TWI659052B - Film, dope composition and production method thereof, and solution casting method - Google Patents

Film, dope composition and production method thereof, and solution casting method Download PDF

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TWI659052B
TWI659052B TW104106321A TW104106321A TWI659052B TW I659052 B TWI659052 B TW I659052B TW 104106321 A TW104106321 A TW 104106321A TW 104106321 A TW104106321 A TW 104106321A TW I659052 B TWI659052 B TW I659052B
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film
fine particles
dope
polymer
solvent
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TW201534641A (en
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継枝愛
池山昭弘
鷲谷公人
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日商富士軟片股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B01F23/57—Mixing high-viscosity liquids with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F31/00—Mixers with shaking, oscillating, or vibrating mechanisms
    • B01F31/80—Mixing by means of high-frequency vibrations above one kHz, e.g. ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Dispersion Chemistry (AREA)
  • Moulding By Coating Moulds (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

本發明提供一種重疊時的貼附得以減少之薄膜、用於製造該薄膜之濃液組成物及其製造方法、以及製造薄膜之溶液製膜方法。本發明的薄膜在由聚合物形成之薄膜面上形成有包含微粒之高度為30nm以上的突起。該高度為30nm以上的突起的密度在104個/mm2以上106個/mm2以下的範圍內。該些突起妨礙在重疊之薄膜中相對向之兩個薄膜面的局部相互直接接觸。藉此，可以減少薄膜重疊時的貼附。 The present invention provides a thin film with reduced adhesion during overlap, a dope composition for manufacturing the thin film, a manufacturing method thereof, and a solution film-forming method for manufacturing the thin film. In the film of the present invention, protrusions having a height of 30 nm or more including fine particles are formed on a film surface made of a polymer. The density of the protrusions having a height of 30 nm or more is in a range of 10 4 / mm 2 or more and 10 6 / mm 2 or less. These protrusions prevent parts of two opposite film faces in the overlapping films from directly contacting each other. This makes it possible to reduce sticking when the films are overlapped.

Description

薄膜、濃液組成物及其製造方法、以及溶液製膜方法 Thin film, dope composition, manufacturing method thereof, and solution film forming method

本發明係有關一種薄膜、用於製造該薄膜之濃液組成物及其製造方法、以及製造薄膜之溶液製膜方法。 The invention relates to a thin film, a dope composition for manufacturing the thin film, a manufacturing method thereof, and a solution film-forming method for manufacturing the thin film.

聚合物薄膜(以下稱為薄膜)作為偏光板的保護膜、相位差膜、防反射膜、透明導電性膜等光學膜被廣泛地利用。 Polymer films (hereinafter referred to as thin films) are widely used as optical films such as protective films for polarizing plates, retardation films, anti-reflection films, and transparent conductive films.

薄膜一般以長形製造，作為製造方法，有溶液製膜方法。溶液製膜方法例如為如下方法：藉由流延模，使聚合物溶於溶劑之溶液(以下稱為濃液)在支撐體的表面上連續流延來形成帶狀的流延膜，並從支撐體剝取後進行乾燥。長形的薄膜捲取於卷芯並以卷狀進行保存。 The thin film is generally manufactured in a long shape. As a manufacturing method, there is a solution film forming method. The solution film forming method is, for example, a method in which a solution in which a polymer is dissolved in a solvent (hereinafter referred to as a dope) is continuously cast on the surface of a support by a casting die, and a tape-shaped casting film is formed from The support is peeled and dried. The long film is taken up on a roll core and stored in a roll shape.

若捲取長形的薄膜，則重疊部份有時會彼此貼附。作為防止貼附的對策，如日本專利公開2006-028251號公報所記載，有如下薄膜：添加微粒，將具有設定為2~20nm的平均突起高度的2倍以上高度的突起的數量設在總突起數量的1.0×10-6以上1.0×10-2以下的範圍內。 When a long film is wound up, the overlapped parts sometimes adhere to each other. As a countermeasure against sticking, as described in Japanese Patent Laid-Open No. 2006-028251, there is a thin film in which fine particles are added, and the number of protrusions having a height that is twice or more the average protrusion height set to 2 to 20 nm is set to the total protrusions. The number ranges from 1.0 × 10 -6 to 1.0 × 10 -2 .

但是，若捲取日本專利公開2006-028251號公報的薄膜，則重疊部份實際上會以一定的概率彼此貼附。尤其，在捲取長形的薄膜時，接觸面壓施加於薄膜的重疊部份之間，因此薄膜的重疊部份以更高的概率彼此貼附。並且，若較薄地製造薄膜、或者較長地製造薄膜、或者製造彈性模量較低的薄膜，則以更高的概率貼附。如此，因過大的壓力施加於薄膜的表面等原因而導致重疊之薄膜彼此貼附，該現象還被稱作黏連(blocking)。並且，由於這種貼附，在捲取成卷狀之薄膜卷上產生被稱作“凹部”之沿周方向的凹陷，且在捲取之薄膜上產生折皺等。 However, when the film of Japanese Patent Laid-Open No. 2006-028251 is wound, the overlapping portions are actually attached to each other with a certain probability. In particular, when the long film is wound, the contact surface pressure is applied between the overlapping portions of the film, so the overlapping portions of the film are attached to each other with a higher probability. In addition, if a thin film is produced, a film is made longer, or a film having a low elastic modulus is produced, the film is attached with a higher probability. As such, overlapping films are attached to each other due to excessive pressure applied to the surface of the film, and this phenomenon is also referred to as blocking. In addition, due to such attachment, a depression in a circumferential direction called a “recess” is generated in a rolled film roll, and wrinkles and the like are generated in the rolled film.

因此，本發明的目的為提供一種重疊時的貼附得以減少之薄膜、用於製造該薄膜之濃液組成物及其製造方法、以及製造薄膜之溶液製膜方法。 Therefore, an object of the present invention is to provide a thin film with reduced adhesion during overlap, a dope composition for manufacturing the thin film, a manufacturing method thereof, and a solution film forming method for manufacturing a thin film.

本發明的薄膜具備：薄膜面，由聚合物形成；及突起，形成於該薄膜面上且高度為30nm以上。突起包含微粒。在薄膜面上每1mm2面積內，以104個以上106個以下的範圍形成有突起。 The film of the present invention includes a film surface formed of a polymer, and protrusions formed on the film surface and having a height of 30 nm or more. The protrusions contain particles. Protrusions are formed in a range of 10 4 or more and 10 6 or less per 1 mm 2 of the film surface.

聚合物為纖維素醯化物為較佳。 It is preferred that the polymer is a cellulose halide.

在薄膜面上每1mm2面積內，以104個以上106個以下的範圍形成有將薄膜面皂化處理之後的突起為較佳。 It is preferable that protrusions after saponifying the film surface are formed in a range of 10 4 or more and 10 6 or less per 1 mm 2 of the film surface.

將偏光膜黏接於皂化處理之後的前述薄膜面來進行使用為較佳。 The polarizing film is preferably adhered to the aforementioned film surface after the saponification treatment and used.

