by the manufacturing method of the present embodiment, it is preferred that the alignment angle θ is inclined in the range of, for example, more than 0° and less than 90° for the winding direction, at least in the width of 1300 mm, and in the width direction. The deviation of the in-plane retardation Ro is 2 nm or less, and the deviation of the alignment angle θ is less than 0.6°. Further, the in-plane retardation value Ro (550) measured at a wavelength of 550 nm of the long beveled stretched 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，藉由本實施形態之製造方法所得之長條斜面延伸薄膜中，面內延遲Ro之偏差於寬度方向之至少1300mm中為2nm以下，較好為1nm以下。藉由使面內延遲Ro之偏差於上述範圍內，於將長條斜面延伸薄膜與偏光器貼合作成圓偏光板，並將其應用於有機EL圖像顯示裝置時，可抑制黑顯示時因外光反射光洩漏所致之色不均。又，將長條斜面延伸薄膜作為例如液晶顯示裝置用之相位差薄膜使用時亦可成為顯示品質良好者。 In the long-slope extended film obtained by the production method 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 width direction. When the deviation of the in-plane retardation Ro is within the above range, when the long beveled stretch film and the polarizer are bonded together to form a circular polarizing plate and applied to an organic EL image display device, the black display time can be suppressed. The color unevenness caused by the leakage of external light reflected light. Further, when the long beveled stretched film is used as, for example, a retardation film for a liquid crystal display device, it can also be a display quality.

又，藉由本實施形態之製造方法所得之長條斜面延伸薄膜中，配向角θ之偏差於寬度方向之至少1300mm中未達0.6°，較好未達0.4°，最好未達0.2°。配向角θ之偏差超過0.6°之長條斜面延伸薄膜與偏光器貼合作成圓偏光板，並將其應用於有機EL顯示裝置等之圖像顯示裝置時，有產生光洩漏，使明暗對比度降低之情況。 Further, in the long bevel stretched film obtained by the production method of the present embodiment, the deviation of the alignment angle θ is less than 0.6° in at least 1300 mm in the width direction, preferably less than 0.4°, and most preferably less than 0.2°. When a long beveled stretch film having a deviation of the alignment angle θ of more than 0.6° is bonded to a polarizer to form a circular polarizing plate, and is applied to an image display device such as an organic EL display device, light leakage occurs to lower the contrast ratio of light and dark. The situation.

藉由本實施形態之製造方法所得之長條斜面延伸薄膜之面內延遲Ro係根據所用之顯示裝置之設計而選擇最適值。又，前述Ro係面內慢軸方向之折射率nx與面內與前述慢軸正交之方向之折射率ny之差乘以薄膜之平均厚度d之值(Ro=(nx-ny)×d)。 The in-plane retardation Ro of the long beveled stretch film obtained by the production method of the present embodiment is selected according to the design of the display device used. Further, the difference between the refractive index nx in the slow axis direction of the Ro-plane and the refractive index ny in the direction orthogonal to the slow axis in the plane is multiplied by the value of the average thickness d of the film (Ro = (nx - ny) × d ).

藉由本實施形態之製造方法所得之長條斜面 延伸薄膜之平均厚度，基於機械強度等之觀點，為1~400μm，較好為10~200μm，進而較好為10~60μm，特佳為15~45μm。 Long bevel obtained by the manufacturing method of the present embodiment The average thickness of the stretched film 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.

藉由本實施形態之製造方法所得之長條斜面延伸薄膜其表面亦可具有功能層。作為功能層可考慮抗反射層、低折射率層、硬塗覆層、光散射層、光擴散層、抗靜電層、導電層、電極層、雙折射層、表面能調整層、UV吸收層、色材層、耐水層、特定氣體障蔽層、耐熱層、磁性層、抗氧化層、上覆層等。 The long beveled stretched film obtained by the production method of the present embodiment may have a functional layer on its surface. 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, an overcoat layer, and the like.

<圓偏光板> <Circular polarizer>

本實施形態之圓偏光板係依序積層偏光保護薄膜、偏光器、λ/4薄膜而成，λ/4薄膜之慢軸與偏光器之吸收軸(或透過軸)所成之角度為45°。本實施形態之圓偏光板使用於有機EL顯示裝置時，上述之偏光板保護薄膜、偏光器、λ/4薄膜分別對應於圖9之保護薄膜313、偏光器311、λ/4薄膜316。本實施形態中，較好依序積層長條狀偏光板保護薄膜、長條狀偏光器、長條狀λ/4薄膜(長條斜面延伸薄膜)而形成。 The circularly polarizing plate of the present embodiment is formed by sequentially depositing a polarizing protective film, a polarizer, and a λ/4 film, and the angle between the slow axis of the λ/4 film and the absorption axis (or transmission axis) of the polarizer is 45°. . When the circularly polarizing plate of the present embodiment is used in an organic EL display device, the polarizing plate protective film, the polarizer, and the λ/4 film described above correspond to the protective film 313, the polarizer 311, and the λ/4 film 316 of Fig. 9, respectively. In the present embodiment, it is preferable to form a strip-shaped polarizing plate protective film, a long-length polarizer, and a long λ/4 film (long beveled stretched film).

又，本實施形態之圓偏光板使用於液晶顯示裝置時，上述之偏光板保護薄膜、偏光器、λ/4薄膜分別對應於圖10之保護薄膜506、偏光器501、λ/4薄膜503。於顯示單元401之外側(視認側)配置保護薄膜506、偏光器501，於偏光器501之更外側(於視認側) 配置有λ/4薄膜503，故自顯示單元401射出並透過偏光器501之直線偏光由λ/4薄膜503轉換為圓偏光或橢圓偏光。因此，觀察者配戴偏光太陽眼鏡觀察顯示裝置400之顯示圖像時，以任何角度觀察時(即使偏光器501之透過軸(垂直於吸收軸)與偏光太陽眼鏡之透過軸如何偏移)，平行於偏光太陽眼鏡之透過軸之光的成分均可導入觀察者眼睛而可觀察顯示圖像，可抑制因觀察角度而難以看見顯示圖像之情況。 Further, when the circularly polarizing plate of the present embodiment is used in a liquid crystal display device, the polarizing plate protective film, the polarizer, and the λ/4 film described above correspond to the protective film 506, the polarizer 501, and the λ/4 film 503 of Fig. 10, respectively. The protective film 506 and the polarizer 501 are disposed on the outer side (the viewing side) of the display unit 401 on the outer side of the polarizer 501 (on the viewing side). Since the λ/4 film 503 is disposed, the linearly polarized light emitted from the display unit 401 and transmitted through the polarizer 501 is converted into circularly polarized or elliptically polarized light by the λ/4 film 503. Therefore, when the observer wears the polarized sunglasses to observe the display image of the display device 400, when viewed at any angle (even if the transmission axis of the polarizer 501 (perpendicular to the absorption axis) is offset from the transmission axis of the polarized sunglasses), The components parallel to the transmission axis of the polarized sunglasses can be introduced into the observer's eyes to observe the displayed image, and it is possible to suppress the display image from being difficult to see due to the observation angle.

本實施形態之圓偏光板係使用將摻雜碘或二色性染料之聚乙烯醇延伸者作為偏光器，以λ/4薄膜/偏光器之構成貼合而製造。偏光器之膜厚為5~40μm，較好為5~30μm，特佳為5~20μm。 The circularly polarizing plate of the present embodiment is produced by bonding a polyvinyl alcohol doped with iodine or a dichroic dye as a polarizer and laminating a λ/4 film/polarizer. The film thickness of the polarizer is 5 to 40 μm, preferably 5 to 30 μm, and particularly preferably 5 to 20 μm.

偏光板可藉一般方法製作。較好將經鹼來鹼化處理之λ/4薄膜，使用完全鹼化型聚乙烯醇溶液貼合於將聚乙烯醇系薄膜於碘溶液中浸漬延伸而製作之偏光器之一面上。 The polarizing plate can be produced by a general method. Preferably, the λ/4 film alkalized by alkali is attached to one surface of a polarizer produced by immersing and stretching a polyvinyl alcohol film in an iodine solution using a fully alkalized polyvinyl alcohol solution.