微粒為二氧化矽為較佳。 More preferably, the particles are silicon dioxide.

本發明的濃液組成物具備：聚合物；溶劑，溶解該聚合物；及微粒，以二次粒子的狀態分散。二次粒徑為0.7μm以上的微粒相對於微粒總數之含有比例至少為30%。 The dope composition of the present invention includes: a polymer; a solvent, which dissolves the polymer; and fine particles, which are dispersed in a state of secondary particles. The content ratio of the particles having a secondary particle diameter of 0.7 μm or more to the total number of particles is at least 30%.

本發明的濃液組成物的製造方法具備原料濃液調製步驟(A步驟)、混合物調製步驟(B步驟)、微粒分散步驟(C步驟)及混合步驟(D步驟)。在A步驟中，將聚合物和溶劑進行混合，並藉由加熱和攪拌中的至少一方，將前述聚合物溶解於前述溶劑來製作原料濃液。在B步驟中，將與上述聚合物及上述溶劑相同成份之聚合物及溶劑和微粒進行混合並攪拌來得到液態的混合物。在C步驟中，使微粒在混合物中作為二次粒子而分散，從而得到微粒分散液。在微粒分散液中，0.7μm以上的二次粒徑的微粒相對於微粒總數之含有比例至少為30%。在D步驟中，將原料濃液和微粒分散液進行混合來得到濃液組成物。 The method for producing a dope composition of the present invention includes a raw material dope preparation step (step A), a mixture preparation step (step B), a fine particle dispersion step (step C), and a mixing step (step D). In step A, the polymer and the solvent are mixed, and the polymer is dissolved in the solvent by at least one of heating and stirring to prepare a raw material dope. In step B, a polymer having the same composition as the polymer and the solvent, a solvent, and fine particles are mixed and stirred to obtain a liquid mixture. In step C, the fine particles are dispersed as secondary particles in the mixture to obtain a fine particle dispersion. In the fine particle dispersion liquid, the content ratio of the fine particles having a secondary particle size of 0.7 μm or more to the total number of fine particles is at least 30%. In step D, the raw material dope and the microparticle dispersion are mixed to obtain a dope composition.

在C步驟中，藉由對混合物施加超音波、或者藉由使用球磨機來使微粒在混合物中作為二次粒子而分散為較佳。 In step C, it is preferable to disperse the fine particles as secondary particles in the mixture by applying an ultrasonic wave to the mixture or by using a ball mill.

本發明的溶液製膜方法具備上述A步驟、上述B步驟、上述C步驟、上述D步驟、流延膜形成步驟(E步驟)及剝取乾燥步驟(F 步驟)。在E步驟中，藉由從流延模向連續行走之支撐體上連續吐出濃液組成物來在支撐體上形成流延膜。在F步驟中，藉由從支撐體剝下流延膜並進行乾燥來得到薄膜。 The solution film forming method of the present invention includes the A step, the B step, the C step, the D step, a cast film forming step (E step), and a peeling and drying step (F step). In step E, a casting film is formed on the support body by continuously ejecting the dope composition from the casting die to the support body that continuously walks. In step F, the cast film is peeled from the support and dried to obtain a film.

依本發明，可以減少薄膜的重疊部份的彼此貼附。因此，可以抑制薄膜卷上之被稱作凹部之沿周方向的凹陷、及捲取之薄膜上之折皺等的產生。 According to the present invention, it is possible to reduce the adhesion of overlapping portions of the film to each other. Therefore, it is possible to suppress the occurrence of depressions in the circumferential direction called recesses on the film roll, and wrinkles on the wound film.

10‧‧‧薄膜 10‧‧‧ film

10a‧‧‧薄膜面 10a‧‧‧ film surface

12‧‧‧薄膜主體 12‧‧‧ film body

13‧‧‧表層 13‧‧‧ surface

14、14a、14b‧‧‧微粒 14, 14a, 14b ‧‧‧ particles

15、15a、15b‧‧‧突起 15, 15a, 15b ‧‧‧ protruding

17‧‧‧偏光膜 17‧‧‧ polarizing film

20‧‧‧偏光板 20‧‧‧ polarizing plate

20a‧‧‧偏光板的表面 20a‧‧‧ surface of polarizing plate

30‧‧‧溶液製膜設備 30‧‧‧Solution film forming equipment

31‧‧‧濃液調製裝置 31‧‧‧Concentrated liquid preparation device

32‧‧‧流延裝置 32‧‧‧casting device

35‧‧‧拉幅機 35‧‧‧Stenter

36‧‧‧輥乾燥裝置 36‧‧‧ roller drying device

37‧‧‧捲取裝置 37‧‧‧ Take-up device

41‧‧‧第1濃液 41‧‧‧The first concentrated solution

42‧‧‧第2濃液 42‧‧‧ 2nd concentrated solution

43‧‧‧溶解部 43‧‧‧Solution Department

46‧‧‧混合部 46‧‧‧ Mixing Department

47‧‧‧分散部 47‧‧‧Scattered Department

48、49‧‧‧過濾部 48, 49‧‧‧Filter Department

52‧‧‧纖維素醯化物 52‧‧‧cellulose trioxide

53‧‧‧溶劑 53‧‧‧ Solvent

54‧‧‧原料濃液 54‧‧‧ raw material concentrate

58‧‧‧微粒分散液 58‧‧‧ microparticle dispersion

59‧‧‧添加劑 59‧‧‧Additives

62‧‧‧傳送帶 62‧‧‧Conveyor

63‧‧‧第1輥 63‧‧‧Roll 1

64‧‧‧第2輥 64‧‧‧ 2nd roller

65‧‧‧流延模 65‧‧‧casting die

65a‧‧‧吐出口 65a‧‧‧Eject

66‧‧‧流延膜 66‧‧‧cast film

70‧‧‧剝取用的輥(剝取輥) 70‧‧‧ peeling roller (stripping roller)

71‧‧‧保持構件 71‧‧‧ holding member

72‧‧‧導管 72‧‧‧ Catheter

73‧‧‧輥 73‧‧‧roller

H15a、H15b‧‧‧高度 H15a, H15b ‧‧‧ height

T10、T12、T13‧‧‧厚度 T10, T12, T13‧‧‧thickness

圖1係表示本發明的一實施形態之薄膜的概要之剖面圖。 FIG. 1 is a cross-sectional view showing an outline of a film according to an embodiment of the present invention.

圖2係放大了圖1的薄膜的薄膜面附近之剖面圖。 FIG. 2 is an enlarged cross-sectional view near the film surface of the film of FIG. 1.

圖3係表示利用圖1的薄膜製作之偏光板的概要之剖面圖。 FIG. 3 is a cross-sectional view showing an outline of a polarizing plate produced using the film of FIG. 1.

圖4係放大了圖1的薄膜彼此重疊之部份和圖3的偏光板彼此重疊之部份之剖面概要圖。 FIG. 4 is an enlarged cross-sectional schematic view of a portion where the films of FIG. 1 overlap each other and a portion where the polarizers of FIG. 3 overlap each other.