偏光板可進而於該偏光板之與偏光板保護薄膜相反面上貼合剝離薄膜而構成。保護薄膜及剝離薄膜係於偏光板出貨時、製品檢查時等用以保護偏光板所使用之目的。 The polarizing plate can be further formed by laminating a release film on the opposite surface of the polarizing plate from the polarizing plate protective film. The protective film and the release film are used for protecting the polarizing plate when the polarizing plate is shipped, and when the product is inspected.

<有機EL顯示裝置> <Organic EL display device>

圖9係顯示作為本實施形態之OLED之有機EL顯示裝置100之概略構成之剖面圖。又，有機EL顯示裝置 100之構成不限定於該等。 FIG. 9 is a cross-sectional view showing a schematic configuration of an organic EL display device 100 as an OLED of the present embodiment. Also, an organic EL display device The configuration of 100 is not limited to these.

有機EL顯示裝置100係藉由於有機EL元件101上透過接著層201形成圓偏光板301而構成。有機EL元件101係於使用玻璃或聚醯亞胺等之基板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而構成。又，金屬電極112亦可由反射電極與透明電極構成。 The organic EL display device 100 is configured by forming the circular polarizing plate 301 through the adhesive layer 201 on the organic EL element 101. The organic EL element 101 is formed by using a substrate 111 such as glass or polyimide, and has a metal electrode 112, a light-emitting layer 113, a transparent electrode (ITO or the like) 114, and a sealing layer 115 in this order. Further, the metal electrode 112 may be composed of a reflective electrode and a transparent electrode.

圓偏光板301係藉由自有機EL元件101側起依序積層λ/4薄膜316、接著層315、偏光器311、接著層312、保護薄膜313、硬化層314而成，偏光器311由λ/4薄膜316與保護薄膜313夾持。藉由使偏光器311之透過軸與由本實施形態之長條斜面延伸薄膜所成之λ/4薄膜316之慢軸所成之角度成為約45°(或135°)之方式貼合兩者，構成圓偏光板301。 The circular polarizing plate 301 is formed by sequentially laminating a λ/4 film 316, an adhesive layer 315, a polarizer 311, a bonding layer 312, a protective film 313, and a hardened layer 314 from the side of the organic EL element 101, and the polarizer 311 is composed of λ. The /4 film 316 is sandwiched by the protective film 313. By bonding the transmission axis of the polarizer 311 to the slow axis of the λ/4 film 316 formed by the long bevel extending film of the present embodiment, the angle is about 45 (or 135). A circular polarizing plate 301 is formed.

上述保護薄膜313上較好積層硬化層314。硬化層314不僅可防止有機EL顯示裝置100之表面傷痕，亦具有防止因圓偏光板301所致之翹曲之效果。進而於硬化層314上亦可形成抗反射層。有機EL元件101本身之厚度為1μm左右。 The hard coat layer 314 is preferably laminated on the protective film 313. The hardened layer 314 not only prevents surface scratches 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 itself has a thickness of about 1 μm.

上述構成中，若對金屬電極112及透明電極114施加電壓，則對於發光層113自金屬電極112及透明電極114中成為陰極之電極注入電子，自成為陽極之電極注入電洞，使兩者於發光層113再結合而發生對應於發光層113之發光特性之可見光線之發光。於發光層113產生 之光直接或由金屬電極112反射後，透過透明電極114及圓偏光板301取出至外部。 In the above configuration, when a voltage is applied to the metal electrode 112 and the transparent electrode 114, electrons are injected into the light-emitting layer 113 from the metal electrode 112 and the electrode serving as the cathode in the transparent electrode 114, and a hole is injected from the electrode serving as the anode. The light-emitting layer 113 is recombined to emit light of visible light rays corresponding to the light-emitting characteristics of the light-emitting layer 113. Produced in the light emitting layer 113 The light is directly or reflected by the metal electrode 112, and then taken out through the transparent electrode 114 and the circular polarizing plate 301 to the outside.

一般於有機EL顯示裝置中，形成於透明基板上依序積層金屬電極及發光層及透明電極之發光體的元件(有機EL元件)。此處，發光層為各種有機薄膜之積層體，已知有例如由三苯胺衍生物等所成之電洞注入層與由蒽等之螢光性有機固體所成之發光層之積層體、或由此等發光層與由苝衍生物等所成之電子注入層之積層體、或該等之電洞注入層、發光層、電子注入層之積層體等之各種組合之構成。 In an organic EL display device, an element (organic EL element) in which a metal electrode, a light-emitting layer, and an illuminant of a transparent electrode are sequentially laminated on a transparent substrate is formed. Here, the light-emitting layer is a laminate of various organic thin films, and for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light-emitting layer made of a fluorescent organic solid such as ruthenium or the like, or The light-emitting layer is composed of a laminate of an electron injection layer made of an anthracene derivative or the like, or a combination of the hole injection layer, the light-emitting layer, and the electron injection layer.

有機EL顯示裝置係藉由下述原理而發光：藉由對透明電極及金屬電極施加電壓，而於發光層注入電洞及電子，藉由該等電洞與電子之再結合產生之能量激發螢光物質，經激發之螢光物質回到基底狀態時放出光。途中再結合之機制與一般二極體相同，如由此可預測般，電流與發光強度伴隨對於施加電壓之整流性而顯示強的非線形性。 The organic EL display device emits light by applying a voltage to the transparent electrode and the metal electrode to inject holes and electrons into the light-emitting layer, and the energy generated by the recombination of the holes and the electrons activates the firefly. The light substance emits light when the excited fluorescent substance returns to the substrate state. The mechanism of recombination on the way is the same as that of a general diode. As can be predicted from this, the current and luminous intensity show strong nonlinearity accompanying the rectification of the applied voltage.

有機EL顯示裝置中，為了取出發光層之發光，至少一電極必須為透明，通常使用以氧化銦錫(ITO)等透明導電體形成之透明電極作為陽極。另一方面，為了使電子注入容易提高發光效率，重要的是於陰極使用功函數小之物質，通常使用Mg-Ag、Al-Li等之金屬電極。 In the organic EL display device, at least one of the electrodes must be transparent in order to extract the light emitted from the light-emitting layer, and a transparent electrode formed of a transparent conductor such as indium tin oxide (ITO) is usually used as the anode. On the other hand, in order to make electron injection easy to improve luminous efficiency, it is important to use a material having a small work function at the cathode, and a metal electrode such as Mg-Ag or Al-Li is usually used.

如此構成之有機EL顯示裝置中，發光層係以 厚度10nm左右之極薄膜形成。因此，發光層亦與透明電極同樣，使光幾乎完全透過。其結果，非發光時自透明基板表面入射，透過透明電極與發光層，被金屬電極反射之光再次朝透明基板表面側射出，而自外部視認時，有機EL顯示裝置之顯示面看起來如鏡面。 In the organic EL display device thus constituted, the light-emitting layer is A thin film having a thickness of about 10 nm is formed. Therefore, the light-emitting layer also transmits light almost completely, similarly to the transparent electrode. As a result, when the non-light-emitting period is incident from the surface of the transparent substrate, the transparent electrode and the light-emitting layer are transmitted, and the light reflected by the metal electrode is again emitted toward the surface side of the transparent substrate, and when viewed from the outside, the display surface of the organic EL display device looks like a mirror surface. .

本實施形態之圓偏光板係應用於此種外光反射特別成為問題之有機EL顯示裝置。 The circularly polarizing plate of the present embodiment is applied to an organic EL display device in which such external light reflection is particularly problematic.

亦即，有機EL元件101之非發光時，因室內照明等自有機EL元件101之外部入射之外光藉由圓偏光板301之偏光器311一半被吸收，剩餘一半作為直線偏光而透過，並入射至λ/4薄膜316。由於偏光器311之透過軸與λ/4薄膜316之慢軸以45°(或135°)交叉之方式配置，故入射至λ/4薄膜316之光藉由透過λ/4薄膜316而轉換為圓偏光。 In other words, when the organic EL element 101 is not emitting light, the light is incident on the outside of the organic EL element 101 by the indoor illumination or the like, and the light is absorbed by the polarizer 311 of the circular polarizing plate 301, and the remaining half is transmitted as linear polarized light, and It is incident on the λ/4 film 316. Since the transmission axis of the polarizer 311 and the slow axis of the λ/4 film 316 are arranged at 45° (or 135°), the light incident on the λ/4 film 316 is converted into the λ/4 film 316 to be converted into Round polarized light.

自λ/4薄膜316射出之圓偏光於以有機EL元件101之金屬電極112鏡面反射時，相位反轉180度，作為轉回之圓偏光而反射。該反射光藉由入射至λ/4薄膜316，而轉換成垂直於偏光器311之透過軸(平行於吸收軸)之直線偏光，由偏光器311全部吸收，未射出至外部。亦即，藉由圓偏光板301，可減低於有機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 reversed by 180 degrees, and is reflected as circularly polarized light. The reflected light is converted into a linearly polarized light perpendicular to the transmission axis (parallel to the absorption axis) of the polarizer 311 by being incident on the λ/4 film 316, and is totally absorbed by the polarizer 311, and is not emitted to the outside. That is, by the circular polarizing plate 301, light reflection outside the organic EL element 101 can be reduced.

<液晶顯示裝置> <Liquid crystal display device>

圖10係顯示作為本實施形態之液晶顯示裝置之顯示 裝置400之概略構成之剖面圖。顯示裝置400於顯示單元401之一面側配置偏光板402而構成。 Figure 10 is a view showing the display of the liquid crystal display device of the embodiment. A cross-sectional view of a schematic configuration of device 400. The display device 400 is configured by arranging a polarizing plate 402 on one surface side of the display unit 401.

又，液晶顯示裝置時，顯示單元401可認為係以一對基板夾持液晶層之液晶單元。又，對於液晶單元於與偏光板402相反側，設置以與偏光板402正交尼柯耳狀態配置之另一偏光板及照明液晶單元之背光單元，但圖10中省略該等圖示。 Further, in the case of the liquid crystal display device, the display unit 401 can be considered to be a liquid crystal cell in which a liquid crystal layer is sandwiched between a pair of substrates. Further, the liquid crystal cell is provided with another polarizing plate disposed in a Nicols state orthogonal to the polarizing plate 402 and a backlight unit for illuminating the liquid crystal cell on the side opposite to the polarizing plate 402, but the illustration is omitted in FIG.

又，顯示裝置400，對於偏光板402於與顯示單元401相反側亦可具有前視窗403。前視窗403係成為顯示裝置400之外裝蓋體者，例如以覆蓋玻璃構成。前視窗403與偏光板402之間填充有例如由紫外線硬化型樹脂所成之填充材404。無填充材404時，由於於前視窗403與偏光板402之間形成空氣層，故藉由前視窗403及偏光板402與空氣層之介面之光反射，而有使顯示圖像之視認性降低之情況。然而，藉由上述填充材404，由於前視窗403與偏光板402之間未形成空氣層，故可避免因於上述介面光之反射所致之顯示圖像視認性之降低。 Further, the display device 400 may have a front window 403 on the side opposite to the display unit 401 of the polarizing plate 402. The front window 403 is a cover body outside the display device 400, and is made of, for example, a cover glass. A filler 404 made of, for example, an ultraviolet curable resin is filled between the front window 403 and the polarizing plate 402. When the filler 404 is not provided, since an air layer is formed between the front window 403 and the polarizing plate 402, the visibility of the display image is lowered by the light reflected from the interface between the front window 403 and the polarizing plate 402 and the air layer. The situation. However, in the filler 404, since the air layer is not formed between the front window 403 and the polarizing plate 402, the deterioration of the visibility of the display image due to the reflection of the interface light can be avoided.

偏光板402具有使特定直線偏光透過之偏光器501。於偏光器501之一面側(與顯示單元401相反側)透過接著層502依序積層λ/4薄膜503、由紫外線硬化型樹脂所成之硬化層504。且，於偏光器501之另一面側(顯示單元401側)透過接著層505貼合保護薄膜506。 The polarizing plate 402 has a polarizer 501 that transmits a specific linearly polarized light. The λ/4 film 503 and the hardened layer 504 made of an ultraviolet curable resin are sequentially laminated on the surface side (the side opposite to the display unit 401) of the polarizer 501 through the adhesive layer 502. Further, the protective film 506 is bonded to the other surface side (the display unit 401 side) of the polarizer 501 through the adhesive layer 505.

偏光器501係藉由使例如聚乙烯醇薄膜以二 色性色素染色並高倍率延伸而得者。偏光器501經鹼處理(亦稱為鹼化處理)後，於一面側透過接著層502貼合λ/4薄膜503，於另一面側透過接著層505貼合保護薄膜506。 The polarizer 501 is made by, for example, making a polyvinyl alcohol film Chromatic pigment dyeing and high magnification extension. After the alkalit treatment (also referred to as alkalization treatment), the polarizer 501 is bonded to the λ/4 film 503 through the adhesive layer 502 on one surface side, and the protective film 506 is bonded to the other surface side through the adhesive layer 505.

接著層502、505係由例如聚乙烯醇接著劑(PVA接著劑、水糊)所成之層，但亦可為由紫外線硬化型接著劑(UV接著劑)所成之層。該等接著劑於塗佈接著面之狀態為液體，塗佈後藉由乾燥或紫外線照射而硬化，而使兩者接著。亦即，接著層502、505係藉由自液狀之狀態變化分別使偏光器501與λ/4薄膜503、偏光器501與保護薄膜506接著。如此，接著層502、505係藉由自液狀之狀態變化使兩者接著之方面，與不引起此種狀態變化而使兩者接著之黏著層(於基材上具有黏著劑之薄片狀黏著層)不同。 Next, the layers 502 and 505 are formed of, for example, a polyvinyl alcohol adhesive (PVA adhesive, water paste), but may be a layer formed of an ultraviolet curable adhesive (UV adhesive). These adhesives are liquid in the state of applying the adhesive surface, and are hardened by drying or ultraviolet irradiation after application, and the two are followed. That is, the subsequent layers 502 and 505 are followed by the polarizer 501, the λ/4 film 503, the polarizer 501, and the protective film 506 by changing from the state of the liquid state. In this way, the subsequent layers 502 and 505 are adhered to each other by the change from the state of the liquid state, and the adhesion layer (the flaky adhesion of the adhesive on the substrate) is caused by not changing the state. Layer) different.

λ/4薄膜503係對於透過光賦予波長之1/4左右之面內相位差之層，於本實施形態中，例如含有纖維素系樹脂(纖維素系聚合物)。又λ/4薄膜503亦可代替纖維素系聚合物而含有聚碳酸酯系樹脂(聚碳酸酯系聚合物)，亦可含有環烯烴系樹脂(環烯烴系聚合物)。惟，基於耐藥品性之觀點，λ/4薄膜503期望含有纖維素系聚合物或聚碳酸酯系聚合物。 The λ/4 film 503 is a layer that imparts an in-plane retardation of about 1/4 of the wavelength to the transmitted light. In the present embodiment, for example, a cellulose resin (cellulose-based polymer) is contained. Further, the λ/4 film 503 may contain a polycarbonate resin (polycarbonate polymer) or a cycloolefin resin (cycloolefin polymer) instead of the cellulose polymer. However, the λ/4 film 503 desirably contains a cellulose-based polymer or a polycarbonate-based polymer from the viewpoint of chemical resistance.

λ/4薄膜503為厚度10μm~70μm之薄膜之λ/4薄膜。又，λ/4薄膜503之慢軸與偏光器501之吸收軸所成之角度(交叉角)為30°~60°，藉此，來自偏光器501 之直線偏光藉由λ/4薄膜503轉換成圓偏光或橢圓偏光。 The λ/4 film 503 is a λ/4 film of a film having a thickness of 10 μm to 70 μm. Moreover, the angle (crossing angle) between the slow axis of the λ/4 film 503 and the absorption axis of the polarizer 501 is 30° to 60°, thereby coming from the polarizer 501. The linearly polarized light is converted into circularly polarized or elliptically polarized light by the λ/4 film 503.