圖5係表示溶液製膜設備的概要之說明圖。 FIG. 5 is an explanatory diagram showing an outline of a solution film forming apparatus.

圖6係表示二次粒徑為0.7μm以上的微粒相對於總微粒數量之含有比例與高度為30nm以上的突起的密度之間的相關性之說明圖。 FIG. 6 is an explanatory diagram showing the correlation between the content ratio of particles having a secondary particle size of 0.7 μm or more with respect to the total number of particles and the density of protrusions having a height of 30 nm or more.

圖7係與實驗1-D中製造之薄膜有關之AFM圖像。 Fig. 7 is an AFM image related to the film produced in Experiment 1-D.

圖8係對於圖7的AFM圖像，將與突起高度10nm對應之亮度作為閾值來進行二值化處理之後的圖像的一例。 FIG. 8 is an example of an image obtained by binarizing the AFM image of FIG. 7 with a luminance corresponding to a protrusion height of 10 nm as a threshold.

圖9係對於圖7的AFM圖像，將與突起高度30nm對應之亮度作為閾值來進行二值化處理之後的圖像的一例。 FIG. 9 is an example of an image obtained by binarizing the AFM image of FIG. 7 with a luminance corresponding to a protrusion height of 30 nm as a threshold.

圖10係表示高度為10nm以上的突起的密度與薄膜的貼附面積的比例之間的相關性之說明圖。 FIG. 10 is an explanatory diagram showing the correlation between the density of the protrusions having a height of 10 nm or more and the ratio of the adhesion area of the thin film.

圖11係表示高度為30nm以上的突起的密度與薄膜的貼附面積的比例之間的相關性之說明圖。 FIG. 11 is an explanatory diagram showing the correlation between the density of the protrusions having a height of 30 nm or more and the ratio of the adhesion area of the thin film.

圖12係表示高度為40nm以上的突起的密度與薄膜的貼附面積的比例之間的相關性之說明圖。 FIG. 12 is an explanatory diagram showing the correlation between the density of the protrusions having a height of 40 nm or more and the ratio of the adhesion area of the thin film.

圖13係表示高度為50nm以上的突起的密度與薄膜的貼附面積的比例 之間的相關性之說明圖。 FIG. 13 shows the ratio of the density of the protrusions to the area of the film to be attached with a height of 50 nm or more. An illustration of the correlation between them.

圖14係表示突起高度與突起對減少貼附的貢獻率之間的相關性之說明圖。 FIG. 14 is an explanatory diagram showing the correlation between the protrusion height and the contribution rate of the protrusion to the reduction of adhesion.

圖15係二次粒徑為0.7μm以上的微粒相對於總微粒數量之含有比例與貼附面積的比例之間的相關性之說明圖。 FIG. 15 is an explanatory diagram of the correlation between the content ratio of particles having a secondary particle diameter of 0.7 μm or more with respect to the total number of particles and the ratio of the attached area.

參閱圖1對本發明的實施形態之薄膜10進行說明。圖1所示之薄膜10具備薄膜主體12及配置於薄膜主體12的兩個面之表層13。薄膜主體12與表層13之間的邊界雖然係無法觀察者，但在圖1中，為了便於說明而圖示出它們的邊界。 A thin film 10 according to an embodiment of the present invention will be described with reference to FIG. 1. The film 10 shown in FIG. 1 includes a film main body 12 and a surface layer 13 disposed on both surfaces of the film main body 12. Although the boundary between the thin film body 12 and the surface layer 13 is not visible, in FIG. 1, the boundaries are illustrated for convenience of explanation.

薄膜主體12由纖維素醯化物和添加劑構成。一對表層13由相同的成份構成，具體而言，任何表層13均由纖維素醯化物、微粒14及添加劑構成，其比率亦相同。添加劑為增塑劑、紫外線吸收劑及控制薄膜10的延遲之延遲抑制劑等。在薄膜主體12和一對表層13中亦可以不包含添加劑。微粒14的表面被疏水基所包覆，係呈現二次粒子態樣之二氧化矽(silicon dioxide，SiO2)。另外，微粒14中可以與二氧化矽一同使用、或者代替二氧化矽而使用二氧化鈦、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、磷酸鈣等的微粒。微粒14的詳細內容將後述。 The film main body 12 is composed of a cellulose halide and an additive. The pair of surface layers 13 is composed of the same components. Specifically, any of the surface layers 13 is composed of cellulose trioxide, fine particles 14 and additives, and their ratios are also the same. The additives are a plasticizer, an ultraviolet absorber, a retardation inhibitor that controls retardation of the film 10, and the like. The film main body 12 and the pair of surface layers 13 may not contain additives. The surface of the microparticles 14 is covered with a hydrophobic group, and it shows silicon dioxide (SiO 2 ) in a secondary particle state. The microparticles 14 may be used together with silicon dioxide, or instead of silicon dioxide, titanium dioxide, aluminum oxide, zirconia, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, Particles of aluminum silicate, magnesium silicate, calcium phosphate, etc. The details of the fine particles 14 will be described later.

薄膜主體12的纖維素醯化物為三醋酸纖維素(Triacetyl Cellulose，TAC)，表層13的纖維素醯化物設為TAC。但是，薄膜主體12和表層13的各纖維素醯化物並不限定於此。例如，亦可以將薄膜主體12的纖維素醯化物設為二醋酸纖維素(Diacetyl Cellulose，DAC)，將表層13的纖維素醯化物設為TAC。並且，在本實施形態中，雖然將薄膜主體12和表層13的各聚合物成份均設為纖維素醯化物，但只要是能夠藉由溶液製膜方法來作成薄膜之聚合物即可。作為其他聚合物，例如有環狀聚烯烴、丙烯酸、聚對苯二甲酸乙二酯(Polyethylene Terephthalate，PET)等。 The cellulose halide of the film main body 12 is Triacetyl Cellulose (TAC), and the cellulose halide of the surface layer 13 is TAC. However, each cellulose halide of the film main body 12 and the surface layer 13 is not limited to this. For example, the cellulose halide of the film main body 12 may be a diacetyl cellulose (DAC), and the cellulose halide of the surface layer 13 may be TAC. In addition, in this embodiment, although each polymer component of the film main body 12 and the surface layer 13 is a cellulose halide, as long as it is a polymer capable of forming a film by a solution film-forming method. Examples of other polymers include cyclic polyolefins, acrylic acid, and polyethylene terephthalate (PET).

當由相同的成份構成兩個表層13時，成份的比率可以相互 不同。並且，可以是只有兩個表層13中的一方包含微粒之態樣。並且，可以設為由薄膜主體12構成之單層結構，而非設置兩個表層13，亦可以係該薄膜主體12由纖維素醯化物、添加劑及微粒14構成之態樣。 When the two surface layers 13 are composed of the same composition, the composition ratios can be made to each other different. In addition, only one of the two surface layers 13 may include particles. In addition, a single-layer structure composed of the film main body 12 may be used instead of providing two surface layers 13, or the film main body 12 may be composed of a cellulose halide, an additive, and fine particles 14.