硬化層504(亦稱為硬塗覆層)係由活性能量線硬化型樹脂(例如紫外線硬化型樹脂)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係由例如纖維素系樹脂(纖維素系聚合物)、丙烯酸樹脂、環狀聚烯烴(COP)、聚碳酸酯(PC)所成之光學薄膜構成。保護薄膜506係作為僅保護偏光器501之背面側之薄膜而設置，但亦可作為兼具有期望光學補償功能之相位差薄膜之光學薄膜而設置。 The protective film 506 is made of, for example, an optical film made of a cellulose resin (cellulose polymer), an acrylic resin, a cyclic polyolefin (COP), or a polycarbonate (PC). The protective film 506 is provided as a film that protects only the back side of the polarizer 501, but may be provided as an optical film having a retardation film having a desired optical compensation function.

又，液晶顯示裝置時，對於顯示單元401(液晶單元)於與偏光板402相反側配置之其他偏光板係偏光器表面由2個光學薄膜夾持而構成，但作為上述偏光器及光學薄膜，可使用與偏光板402之偏光器501及保護薄膜506同樣者。 Further, in the liquid crystal display device, the surface of the other polarizing plate type polarizer disposed on the opposite side of the polarizing plate 402 from the display unit 401 (liquid crystal cell) is sandwiched between two optical films, but as the polarizer and the optical film, The same as the polarizer 501 and the protective film 506 of the polarizing plate 402 can be used.

此處，上述偏光器501及λ/4薄膜503各可為長條狀。該情況下，期望λ/4薄膜503之慢軸相對於λ/4薄膜503之長度方向傾斜30°~60°。該情況下，長條狀之λ/4薄膜503藉由斜面延伸製作而作成輥狀之薄膜，將其與輥狀之偏光器501以所謂輥對輥方式貼合而製作長條狀偏光板402。因此，與逐片貼合薄膜片之批式製作偏光板402之情況相比，生產性飛躍性提高，良率亦可大幅改善。 Here, each of the polarizer 501 and the λ/4 film 503 may be elongated. In this case, it is desirable that the slow axis of the λ/4 film 503 is inclined by 30 to 60 with respect to the longitudinal direction of the λ/4 film 503. In this case, the long λ/4 film 503 is formed into a roll-shaped film by obliquely extending the surface, and is bonded to the roll-shaped polarizer 501 by a so-called roll-to-roll method to form the elongated polarizing plate 402. . Therefore, the productivity is drastically improved and the yield can be greatly improved as compared with the case where the polarizing plate 402 is produced by batch-bonding the film sheets one by one.

又於λ/4薄膜503之接著層502側，亦可設置用以提高λ/4薄膜503之接著性之易接著層。易接著層係藉由於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，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、底塗塗佈處理等，但只要實施該等中至少一種即可。該等易接著處理中，基於生產性之觀點，較好以電暈處理、電漿處理作為易接著處理。 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-to-continue layer is formed by the easy-to-continue processing of the layer 502 of the λ/4 film 503 to make. 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 coating treatment, etc., but at least one of them may be carried out. In the easy-to-continue processing, it is preferable to use corona treatment or plasma treatment as an easy-to-continue treatment based on the viewpoint of productivity.

<實施例> <Example>

以下，針對本實施形態之斜面延伸薄膜之製造有關之具體例之實施例亦舉例比較例加以說明。又，本發明不限於以下實施例者。又以下中，使用「份」或「%」之表記，只要未特別限定，則該等表示為「質量份」或「質量%」。 Hereinafter, examples of specific examples relating to the manufacture of the bevel stretch film of the present embodiment will also be described by way of comparative examples. Further, the present invention is not limited to the following embodiments. In the following, the expression "part" or "%" is used, and unless otherwise specified, these are expressed as "parts by mass" or "mass%".

[坯片薄膜之製作] [Production of blank film]

藉由以下方法，製作作為坯片薄膜之長條薄膜1。又，長條薄膜1係纖維素酯系樹脂薄膜。 A long film 1 as a green film was produced by the following method. Further, the long film 1 is a cellulose ester resin film.

《微粒子分散液》 Microparticle Dispersion

以上以溶解器攪拌混合50分鐘後，以MENTON GORLIN均質機進行分散，調製微粒子分散液1。 The mixture was stirred and mixed for 50 minutes with a dissolver, and then dispersed by a MENTON GORLIN homogenizer to prepare a fine particle dispersion 1.

《微粒子添加液》 Microparticle Addition Liquid

基於以下組成，於饋入二氯甲烷之溶解槽中邊充分攪拌邊緩慢添加上述微粒子分散液。進而以磨碎機進行分散以使二次粒子粒徑成為特定大小。將其以日本精線(股)製之FINEMAT NF過濾，調製微粒子添加液1。 The fine particle dispersion was slowly added while sufficiently stirring in a dissolution tank fed into dichloromethane based on the following composition. Further, it is dispersed by an attritor so that the secondary particle diameter becomes a specific size. This was filtered with FINEMAT NF manufactured by Nippon Seisaku Co., Ltd. to prepare a fine particle addition liquid 1.

《主濃液》 "Main Concentrate"

調製下述組成之主濃液。首先於加壓溶解槽中添加二氯甲烷及乙醇。於饋入溶劑之加壓溶解槽中邊攪拌邊投入纖維素乙酸酯。將其邊加熱邊攪拌而完全溶解，將其以安積濾紙(股)製之安積濾紙No.244過濾，調製主濃液。又，糖酯化合物及酯化合物係使用由以下合成例合成之化合物。 The main dope of the following composition was prepared. First, dichloromethane and ethanol were added to the pressure dissolution tank. The cellulose acetate was introduced while stirring in a pressure-dissolving tank fed with a solvent. The mixture was stirred while being heated, and completely dissolved. The mixture was filtered through a filter paper No. 244 made of a filter paper (strand) to prepare a main dope. Further, as the sugar ester compound and the ester compound, a compound synthesized by the following synthesis examples is used.

《主濃液之組成》 "The composition of the main concentrated liquid"

微粒子添加液1 1質量份 Microparticle addition solution 1 part by mass

《糖酯化合物之合成》 "Synthesis of sugar ester compounds"

藉以下步驟合成糖酯化合物。 The sugar ester compound is synthesized by the following steps.

於具備攪拌裝置、回流冷卻器、溫度計及氮氣導入管之四頸梨型瓶中饋入蔗糖34.2g(0.1莫耳)、苯 甲酸酐180.8g(0.6莫耳)、吡啶379.7g(4.8莫耳)，攪拌下自氮氣導入管通入氮氣邊升溫，於70℃進行5小時酯化反應。 Feeding sucrose 34.2g (0.1m) and benzene in a four-neck pear bottle with a stirring device, a reflux cooler, a thermometer and a nitrogen inlet tube 180.8 g (0.6 mol) of acetic anhydride and 379.7 g (4.8 mol) of pyridine were heated while stirring with nitrogen gas through a nitrogen introduction tube, and the esterification reaction was carried out at 70 ° C for 5 hours.

其次將梨型瓶內減壓至4×102Pa以下，於60℃餾除多餘的吡啶後，將梨型瓶內減壓至1.3×10Pa以下，升溫至120℃，餾除苯甲酸酐、生成之苯甲酸之大部分。 Next, the inside of the pear-shaped bottle was depressurized to 4 × 10 2 Pa or less, and the excess pyridine was distilled off at 60 ° C, and then the inside of the pear-shaped bottle was depressurized to 1.3 × 10 Pa or less, and the temperature was raised to 120 ° C to distill off the benzoic anhydride. The majority of the benzoic acid produced.

最後，於分取之甲苯層中添加水100g，於常溫水洗30分鐘後，分取甲苯層，減壓下(4×102Pa以下)，於60℃餾除甲苯，獲得化合物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, and after washing at room temperature for 30 minutes, the toluene layer was separated, and under reduced pressure (4×10 2 Pa or less), toluene was distilled off at 60° C. to obtain a compound A-1. A mixture of A-2, A-3, A-4 and A-5 (sugar ester compound).