薄膜10的厚度T10設為60μm，薄膜主體12的厚度T12設為54μm，表層13的厚度T13設為3μm。但是，各厚度並不限於此，只要厚度T10在10μm以上80μm以下的範圍內厚度T12在8μm以上75μm以下的範圍內，厚度T13在1μm以上10μm以下的範圍內即可。當厚度T10在15μm以上60μm以下的範圍內時，本發明的捲取薄膜10時減少重疊部份彼此的貼附之效果尤其大。厚度T10、T12、T13能夠藉由計算，依據後述第1濃液41(參閱圖5)和第2濃液42(參閱圖5)的各固形物的濃度和流向流延模65(參閱圖5)的量來求出。 The thickness T10 of the film 10 is set to 60 μm, the thickness T12 of the film body 12 is set to 54 μm, and the thickness T13 of the surface layer 13 is set to 3 μm. However, each thickness is not limited to this, as long as the thickness T10 is within a range of 10 μm to 80 μm, the thickness T12 is within a range of 8 μm to 75 μm, and the thickness T13 is within a range of 1 μm to 10 μm. When the thickness T10 is in the range of 15 μm to 60 μm, the effect of reducing the adhesion of the overlapping portions to each other when the rolled film 10 of the present invention is large is particularly great. The thicknesses T10, T12, and T13 can be calculated based on the concentration and flow direction of each solid matter in the first dope 41 (see FIG. 5) and the second dope 42 (see FIG. 5) and the casting direction 65 (see FIG. 5). ).

並且，當薄膜10係彈性模量為3.0GPa以下之低彈性模量薄膜時，減少薄膜10彼此的貼附之效果亦同樣較大。在此，由薄膜10製作2cm×15cm的樣品切片，並對該樣品切片進行拉伸試驗，藉此測定薄膜10的彈性模量。拉伸試驗例如使用Toyo Seiki Seisaku-Sho Ltd.製造之Strograph來進行。拉伸試驗的條件係把持樣品切片之兩個卡盤之間的距離為10cm，且十字頭的速度為200mm/分鐘。 In addition, when the film 10 is a low elastic modulus film having an elastic modulus of 3.0 GPa or less, the effect of reducing the adhesion between the films 10 is also large. Here, a sample slice of 2 cm × 15 cm is prepared from the film 10, and a tensile test is performed on the sample slice to measure the elastic modulus of the film 10. The tensile test is performed using, for example, a Strograph manufactured by Toyo Seiki Seisaku-Sho Ltd. The conditions of the tensile test are that the distance between the two chucks holding the sample section is 10 cm, and the speed of the crosshead is 200 mm / min.

薄膜10中的微粒14的一部份設置為從由作為聚合物成份之TAC形成之薄膜面10a突出一定高度以上，其中的每一個均發揮突起15之功能。例如，如圖2所示，微粒14a構成從薄膜面10a突出之高度為H15a的突起15a，微粒14b構成該高度為H15b的突起15b。在此，從薄膜面10a突出之高度H[單位：nm]定義為薄膜面10a與從薄膜面10a露出之部份的頂點之間的距離。另外，在第1、第2及圖4中，為了便於說明，示出了僅由微粒14形成者來作為突起15，但突起15的態樣並不限於此。突起15亦可以為以微粒14為基點而形成之任何態樣，例如可以由在微粒14中複合添加劑和纖維素醯化物而成者來形成。當突起15僅由微粒14形成時，決定高度H之頂點成為微粒14的頂點。當突起15由在微粒14中複合添加劑和纖維素醯化物而成者來形成時，決定高度H之頂點成為微粒的頂點、 添加劑的頂點、纖維素醯化物的頂點中最遠離薄膜面10a之頂點。 A part of the fine particles 14 in the film 10 is provided so as to protrude from a film surface 10 a formed of TAC as a polymer component by a certain height or more, and each of them functions as a protrusion 15. For example, as shown in FIG. 2, the fine particles 14 a constitute protrusions 15 a having a height of H15 a protruding from the film surface 10 a, and the fine particles 14 b constitute protrusions 15 b having a height of H15 b. Here, the height H [unit: nm] protruding from the film surface 10a is defined as the distance between the film surface 10a and the vertex of the portion exposed from the film surface 10a. In addition, in the first, second, and FIG. 4, for convenience of explanation, the protrusion 15 is shown only by the particles 14, but the aspect of the protrusion 15 is not limited to this. The protrusions 15 may be formed in any form using the microparticles 14 as a base point. For example, the protrusions 15 may be formed by compounding an additive and a cellulose halide in the microparticles 14. When the protrusion 15 is formed of only the particles 14, the vertex which determines the height H becomes the vertex of the particles 14. When the protrusions 15 are formed by compounding the additive and the cellulose halide in the fine particles 14, the vertex determining the height H becomes the apex of the fine particles, The apex of the additive and the apex of the cellulose halide are farthest from the apex of the film surface 10a.

藉由微粒14在薄膜面10a上設置複數個突起15，藉此在薄膜面10a上形成微小的凹凸，對薄膜面10a賦予一定的粗糙度。藉由該凹凸，即使薄膜10彼此重疊亦不會相互貼附，可以確保薄膜10彼此的滑動，從而顯現出一定的抗劃傷性。如此，微粒14發揮所謂的去光劑之功能。 The fine particles 14 are provided with a plurality of protrusions 15 on the film surface 10a, thereby forming minute irregularities on the film surface 10a, and imparting a certain roughness to the film surface 10a. By this unevenness, even if the films 10 overlap each other, they do not stick to each other, and it is possible to ensure the sliding of the films 10 to each other, thereby showing a certain scratch resistance. In this way, the fine particles 14 function as a so-called delustering agent.

當突起15的高度H為30nm以上時，與突起15的高度H小於30nm之情況相比，減少薄膜10彼此的貼附或者提高滑動性之效果較大。隨著突起15變高，減少貼附或者提高滑動性之效果增大，當突起15的高度H為40nm以上時，減少薄膜10彼此的貼附或者提高滑動性之效果進一步增大。並且，當突起15的高度H為100nm以下時，與高度H高於100nm之情況相比，薄膜10的霧度較低，因此為較佳。 When the height H of the protrusions 15 is 30 nm or more, compared with the case where the height H of the protrusions 15 is less than 30 nm, the effects of reducing the adhesion of the films 10 to each other or improving the sliding properties are greater. As the protrusions 15 become higher, the effect of reducing the attachment or improving the sliding property increases. When the height H of the protrusions 15 is 40 nm or more, the effect of reducing the attachment of the films 10 or improving the sliding property further increases. In addition, when the height H of the protrusions 15 is 100 nm or less, the haze of the thin film 10 is lower than that of the case where the height H is higher than 100 nm, and therefore, it is preferable.

將在薄膜面10a的每1mm2內存在之高度為H以上的突起15的個數設為突起密度D(H)[單位：個/mm2]。高度為30nm以上的突起密度D(30)在104個/mm2以上106個/mm2以下的範圍內。當高度為30nm以上的突起密度D(30)為104個/mm2以上時，與突起密度D(30)小於104個/mm2之情況相比，減少貼附之效果和賦予滑動性之效果較大。隨著突起密度D(30)的增加，減少貼附之效果和賦予滑動性之效果增大，當突起密度D(30)為2×104個/mm2以上時，減少貼附之效果和賦予滑動性之效果進一步增大。並且，當突起密度D(30)為106個/mm2以下時，與突起密度D(30)大於106個/mm2之情況相比，將薄膜10的霧度抑制得較低。當突起密度D(30)為5×105個/mm2以下時，將薄膜10的霧度抑制得更低。另外，關於突起密度D(40)，減少貼附之效果和賦予滑動性之效果較大的範圍和將霧度抑制得較低之範圍亦與突起密度D(30)相同。 The number of protrusions 15 having a height of H or more per 1 mm 2 of the film surface 10 a is defined as the protrusion density D (H) [unit: pieces / mm 2 ]. The protrusion density D (30) having a height of 30 nm or more is in a range of 10 4 / mm 2 or more and 10 6 / mm 2 or less. When the protrusion density D (30) with a height of 30 nm or more is 10 4 pieces / mm 2 or more, compared with the case where the protrusion density D (30) is less than 10 4 pieces / mm 2 , the effect of reducing adhesion and imparting sliding properties are improved. The effect is greater. As the protrusion density D (30) increases, the effect of reducing attachment and imparting sliding properties increases. When the protrusion density D (30) is 2 × 10 4 pieces / mm 2 or more, the effect of reducing attachment and The effect of imparting sliding properties is further increased. In addition, when the protrusion density D (30) is 10 6 pieces / mm 2 or less, the haze of the film 10 is suppressed to be low as compared with the case where the protrusion density D (30) is more than 10 6 pieces / mm 2 . When the protrusion density D (30) is 5 × 10 5 pieces / mm 2 or less, the haze of the film 10 is suppressed to be lower. In addition, the protrusion density D (40) is the same as the protrusion density D (30) in a range in which the effect of reducing the adhesion and the effect of imparting sliding properties are large and a range in which the haze is suppressed to be low.

當使用薄膜10作為偏光板的保護膜時，對薄膜10進行皂化處理。如圖3所示，偏光板20具備偏光膜17和一對薄膜10，薄膜10配置於偏光膜17的各個面。皂化處理係為了提高與偏光膜17的黏接力而進行者。薄膜10的與和偏光膜17黏接之薄膜面10a相反一側的薄膜面10a成為偏光板20的表面20a。另外，皂化處理通常在薄膜10的兩個薄膜面 10a上進行，本實施形態中亦是對兩個薄膜面10a進行。 When the thin film 10 is used as a protective film of a polarizing plate, the thin film 10 is subjected to a saponification treatment. As shown in FIG. 3, the polarizing plate 20 includes a polarizing film 17 and a pair of thin films 10. The thin films 10 are arranged on each surface of the polarizing film 17. The saponification process is performed in order to improve the adhesive force with the polarizing film 17. The film surface 10 a of the film 10 on the opposite side to the film surface 10 a to which the polarizing film 17 is adhered becomes the surface 20 a of the polarizing plate 20. In addition, saponification is usually performed on both film surfaces of the film 10. 10a is performed, and in this embodiment, the two film surfaces 10a are also performed.

薄膜10的皂化處理可以是任何條件，在本實施形態中，具有皂化製程、第1清洗製程、中和製程、第2清洗製程及乾燥製程。在皂化製程中，在鹼水溶液中浸漬薄膜10而使薄膜面10a皂化。作為鹼，例如可使用氫氧化鉀(KOH)。在第1清洗製程中，清洗經皂化製程之薄膜10。清洗例如用純水進行。在中和製程中，將酸或酸水溶液作為中和液，用該中和液使經第1清洗製程之薄膜10中和。在第2清洗製程中，例如用純水清洗經中和製程之薄膜10。在乾燥製程中，對經第2清洗製程之薄膜10進行乾燥。 The saponification process of the film 10 may be any condition, and in this embodiment, it has a saponification process, a first cleaning process, a neutralization process, a second cleaning process, and a drying process. In the saponification process, the film 10 is immersed in an alkaline aqueous solution to saponify the film surface 10a. As the base, for example, potassium hydroxide (KOH) can be used. In the first cleaning process, the saponified film 10 is cleaned. The washing is performed, for example, with pure water. In the neutralization process, an acid or an acid aqueous solution is used as a neutralizing solution, and the neutralizing solution is used to neutralize the film 10 after the first cleaning process. In the second cleaning process, for example, the film 10 subjected to the neutralization process is washed with pure water. In the drying process, the film 10 after the second cleaning process is dried.

皂化處理具有較強條件的皂化(以下稱為較強的皂化)處理和較緩條件的皂化(以下稱為較弱的皂化)處理，可以是其中任意一種。較強的皂化處理的各製程條件如下。在皂化製程中，將濃度在1.5mol/L以上5.0mol/L以下的範圍內之KOH水溶液用作鹼水溶液，該KOH水溶液的溫度在45℃以上60℃以下的範圍內，針對該KOH水溶液的薄膜10的浸漬時間在30秒以上130秒以下的範圍內。在第1清洗製程中，用純水進行清洗，清洗時間在10秒以上20秒以下的範圍內。在中和製程中，將濃度在0.05mol/L以上0.4mol/L以下的範圍內的硫酸水溶液(H2SO4aq)用作中和液，該H2SO4aq的溫度在20℃以上30℃以下的範圍內，中和時間在10秒以上30秒以下的範圍內。在第2清洗製程中，用純水進行清洗，清洗時間在100秒以上130秒以下的範圍內。在乾燥製程中，藉由在100℃以上130℃以下的範圍內的溫度環境下將薄膜10放置40秒以上100秒以下的時間來進行乾燥。 The saponification treatment may be either a saponification treatment with a stronger condition (hereinafter referred to as a stronger saponification) treatment and a saponification treatment with a milder condition (hereinafter referred to as a weaker saponification) treatment. Each process condition of the strong saponification process is as follows. In the saponification process, an aqueous KOH solution having a concentration in a range of 1.5 mol / L to 5.0 mol / L is used as an alkaline aqueous solution. The temperature of the KOH aqueous solution is in a range of 45 ° C to 60 ° C. The immersion time of the film 10 is in a range of 30 seconds to 130 seconds. In the first washing process, washing is performed with pure water, and the washing time is within a range of 10 seconds to 20 seconds. In the neutralization process, a sulfuric acid aqueous solution (H 2 SO 4 aq) having a concentration in a range of 0.05 mol / L to 0.4 mol / L is used as a neutralizing solution, and the temperature of the H 2 SO 4 aq is above 20 ° C. In the range of 30 ° C or lower, the neutralization time is in the range of 10 seconds to 30 seconds. In the second washing process, washing is performed with pure water, and the washing time is within a range of 100 seconds to 130 seconds. In the drying process, the film 10 is dried by leaving the film 10 in a temperature environment in a range of 100 ° C. to 130 ° C. for a period of 40 seconds to 100 seconds.