所得混合物以HPLC及LC-MASS解析後，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。 After the obtained mixture was analyzed 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, A-4 was 31.7% by mass, and A-5 was 40.5% by mass. . The average degree of substitution is 5.5.

《HPLC-MS之測定條件》 "Determination conditions of HPLC-MS"

1)LC部 1) LC department

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)、脫氣機(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 SCIENCE(股)製) Column: Inertsil ODS-3 particle size 5μm 4.6×250mm (made by GL SCIENCE)

管柱溫度：40℃ Column temperature: 40 ° C

流速：1ml/min Flow rate: 1ml/min

移動相：THF(1%乙酸)：H2O(50：50) Mobile phase: THF (1% acetic acid): H 2 O (50:50)

注入量：3μl Injection volume: 3μl

2)MS部 2) MS Department

裝置：LCQ DECA(Thermo Quest(股)製) Device: LCQ DECA (Thermo Quest system)

離子化法：電子噴霧器離子化(ESI)法 Ionization method: electron atomizer ionization (ESI) method

噴霧電壓：5kV Spray voltage: 5kV

毛細管溫度：180℃ Capillary temperature: 180 ° C

蒸氣化器溫度：450℃ Vaporizer temperature: 450 ° C

《酯化合物之合成》 "Synthesis of Ester Compounds"

藉由以下步驟合成酯化合物。 The ester compound was synthesized by the following procedure.

將1,2-丙二醇251g、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饋入具備溫度計、攪拌器、緩急冷卻管之2L四頸燒瓶中，於氮氣流中邊攪拌邊緩慢升溫至230℃。進行15小時脫水縮合反應，反應結束後於200℃減壓餾除未反應之1,2-丙二醇，而獲得酯化合物。酯化合物於使1,2-丙二醇、苯二甲酸酐及己二酸縮合所形成之聚酯鏈之末端具有苯甲酸之酯。酯化合物之酸價為0.10，數平均分子量為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 fed into a 2 L equipped with a thermometer, a stirrer, and a rapid cooling tube. In a four-necked flask, the temperature was slowly raised to 230 ° C while stirring in a nitrogen stream. After 15 hours of dehydration condensation reaction, after the completion of the reaction, unreacted 1,2-propanediol was distilled off under reduced pressure at 200 ° C to obtain an ester compound. The ester compound has an ester of benzoic acid at the end of the polyester chain formed by condensing 1,2-propylene glycol, phthalic anhydride, and adipic acid. The ester compound had an acid value of 0.10 and a number average molecular weight of 450.

其次，使用環形帶澆鑄裝置，於不鏽鋼帶支撐體上均一澆鑄。 Next, an annular belt casting device was used to uniformly cast the stainless steel belt support.

以環形帶澆鑄裝置，將上述主濃液均一澆鑄 於不鏽鋼帶支撐體上。於不鏽鋼帶支撐體上，將溶劑蒸發直至澆鑄(cast)之長條薄膜中之殘留溶劑量為75%，自不鏽鋼帶支撐體剝離，邊以多數輥邊送邊結束乾燥，獲得寬1500mm之長條薄膜1。 The main concentrated liquid is uniformly cast by an annular belt casting device On the stainless steel belt support. On the stainless steel belt support, the solvent is evaporated until the amount of residual solvent in the cast strip is 75%, and the stainless steel strip support is peeled off, and the drying is completed by a plurality of rolls, and the length is 1500 mm. Strip film 1.

[斜面延伸薄膜之製作] [Production of beveled stretch film]

將上述製造之由纖維素酯系樹脂所成之長條薄膜1供給於圖1之製造裝置1之延伸部5進行斜面延伸，控制延伸部5各區域之溫度，獲得長條斜面延伸薄膜(參考表1之實施例1~13、比較例1~5)。此時，於延伸部5，以薄膜之配向角(慢軸與寬度方向所成之角度)約為45°之方式進行斜面延伸，薄膜搬送速度設為15m/分鐘。且延伸前後之薄膜延伸倍率於實施例1~12及比較例1~4設為1.2倍，實施例13及比較例5設為1.4倍，施以修整處理後之最終薄膜寬度為2000mm。而且將延伸部5之溫度條件如表1般進行各種變更，製造斜面延伸薄膜。又，此時之斜面延伸薄膜之設計膜厚設為表1所示之值。 The long film 1 made of the cellulose ester resin produced above is supplied to the extending portion 5 of the manufacturing apparatus 1 of Fig. 1 to be inclined, and the temperature of each region of the extending portion 5 is controlled to obtain a long bevel extending film (refer to Examples 1 to 13 and Comparative Examples 1 to 5) of Table 1. At this time, in the extending portion 5, the inclined surface was extended so that the alignment angle of the film (the angle formed by the slow axis and the width direction) was about 45, and the film transport speed was set to 15 m/min. The film stretching ratio before and after the stretching was 1.2 times in Examples 1 to 12 and Comparative Examples 1 to 4, 1.4 times in Example 13 and Comparative Example 5, and the final film width after the trimming treatment was 2000 mm. Further, the temperature conditions of the extending portion 5 were variously changed as shown in Table 1, and a beveled stretched film was produced. Further, the design film thickness of the beveled stretched film at this time was set to the value shown in Table 1.

此處，延伸部5之延伸區域Z2(尤其斜面延伸區域Z2-2)及緩和區域Z3中分別配置圖6所示之加熱部11、12(噴嘴)。接著，於斜面延伸區域Z2-2，於通過圖3之斜面延伸結束位置P、Q之方向，形成以圖4之直線a1表示之第1溫度分佈。且於緩和區域Z3，於通過中間點M3且與上述搬送方向垂直之寬度方向，形成圖5之直線b1表示之第2溫度分佈。 Here, the heating portions 11 and 12 (nozzles) shown in FIG. 6 are disposed in the extending region Z2 (particularly, the inclined surface extending region Z2-2) of the extending portion 5 and the tempered region Z3. Next, in the inclined surface extending region Z2-2, the first temperature distribution indicated by the straight line a1 of Fig. 4 is formed in the direction extending from the inclined surface end positions P and Q of Fig. 3 . In the relaxation zone Z3, the second temperature distribution indicated by the straight line b1 of Fig. 5 is formed in the width direction passing through the intermediate point M3 and perpendicular to the conveyance direction.

關於第1溫度分佈中之延遲側之溫度T1(℃)及先行側之溫度T2(℃)，係測定進入到僅鐵道寬度(鐵道間隔)×5%之鐵道內側之2點即位於通過斜面延伸結束位置P、Q之線上之2點溫度，所測定之延遲側及先行側溫度分別設為溫度T1及溫度T2。且，關於第2溫度分佈中之先行側之溫度T3(℃)及延遲側之溫度T4(℃)，係測定進入到僅鐵道寬度×5%之鐵道內側之2點即位於通過上述中間點M3之寬度方向之2點溫度，所測定之先行側及延遲側溫度分別設為溫度T3及溫度T4。再者，斜面延伸區域Z2-2之上述第1位置M1之溫度設為T5(℃)，緩和區域Z3之上述中間點M3之溫度設為T6(℃)，測定各溫度T5、T6。且上述溫度T1~T6係使用耐熱型非接觸溫度感測器(IRtec Rayomatic 14，YIH TROUN(股)製)，自於各區域內搬送之薄膜下方150mm之位置測定薄膜側之溫度而獲得。 The temperature T1 (°C) on the retard side and the temperature T2 (°C) on the leading side in the first temperature distribution are measured at two points on the inner side of the railway having a railway width (railway interval) × 5%, that is, extending through the inclined surface. The temperature at the two points on the line of the end positions P and Q is measured as the temperature T1 and the temperature T2, respectively. Further, the temperature T3 (°C) on the leading side and the temperature T4 (°C) on the retard side in the second temperature distribution are measured at two points passing through the inner side of the railway having only the railway width × 5%, that is, passing through the intermediate point M3. At the two-point temperature in the width direction, the measured front side and retard side temperatures are respectively set to temperature T3 and temperature T4. Further, the temperature of the first position M1 of the slope extending region Z2-2 is T5 (°C), and the temperature of the intermediate point M3 of the relaxation region Z3 is T6 (°C), and the respective temperatures T5 and T6 are measured. Further, the temperature T1 to T6 were obtained by measuring the temperature of the film side from a position 150 mm below the film conveyed in each region using a heat-resistant non-contact temperature sensor (IRtec Rayomatic 14, manufactured by YIH TROUN Co., Ltd.).