較強的皂化處理條件的第1例(以下稱為第1皂化條件)如下。 A first example of a strong saponification treatment condition (hereinafter referred to as a first saponification condition) is as follows.

皂化製程：在KOH水溶液(KOH濃度為2.0mol/L，溫度為55℃)中浸漬120秒鐘 Saponification process: immersed in KOH aqueous solution (KOH concentration is 2.0mol / L, temperature is 55 ° C) for 120 seconds

第1清洗製程：用純水清洗15秒鐘 The first cleaning process: 15 seconds with pure water

中和製程：在H2SO4aq(H2SO4濃度為0.05mol/L，溫度為30℃)中浸 漬20秒鐘 Neutralization process: immersed in H 2 SO 4 aq (H 2 SO 4 concentration is 0.05mol / L, temperature is 30 ° C) for 20 seconds

第2清洗製程：用純水清洗120秒鐘 The second cleaning process: 120 seconds with pure water

乾燥製程：在100℃的溫度環境下放置60秒鐘 Drying process: Leave it at 100 ℃ for 60 seconds

較強的皂化處理條件的第2例(以下稱為第2皂化條件)如下。 A second example of a strong saponification treatment condition (hereinafter referred to as a second saponification condition) is as follows.

皂化製程：在KOH水溶液(KOH濃度為1.5mol/L，溫度為55℃)中浸漬120秒鐘 Saponification process: immersed in KOH aqueous solution (KOH concentration is 1.5mol / L, temperature is 55 ° C) for 120 seconds

第1清洗製程：用純水清洗15秒鐘 The first cleaning process: 15 seconds with pure water

中和製程：在H2SO4aq(H2SO4濃度為0.1mol/L，溫度為30℃)中浸漬20秒鐘 Neutralization process: immersed in H 2 SO 4 aq (H 2 SO 4 concentration is 0.1mol / L, temperature is 30 ° C) for 20 seconds

第2清洗製程：用純水清洗120秒鐘 The second cleaning process: 120 seconds with pure water

乾燥製程：在120℃的溫度環境下放置60秒鐘 Drying process: Leave it at 120 ℃ for 60 seconds

較弱的皂化處理的皂化製程條件如下：將濃度為1.0mol/L以上1.4mol/L以下的範圍內之KOH水溶液用作鹼水溶液，該KOH水溶液的溫度在20℃以上40℃以下的範圍內，針對該KOH水溶液的薄膜10的浸漬時間在30秒以上130秒以下的範圍內。另外，較弱的皂化處理中之第1清洗製程、中和製程、第2清洗製程及乾燥製程的各條件係分別與上述較強的皂化處理中者相同。 The saponification process conditions of the weaker saponification process are as follows: a KOH aqueous solution having a concentration in a range of 1.0 mol / L and 1.4 mol / L is used as an alkaline aqueous solution, and the temperature of the KOH aqueous solution is in a range of 20 ° C to 40 ° C The immersion time of the thin film 10 for the KOH aqueous solution is in a range of 30 seconds to 130 seconds. In addition, the respective conditions of the first washing process, the neutralization process, the second washing process, and the drying process in the weak saponification process are the same as those in the strong saponification process described above.

較弱的皂化處理條件的例子(以下稱為第3皂化條件)如下。 Examples of weaker saponification treatment conditions (hereinafter referred to as third saponification conditions) are as follows.

皂化製程：在KOH水溶液(KOH濃度為1.1mol/L，溫度為35℃)中浸漬120秒鐘 Saponification process: immersed in KOH aqueous solution (KOH concentration is 1.1mol / L, temperature is 35 ° C) for 120 seconds

第1清洗製程：用純水清洗15秒鐘 The first cleaning process: 15 seconds with pure water

中和製程：在H2SO4aq(H2SO4濃度為0.1mol/L，溫度為30℃)中浸漬20秒鐘 Neutralization process: immersed in H 2 SO 4 aq (H 2 SO 4 concentration is 0.1mol / L, temperature is 30 ° C) for 20 seconds

第2清洗製程：用純水清洗120秒鐘 The second cleaning process: 120 seconds with pure water

乾燥製程：在120℃的溫度環境下放置60秒鐘 Drying process: Leave it at 120 ℃ for 60 seconds

藉由使包含碘之化合物分子吸附於由聚乙烯醇(Polyvinyl Alcohol，PVA)構成之薄膜並使PVA和包含碘之化合物分子取向來製作偏光膜17。在薄膜10和偏光膜17的黏接中使用PVA系的黏接劑。另外，偏光膜17並不限於此，只要是一般用作偏光膜者，则可以係任意者。並且，在本實施形態中，在偏光膜17的兩個面黏接薄膜10而成為偏光板20，但並不限於該構成。例如，亦可以僅在偏光膜17的單面黏接薄膜10，還可以在偏光膜17的兩個面上黏接有薄膜10之最外表面設置PET等保護膜層。 By adsorbing molecules of compounds containing iodine to polyvinyl alcohol (Polyvinyl Alcohol (PVA) is used to form a polarizing film 17 by orienting PVA and molecular compounds containing iodine. For the adhesion between the thin film 10 and the polarizing film 17, a PVA-based adhesive is used. The polarizing film 17 is not limited to this, and may be any one as long as it is generally used as a polarizing film. Furthermore, in this embodiment, the thin film 10 is adhered to both surfaces of the polarizing film 17 to form the polarizing plate 20, but it is not limited to this configuration. For example, the thin film 10 may be adhered to only one side of the polarizing film 17, or the outermost surface of the thin film 10 may be adhered to both sides of the polarizing film 17, and a protective film layer such as PET may be provided.