又，若舉溫度T1~T6之一例，則實施例1之斜面延伸薄膜之製造中，T1=200.5℃，T2=199.5℃，T3=197.5℃，T4=192.5℃，T5=200℃，T6=195℃。且其他實施例及比較例中，以如表1所示之溫度差控制延伸部5之各區域溫度。又，預熱區域Z1及橫延伸區域Z2-1之溫度相同且斜面延伸區域Z2-2之延遲側之溫度T1大致相同。 Further, in the case of one of the temperatures T1 to T6, in the manufacture of the bevel stretch film of Example 1, T1 = 200.5 ° C, T2 = 199.5 ° C, T3 = 197.5 ° C, T4 = 192.5 ° C, T5 = 200 ° C, T6 = 195 ° C. In the other examples and comparative examples, the temperature of each region of the extending portion 5 was controlled by the temperature difference as shown in Table 1. Further, the temperatures of the preheating zone Z1 and the lateral extension zone Z2-1 are the same and the temperature T1 of the retard side of the bevel extension zone Z2-2 is substantially the same.

[評價] [Evaluation] (膜厚偏差之評價) (Evaluation of film thickness deviation)

針對以表1之溫度條件製造之各斜面延伸薄膜，使用電子厚度計(Digimatic Thickness Gage)(Mitutoyo製)，於寬度方向以100mm間隔測定膜厚。而且，此膜厚測定於薄膜搬送方向(長度方向)每50m進行5次，求出上述所有數據(厚度值)之最大值與最小值之差作為膜厚偏差(μm)，基於以下基準評價膜厚偏差。 The film thickness was measured at intervals of 100 mm in the width direction using an electronic thickness meter (Digimatic Thickness Gage) (manufactured by Mitutoyo) for each of the beveled stretched films produced under the temperature conditions of Table 1. In addition, the film thickness was measured five times per 50 m in the film transport direction (longitudinal direction), and the difference between the maximum value and the minimum value of all the above data (thickness values) was determined as the film thickness deviation (μm), and the film was evaluated based on the following criteria. Thick deviation.

《評價基準》 Evaluation Benchmark

◎：膜厚偏差大於0μm且0.5μm以下。 ◎: The film thickness deviation is more than 0 μm and 0.5 μm or less.

○：膜厚偏差大於0.5μm且1.0μm以下。 ○: The film thickness deviation was more than 0.5 μm and 1.0 μm or less.

×：膜厚偏差大於1.0μm且1.5μm以下。 ×: The film thickness deviation is more than 1.0 μm and 1.5 μm or less.

××：膜厚偏差大於1.5μm。 ××: The film thickness deviation is more than 1.5 μm.

(皺褶評價) (wrinkle evaluation)

目視觀察以表1之溫度條件製造之各斜面延伸薄膜，基於以下之評價基準評價有無條狀皺褶(表面凹凸不平)。 Each of the bevel-stretched films produced under the temperature conditions of Table 1 was visually observed, and the presence or absence of strip wrinkles (surface irregularities) was evaluated based on the following evaluation criteria.

《評價基準》 Evaluation Benchmark

○：幾乎未觀察到皺褶。 ○: Wrinkles were hardly observed.

△：雖觀察到微小皺褶，但為實際使用尚無問題之程度。 △: Although minute wrinkles were observed, there was no problem in practical use.

×：觀察到實際使用時成為問題之大皺褶。 ×: A large wrinkle which became a problem in actual use was observed.

表1顯示針對各斜面延伸薄膜之評價結果。 Table 1 shows the evaluation results for the respective bevel stretched films.

表1之實施例1~13之斜面延伸薄膜，獲得膜厚偏差之評價為○或◎之良好結果。此認為係因為實施例1~13之斜面延伸薄膜之製造中，滿足1℃≦(T1-T2)≦15℃、5℃≦(T3-T4)≦30℃、5℃≦(T5-T6)≦40℃之故。亦即認為是因為，藉由滿足上述溫度條件，藉由於斜面延伸區域Z2-2之斜面延伸，儘管於延遲側膜厚較薄，先行側之膜厚較厚，於緩和區域Z3之先行側，亦可促進殘留應力緩和且減少膜厚，藉此，可使薄膜寬度方向之膜厚差減小。又，實施例1~13之斜面延伸薄膜，皺褶之評價亦為△或○而良好，此認為係因為於緩和區域Z3中殘留應力於寬度方向被適當緩和之結果，而抑制起因於殘留應力之皺褶發生。 The bevel-stretched film of Examples 1 to 13 of Table 1 was evaluated as a good result of evaluation of film thickness deviation of ○ or ◎. This is considered to be due to the 1°C≦(T1-T2)≦15°C, 5°C≦(T3-T4)≦30°C, 5°C≦(T5-T6) in the manufacture of the beveled stretch film of Examples 1-13. ≦ 40 ° C. That is, it is considered that, by satisfying the above temperature condition, the slope of the inclined surface extending region Z2-2 is extended, and although the film thickness on the retard side is thin, the film thickness on the leading side is thicker, on the leading side of the relaxation region Z3, It is also possible to promote the relaxation of the residual stress and reduce the film thickness, whereby the film thickness difference in the film width direction can be reduced. Further, in the beveled stretched films of Examples 1 to 13, the evaluation of the wrinkles was also good for Δ or ○, and it is considered that the residual stress in the relaxation region Z3 was appropriately moderated in the width direction, and the residual stress was suppressed. The wrinkles occur.

相對於此，比較例1~5之斜面延伸薄膜之膜厚偏差評價為×或××。此認為是因為比較例1~5之斜面延伸薄膜之製造中，並未滿足1℃≦(T1-T2)≦15℃、5℃≦(T3-T4)≦30℃、5℃≦(T5-T6)≦40℃之任一條件，而為使寬度方向膜厚偏差變小，於緩和區域Z3殘留應力並未緩和，或相反地殘留應力過度緩和，而產生膜厚偏差。尤其，比較例1之斜面延伸薄膜中，認為殘留應力未適當緩和之結果，而產生起因於殘留應力之皺褶。 On the other hand, the film thickness deviation of the beveled stretch film of Comparative Examples 1 to 5 was evaluated as × or ××. This is considered to be because the production of the beveled stretch film of Comparative Examples 1 to 5 did not satisfy 1 ° C (T1-T2) ≦ 15 ° C, 5 ° C ≦ (T3-T4) ≦ 30 ° C, 5 ° C ≦ (T5- T6) ≦ 40 ° C, in order to reduce the film thickness deviation in the width direction, the residual stress in the relaxation region Z3 is not alleviated, or conversely, the residual stress is excessively relaxed, and the film thickness variation occurs. In particular, in the bevel stretch film of Comparative Example 1, it was considered that the residual stress was not moderately relaxed, and wrinkles due to residual stress were caused.

又，由實施例11、12之結果，可說是即使膜厚較薄，藉由於斜面延伸區域Z2-2及緩和區域Z3中適當溫度控制，亦可減低膜厚偏差及皺褶發生。 Further, as a result of the examples 11 and 12, it can be said that even if the film thickness is thin, the film thickness variation and the occurrence of wrinkles can be reduced by appropriate temperature control in the slope extending region Z2-2 and the relaxation region Z3.