薄膜10藉由實施皂化處理而膨潤，進一步吸濕而變得容易膨潤。因此，實施皂化處理之後(皂化處理後)的微粒14從薄膜面10a突出之高度Hk[單位：nm]低於實施皂化處理之前(皂化處理前)的高度H。關於皂化處理後的薄膜10，亦與皂化處理前的薄膜10相同，當突起15的高度Hk為30nm以上時，與突起15的高度Hk小於30nm之情況相比，減少重疊之薄膜10的局部彼此的貼附或者提高滑動性之效果較大。隨著突起15變高，減少貼附或者提高滑動性之效果增大，當突起15的高度Hk為40nm以上時，減少重疊之薄膜10的局部彼此的貼附或者提高滑動性之效果進一步增大。當薄膜10在前述較強的皂化條件下進行皂化處理時，皂化處理後之減少貼附和賦予滑動性的效果尤為高。並且，與皂化處理前相同，即使在皂化處理後，突起15的高度Hk為100nm以下時，與高度Hk高於100nm之情況相比，薄膜10的霧度亦較低，因此為較佳。 The film 10 is swelled by performing a saponification treatment, and further swells by absorbing moisture. Therefore, the height Hk [unit: nm] of the fine particles 14 protruding from the film surface 10a after the saponification treatment (after the saponification treatment) is lower than the height H before the saponification treatment (before the saponification treatment). The thin film 10 after the saponification treatment is also the same as the thin film 10 before the saponification treatment. When the height Hk of the protrusions 15 is 30 nm or more, compared with the case where the height Hk of the protrusions 15 is less than 30 nm, the overlapping portions of the thin film 10 are reduced. The effect of attaching or improving the sliding property is great. As the protrusions 15 become higher, the effect of reducing attachment or improving the sliding property increases. When the height Hk of the protrusions 15 is 40 nm or more, the effect of reducing the partial attachment of the overlapping films 10 or improving the sliding property further increases. . When the film 10 is subjected to a saponification treatment under the aforementioned strong saponification conditions, the effects of reducing adhesion and imparting sliding properties after the saponification treatment are particularly high. In addition, similar to before the saponification treatment, even when the height Hk of the protrusions 15 is 100 nm or less after the saponification treatment, the haze of the thin film 10 is lower than that of the case where the height Hk is higher than 100 nm.

並且，在皂化處理後的薄膜10中，與皂化處理前的薄膜10相比，雖然高度Hk為30nm以上的突起的數量較少，但具有減少貼附之效果。在此，將在皂化處理後的薄膜面10a的每1mm2內存在之高度為Hk以上的突起15的個數設為突起密度Dk(Hk)[單位：個/mm2]。高度為30nm以上的突起密度Dk(30)在104個/mm2以上106個/mm2以下的範圍內為較佳。關於皂化處理後的薄膜10，亦與皂化處理前的薄膜10相同，當高度為30nm以上的突起密度Dk(30)為104個/mm2以上時，與突起密度Dk(30)小於104個/mm2之情況相比，減少貼附之效果和賦予滑動性之效果較大。隨著突起密度Dk(30)的增加，減少貼附之效果和賦予滑動性之效果增大，當突起密度Dk(30)為2×104個/mm2以上時，減少貼附之效果和賦 予滑動性之效果進一步增大。並且，當突起密度Dk(30)為106個/mm2以下時，與突起密度Dk(30)大於106個/mm2之情況相比，將薄膜10的霧度抑制得較低。當突起密度Dk(30)為5×105個/mm2以下時，將薄膜10的霧度抑制得更低。另外，關於突起密度Dk(40)，減少貼附之效果和賦予滑動性之效果較大的範圍和將霧度抑制得較低之範圍亦與突起密度Dk(30)相同。 In addition, in the film 10 after the saponification treatment, the number of protrusions having a height Hk of 30 nm or more is smaller than that of the film 10 before the saponification treatment, but has the effect of reducing attachment. Here, the number of protrusions 15 having a height of Hk or more per 1 mm 2 of the film surface 10 a after the saponification treatment is defined as the protrusion density Dk (Hk) [unit: pieces / mm 2 ]. The protrusion density Dk (30) having a height of 30 nm or more is preferably within a range of 10 4 / mm 2 or more and 10 6 / mm 2 or less. The film 10 after the saponification treatment is also the same as the film 10 before the saponification treatment. When the protrusion density Dk (30) having a height of 30 nm or more is 10 4 pieces / mm 2 or more, the protrusion density Dk (30) is less than 10 4 Compared with the case of / mm 2 , the effect of reducing attachment and the effect of imparting sliding properties are greater. With the increase of the protrusion density Dk (30), the effect of reducing the attachment and the effect of imparting sliding properties increase. When the protrusion density Dk (30) is 2 × 10 4 pieces / mm 2 or more, the effect of reducing the attachment and The effect of imparting sliding properties is further increased. In addition, when the protrusion density Dk (30) is 10 6 pieces / mm 2 or less, the haze of the film 10 is suppressed to be low as compared with the case where the protrusion density Dk (30) is more than 10 6 pieces / mm 2 . When the protrusion density Dk (30) is 5 × 10 5 pieces / mm 2 or less, the haze of the film 10 is suppressed to be lower. The protrusion density Dk (40) is also the same as the protrusion density Dk (30) in a range in which the effect of reducing adhesion and a effect of imparting sliding properties are large and a range in which haze is suppressed to be low.

並且，偏光板20的表面20a由於具有與皂化處理後的薄膜面10a相同的構成，因此關於偏光板20，在與上述皂化處理後的薄膜10相同的條件下，亦具有減少偏光板20彼此的貼附和賦予滑動性之效果。 In addition, since the surface 20a of the polarizing plate 20 has the same structure as the film surface 10a after the saponification treatment, the polarizing plate 20 also has a reduced number of polarizing plates 20 under the same conditions as the film 10 after the saponification treatment. The effect of attaching and imparting sliding properties.

以下，利用圖4對重疊有兩片皂化處理前的薄膜10、皂化處理後的薄膜10或偏光板20(統稱時，稱為薄膜等10、20)之情況、及捲取成卷狀而成為薄膜卷之情況進行說明。若重疊有兩片薄膜等10、20，則各薄膜等10、20中任一方的薄膜面10a、20a彼此相對向接觸。另一方面，在薄膜卷中，在薄膜等10、20的捲取重疊部份，薄膜面10a、20a不僅彼此相對向接觸，而且還被施加接觸面壓。在薄膜卷中，薄膜等10、20越薄，施加於捲取重疊部份之接觸面壓越高。並且，薄膜等10、20的彈性模量越低，施加於捲取重疊部份之接觸面壓越高。並且，薄膜等10、20的長度越長，由於捲緊而施加於捲取重疊部份之接觸面壓越高。 Hereinafter, the case where two sheets of the saponified film 10, the saponified film 10, or the polarizing plate 20 (collectively referred to as films and the like 10 and 20 when collectively referred to) are stacked with each other using FIG. The case of a film roll is demonstrated. When two sheets of films 10 and 20 are overlapped, any one of the film surfaces 10a and 20a of each of the films 10 and 20 is in contact with each other. On the other hand, in the film roll, not only the film surfaces 10a, 20a are in contact with each other, but also the contact surface pressure is applied to the overlapping portions of the films 10, 20 and the like. In a film roll, the thinner the film 10 or 20, the higher the contact surface pressure applied to the winding overlapped portion. In addition, the lower the elastic modulus of the film 10 or 20, the higher the contact surface pressure applied to the overlapping portion. In addition, the longer the length of the film 10 or 20, the higher the contact surface pressure applied to the overlapping portion due to the tight winding.