又，由實施例13之結果，可說是即使延伸倍 率產生變化，藉由於斜面延伸區域Z2-2及緩和區域Z3中適當溫度控制，亦可減低膜厚偏差及皺褶發生。又，延伸倍率為1.4倍之比較例5與延伸倍率為1.2倍之比較例4同樣，認為由於未滿足5℃≦(T5-T6)≦40℃，故產生膜厚偏差。 Moreover, the result of the embodiment 13 can be said to be even the extension The rate changes, and the film thickness deviation and wrinkle occurrence can also be reduced by proper temperature control in the slope extension zone Z2-2 and the relaxation zone Z3. Further, in Comparative Example 5 in which the stretching ratio was 1.4 times, as in Comparative Example 4 in which the stretching ratio was 1.2 times, it was considered that the film thickness variation occurred because 5 ° C (T5 - T6) ≦ 40 ° C was not satisfied.

如以上，實施例1~13之斜面延伸薄膜之製造中，即使使用寬度方向膜厚均一之坯片薄膜進行斜面延伸，亦可製造寬度方向膜厚大致均一之斜面延伸薄膜，故作為坯片薄膜，並無必要製造且事先準備於寬度方向使膜厚變化之特殊薄膜。其結果，可提高斜面延伸薄膜之生產性。而且，由於亦可減低起因於殘留應力之皺褶發生，故可減低皺褶發生且提高斜面延伸薄膜之生產性。 As described above, in the manufacture of the beveled stretched films of Examples 1 to 13, even if the green sheet film having a uniform film thickness in the width direction is inclined to be stretched, a beveled film having a substantially uniform film thickness in the width direction can be produced, so that it is used as a green film. There is no need to manufacture and prepare a special film which changes the film thickness in the width direction. As a result, the productivity of the bevel stretch film can be improved. Moreover, since the occurrence of wrinkles due to residual stress can be reduced, the occurrence of wrinkles can be reduced and the productivity of the bevel stretched film can be improved.

又，以上，可知斜面延伸區域Z2-2中形成之第1溫度分佈設為以圖4所示之直線a1之分佈，但即使為其他之曲線a2、a3所示之分佈，藉由適當設定T1-T2，亦可獲得與實施例1~13同樣之結果。因此可說是，斜面延伸區域Z2-2中形成之第1溫度分佈只要為自延遲側至先行側，溫度單調減少之分佈即可。 Further, as described above, it is understood that the first temperature distribution formed in the slope extending region Z2-2 is a distribution of the straight line a1 shown in FIG. 4, but the distribution shown by the other curves a2 and a3 is appropriately set by T1. -T2, the same results as in Examples 1 to 13 were also obtained. Therefore, it can be said that the first temperature distribution formed in the slope extending region Z2-2 may be a distribution in which the temperature monotonously decreases as long as it is from the retard side to the leading side.

又，以上，可知緩和區域Z3中形成之第2溫度分佈設為以圖5所示之直線b1之分佈，但即使為其他之曲線b2、b3所示之分佈，藉由適當設定T3-T4，亦可獲得與實施例1~13同樣之結果。因此可說是，緩和區域Z3中形成之第2溫度分佈只要為自延遲側至先行側，溫度單調增加之分佈即可。 In addition, as described above, it is understood that the second temperature distribution formed in the relaxation region Z3 is a distribution of the straight line b1 shown in FIG. 5. However, even if the distribution shown by the other curves b2 and b3 is set as appropriate, T3-T4 is set. The same results as in Examples 1 to 13 were also obtained. Therefore, it can be said that the second temperature distribution formed in the relaxation zone Z3 may be a distribution in which the temperature monotonously increases as long as it is from the retard side to the leading side.

又，以上係針對使薄膜配向角成為約45°之方式進行斜面延伸之例加以說明，但可知即使薄膜配向角成為30°或60°之方式進行斜面延伸之情況，藉由與實施例1~13同樣之溫度控制，亦可獲得與實施例1~13同樣之結果。 Further, although the above description has been made on the case where the film has an oblique angle extending so that the film alignment angle is about 45°, it is understood that the bevel is extended even if the film alignment angle is 30° or 60°, and the embodiment 1~ 13 The same results as in Examples 1 to 13 were obtained by the same temperature control.

且，以上針對使用纖維素酯系樹脂製造斜面延伸薄膜之情況加以說明，但可知使用COP或PC等之纖維素酯系樹脂以外之樹脂，藉由與實施例1~13同樣之溫度控制製造斜面延伸薄膜，亦可獲得與實施例1~13同樣之結果。 In the above, the case of producing a beveled stretched film using a cellulose ester-based resin will be described. However, it is known that a resin other than the cellulose ester-based resin such as COP or PC is used to produce a bevel at the same temperature as in Examples 1 to 13. The same results as in Examples 1 to 13 were obtained by stretching the film.

以上說明之本實施形態之斜面延伸薄膜之製造方法可如以下表現。 The method for producing the bevel stretch film of the present embodiment described above can be expressed as follows.

1.一種斜面延伸薄膜之製造方法，其特徵為具有斜面延伸步驟，其係以一對把持具把持薄膜寬度方向之兩端而搬送前述薄膜，同時於斜面延伸區域使前述薄膜之搬送方向於中途改變，藉由使一把持具相對先行，並使另一把持具相對延遲，使前述薄膜對於寬度方向往斜面方向延伸，且於前述斜面延伸步驟結束後，進一步具有緩和步驟，其係於前述薄膜之搬送方向固定之緩和區域，使斜面延伸產生之前述薄膜之殘留應力緩和；於前述薄膜之寬度方向中，將斜面延伸時使前述一對把持具之一者先行而行走之側設為先行側，將另一者延遲行走之側設為延遲側時， 前述斜面延伸區域中，於前述先行側與前述延遲側之間，以使前述先行側之溫度比前述延遲側之溫度低1~15℃之方式形成第1溫度分佈， 於前述緩和區域中，於前述先行側與前述延遲側之間，以前述先行側之溫度比前述延遲側之溫度高5~30℃之方式形成第2溫度分佈， 前述斜面延伸區域之溫度比前述緩和區域之溫度高5~40℃。 A method for producing a beveled stretched film, characterized by comprising a bevel extending step of transporting the film by gripping both ends of the film in the width direction of the pair of grippers, and moving the film in the middle of the bevel extending region Changing, the film is stretched in the direction of the width direction by the relative advance of the holder, and the other holder is relatively delayed, and further has a relaxation step after the step of extending the slope, which is attached to the film The mitigation region in which the conveying direction is fixed is used to relax the residual stress of the film caused by the slanting surface extension; in the width direction of the film, when the slanting surface is extended, the side on which one of the pair of holding tools is advanced is set as the leading side When the other side of the delayed walking is set as the delay side, In the inclined surface extending region, a first temperature distribution is formed between the leading side and the retard side such that the temperature of the leading side is lower than the temperature of the retard side by 1 to 15 ° C. In the tempered region, a second temperature distribution is formed between the preceding side and the retard side such that the temperature on the preceding side is 5 to 30 ° C higher than the temperature on the retard side. The temperature of the inclined surface extending region is 5 to 40 ° C higher than the temperature of the relaxation region.

2.如前述1之斜面延伸薄膜之製造方法，其中於前述斜面延伸區域，於前述一對把持具分別到達斜面延伸結束位置時之連結前述一對把持具之方向，形成前述第1溫度分佈。 2. The method for producing a beveled stretch film according to the above aspect, wherein the first temperature distribution is formed in a direction in which the pair of grippers are connected to each of the pair of grippers when the pair of grippers reach a position where the pair of grippers extend to the inclined surface extending region.

3.如前述2之斜面延伸薄膜之製造方法，其中於前述緩和區域，於通過該緩和區域之中間點且垂直於前述搬送方向之寬度方向，形成前述第2溫度分佈， 前述中間點係連結第1位置與第2位置之區間之中間位置，該第1位置係在前述延伸區域於前述一對把持具分別到達斜面延伸結束位置時之連結前述一對把持具之區間之中間，前述第2位置係前述緩和區域之出口之寬度方向之中間。 3. The method for producing a bevel-stretched film according to the above 2, wherein the second temperature distribution is formed in the relaxation region at a midpoint passing through the intermediate portion of the relaxation region and perpendicular to the transport direction. The intermediate point is connected to a middle position between the first position and the second position, and the first position is a section connecting the pair of grippers when the pair of grippers reach the end position of the slope extension in the extension region In the middle, the second position is in the middle of the width direction of the exit of the relaxation region.

4.如前述1至3中任一項之斜面延伸薄膜之製造方法，其中前述斜面延伸區域之溫度係於前述一對把持具分別到達斜面延伸結束位置時之連結前述一對把持具之區間之中間的第1位置之溫度， 前述緩和區域之溫度係連結前述第1位置與前述緩和區域之出口之寬度方向之中間的第2位置之區間的中間之第3位置之溫度， 前述第1溫度比前述第3溫度高5~40℃。 4. The method of manufacturing a beveled stretch film according to any one of the above 1 to 3, wherein the temperature of the slope extending region is a section connecting the pair of grippers when the pair of grippers respectively reach a position at which the inclined surface extends. The temperature at the first position in the middle, The temperature of the relaxation region is a temperature at a third position intermediate the interval between the first position and the second position in the width direction of the outlet of the relaxation region, The first temperature is 5 to 40 ° C higher than the third temperature.

5.如前述1至4中任一項之斜面延伸薄膜之製造方法，其中前述第1分佈溫度係自前述延遲側朝向前述先行側，溫度單調減少之分佈。 5. The method of producing a bevel-stretched film according to any one of the above 1 to 4, wherein the first distribution temperature is a monotonously decreasing distribution of temperature from the retardation side toward the preceding side.

6.如前述1至5中任一項之斜面延伸薄膜之製造方法，其中前述第2分佈溫度係自前述延遲側朝向前述先行側，溫度單調增加之分佈。 6. The method for producing a bevel stretched film according to any one of the above 1 to 5, wherein the second distribution temperature is a monotonously increasing distribution of temperature from the retard side toward the preceding side.

7.如上述1至6中任一項之斜面延伸薄膜之製造方法，其中前述斜面延伸區域係以使相對於前述薄膜之寬度方向，慢軸成為約45°之角度之方式，使前述薄膜於斜面方向延伸。 7. The method for producing a beveled stretched film according to any one of the above 1 to 6, wherein the inclined surface extending region is such that the film is at an angle of about 45° with respect to a width direction of the film. It extends in the direction of the slope.

[產業上之可利用性] [Industrial availability]

本發明之斜面延伸薄膜之製造方法可利用於製造應用於例如有機EL圖像顯示裝置或液晶顯示裝置之λ/4薄膜。 The method for producing a beveled stretched film of the present invention can be utilized for producing a λ/4 film applied to, for example, an organic EL image display device or a liquid crystal display device.

Claims (7)

一種斜面延伸薄膜之製造方法，其特徵為具有斜面延伸步驟，其係以一對把持具把持薄膜寬度方向之兩端而搬送前述薄膜，同時於斜面延伸區域使前述薄膜之搬送方向於中途改變，藉由使一把持具相對先行，並使另一把持具相對延遲，使前述薄膜對於寬度方向往斜面方向延伸，且於前述斜面延伸步驟結束後，進一步具有緩和步驟，其係於前述薄膜搬送方向固定之緩和區域，使斜面延伸產生之前述薄膜殘留應力緩和；於前述薄膜之寬度方向中，將斜面延伸時使前述一對把持具之一者先行而行走之側設為先行側，將另一者延遲行走之側設為延遲側時，前述斜面延伸區域中，於前述先行側與前述延遲側之間，以使前述先行側之溫度比前述延遲側之溫度低1~15℃之方式形成第1溫度分佈，於前述緩和區域中，於前述先行側與前述延遲側之間，以前述先行側之溫度比前述延遲側之溫度高5~30℃之方式形成第2溫度分佈，前述斜面延伸區域之溫度比前述緩和區域之溫度高5~40℃。 A method for producing a beveled stretched film, characterized by having a bevel extending step of transporting the film by gripping both ends of the film in the width direction of the pair of grippers, and changing the conveying direction of the film in the middle of the inclined surface. The film is extended in the direction of the slope direction by the relative advance of the holder, and the other holder is relatively delayed, and after the step of extending the slope, the step of stretching is further performed in the film transport direction. The mitigating region of the fixing causes the film residual stress generated by the slanting surface to be relaxed; in the width direction of the film, when the slanting surface is extended, one side of the pair of holding tools is advanced and the side walking is set as the leading side, and the other side is When the side on which the delay travel is the retard side, the slope extending region is formed between the preceding side and the retard side such that the temperature of the preceding side is lower by 1 to 15 ° C than the temperature of the retard side. a temperature distribution in the mitigation region between the preceding side and the retard side, and the preceding side The ratio of the high temperature-side delay 5 ~ 30 ℃ the second temperature profile is formed, the inclined surface area stretching temperature higher than the temperature of the relaxation region 5 ~ 40 ℃. 如請求項1之斜面延伸薄膜之製造方法，其中於前述斜面延伸區域，於前述一對把持具分別到達斜面延伸結束位置時之連結前述一對把持具之方向，形成前述第1 溫度分佈。 The method of manufacturing a beveled stretch film according to claim 1, wherein in the inclined surface extending region, the first pair of grippers are connected to each other in a direction in which the pair of grippers extend to a position at which the pair of grippers extend to form the first Temperature Distribution. 如請求項1之斜面延伸薄膜之製造方法，其中於前述緩和區域，於通過該緩和區域之中間點且垂直於前述搬送方向之寬度方向，形成前述第2溫度分佈，前述中間點係連結第1位置與第2位置之區間之中間位置，該第1位置係在前述延伸區域於前述一對把持具分別到達斜面延伸結束位置時之連結前述一對把持具之區間之中間，前述第2位置係前述緩和區域之出口之寬度方向之中間。 The method for producing a beveled stretched film according to claim 1, wherein the second temperature distribution is formed in a width direction of an intermediate portion passing through the relaxation region and perpendicular to the transport direction in the relaxation region, and the intermediate point is connected to the first a position intermediate the position and the second position, wherein the first position is in a middle of a section connecting the pair of grippers when the pair of grippers respectively reach a position where the pair of grippers extend to the end position of the pair of grippers, and the second position is The middle of the width direction of the exit of the aforementioned relaxation zone. 如請求項1之斜面延伸薄膜之製造方法，其中前述斜面延伸區域之溫度係於前述一對把持具分別到達斜面延伸結束位置時之連結前述一對把持具之區間之中間的第1位置之溫度，前述緩和區域之溫度係連結前述第1位置與前述緩和區域之出口之寬度方向之中間的第2位置之區間的中間之第3位置之溫度，前述第1溫度比前述第3溫度高5~40℃。 The method for manufacturing a beveled stretched film according to claim 1, wherein the temperature of the inclined surface extending region is a temperature at a first position in a middle of a section connecting the pair of gripping members when the pair of gripping members respectively reach a position at which the inclined surface extends The temperature of the relaxation region is a temperature at a third position in the middle of a section between the first position and the second position in the width direction of the outlet of the relaxation region, and the first temperature is higher than the third temperature by 5~ 40 ° C. 如請求項1之斜面延伸薄膜之製造方法，其中前述第1分佈溫度係自前述延遲側朝向前述先行側，溫度單調減少之分佈。 The method for producing a bevel-stretched film according to claim 1, wherein the first distribution temperature is a monotonously decreasing distribution of temperature from the retardation side toward the preceding side. 如請求項1之斜面延伸薄膜之製造方法，其中前述第2分佈溫度係自前述延遲側朝向前述先行側，溫度單調增加之分佈。 The method for producing a bevel-stretched film according to claim 1, wherein the second distribution temperature is a monotonously increasing temperature distribution from the retard side toward the preceding side. 如請求項1至6中任一項之斜面延伸薄膜之製造 方法，其中前述斜面延伸區域係以使相對於前述薄膜之寬度方向，慢軸成為約45°之角度之方式，使前述薄膜於斜面方向延伸。 Manufacture of a beveled stretch film according to any one of claims 1 to 6 In the method, the inclined surface extending region is such that the film extends in a slope direction so that the slow axis is at an angle of about 45 with respect to the width direction of the film.
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