無論在重疊有兩片皂化處理前的薄膜10時，還是在成為薄膜卷時，在相對向之兩個薄膜面10a上均形成有由微粒14形成之突起15。藉由該些突起15，可以局部防礙相對向之兩個薄膜面10a相互直接接觸。因此，重疊之薄膜10不會局部相互貼附。 When two sheets of the film 10 before the saponification treatment are superposed or when a film roll is formed, protrusions 15 made of fine particles 14 are formed on the two opposite film surfaces 10a. By these protrusions 15, it is possible to partially prevent the two film surfaces 10a facing each other from directly contacting each other. Therefore, the overlapping films 10 are not locally adhered to each other.

當皂化處理前的薄膜10捲取成薄膜卷狀時，接觸面壓進一步施加於相對向之兩個薄膜面10a。此時，亦藉由突起15，局部防礙相對向之兩個薄膜面10a相互直接接觸，薄膜10的重疊部份不會局部相互貼附。因此，即使受到接觸面壓的影響，亦在薄膜10的重疊部份之間產生滑動。 When the film 10 before being saponified is rolled into a film roll shape, the contact surface pressure is further applied to the two opposite film surfaces 10a. At this time, the two film surfaces 10a facing each other are also prevented from directly contacting each other by the protrusions 15, and the overlapping portions of the films 10 are not locally adhered to each other. Therefore, even under the influence of the contact surface pressure, slippage occurs between the overlapping portions of the film 10.

並且，由於薄膜10變薄、或者加長薄膜10、或者減小薄膜10的彈性模量，因此施加於薄膜10之接觸面壓較高時，亦與施加於薄膜 10之接觸面壓較低之情況相同，藉由突起15減小薄膜10的重疊部份的相互貼附。亦即，減少黏連的產生。因此，薄膜10的重疊部份之間的靜摩擦係數保持得較低，在它們之間產生滑動。藉此，不會在薄膜卷上產生凹部，且不會在捲取之薄膜10上產生折皺等。 In addition, since the film 10 becomes thinner, or the film 10 is elongated, or the elastic modulus of the film 10 is reduced, when the contact surface pressure applied to the film 10 is high, it is also the same as that applied to the film. The case where the contact surface pressure of 10 is low is the same, and the overlapping of the overlapping portions of the film 10 is reduced by the protrusion 15. That is, the occurrence of adhesion is reduced. Therefore, the static friction coefficient between the overlapping portions of the film 10 is kept low, and slippage occurs between them. Thereby, no recesses are generated in the film roll, and no wrinkles or the like are generated in the rolled film 10.

以往，薄膜的長度越長，例如在2000m以上10000m以下的範圍，則薄膜卷上重疊部份因接觸面壓越是彼此貼附。相對於此，在薄膜10中，即使為這種長度，亦不會在薄膜卷上產生貼附。並且，無論是薄膜10是彈性模量較低時的薄膜卷，還是較薄時的薄膜卷，均可以減少貼附。 Conventionally, as the length of the film is longer, for example, in the range of 2,000 m to 10,000 m, the overlapping portions on the film roll are adhered to each other due to the contact surface pressure. On the other hand, in the film 10, even if it is such a length, it does not attach to a film roll. In addition, it is possible to reduce sticking regardless of whether the film 10 is a film roll having a low elastic modulus or a thin film roll.

即使在重疊有兩片皂化處理後的薄膜10時，亦與上述皂化處理前的薄膜10之情況相同，兩片薄膜10不會局部相互貼附。並且，即使在皂化處理後的薄膜10捲取成薄膜卷狀時亦相同，薄膜10的重疊部份不會局部相互貼附。而且，不會在薄膜卷上產生凹部，且不會在捲取之薄膜10上產生折皺等。無論是重疊有兩片偏光板20之情況，還是偏光板20捲取成薄膜卷狀之情況均相同。 Even when two sheets of the saponified film 10 are superimposed, as in the case of the aforementioned film 10 before the saponified process, the two films 10 are not locally adhered to each other. In addition, the same applies even when the film 10 after being saponified is rolled into a film roll shape, and the overlapping portions of the film 10 are not locally adhered to each other. Further, no recesses are generated in the film roll, and no wrinkles or the like are generated in the rolled film 10. The same applies to the case where the two polarizing plates 20 are overlapped and the case where the polarizing plate 20 is rolled into a film roll.

藉由後述溶液製膜設備30(參閱圖5)，由第1濃液41和第2濃液42製造薄膜10。形成薄膜主體12之第1濃液41為包含作為聚合物之纖維素醯化物、添加劑及溶劑之液態的第1濃液組成物。纖維素醯化物和添加劑作為固形物而包含於第1濃液組成物中。纖維素醯化物溶解於溶劑中，添加劑不溶解於溶劑而分散於溶劑中。第1濃液41中之纖維素醯化物與添加劑的比率與薄膜主體12的各成份比相同。 The thin film 10 is produced from the first dope 41 and the second dope 42 by a solution film forming apparatus 30 (see FIG. 5) described later. The first dope 41 forming the film main body 12 is a liquid first dope composition containing a cellulose halide as a polymer, an additive, and a solvent. The cellulose mash and the additive are contained as a solid substance in the first dope composition. The cellulose halide is dissolved in the solvent, and the additives are not dissolved in the solvent but dispersed in the solvent. The ratio of the cellulose halide and the additive in the first dope 41 is the same as the ratio of each component of the film main body 12.

形成表層13之第2濃液42為除了包含與第1濃液41相同的固形物及溶劑以外，還包含作為固形物的微粒14之液態的第2濃液組成物。第2濃液42中之纖維素醯化物、添加劑及微粒14的比率與表層13的各成份比相同。構成第1濃液41、第2濃液42之成份的比率分別考慮各濃液的固形物的濃度及構成薄膜主體12、表層13之成份的比率而決定。 The second dope 42 forming the surface layer 13 is a second dope composition in a liquid state containing the same solid matter and solvent as the first dope 41 and a fine particle 14 as a solid. The ratio of the cellulose mash, the additive, and the fine particles 14 in the second dope 42 is the same as the respective component ratios of the surface layer 13. The ratio of the components constituting the first dope 41 and the second dope 42 is determined in consideration of the concentration of the solid matter of each dope and the ratio of the components constituting the film body 12 and the surface layer 13.

在此，微粒14通常以分散於分散劑中之分散液的狀態作為第2濃液42的原料，並用於調製第2濃液42。亦可以同時使用第1微粒14分散於第1分散劑中之第1分散液和第2微粒14分散於第2分散劑中 之第2分散液。在此，第2濃液42中的微粒14的分散狀態與該分散液中的微粒14的分散狀態大致相同，因此以後將第2濃液42中的微粒14的分散狀態記為與用於調製第2濃液42之微粒14在分散液中的分散狀態相同者。 Here, the fine particles 14 are generally used as a raw material of the second dope 42 in a state of a dispersion liquid dispersed in a dispersant, and are used to prepare the second dope 42. The first dispersion liquid in which the first fine particles 14 are dispersed in the first dispersant and the second fine particles 14 in the second dispersant may also be used simultaneously. The second dispersion. Here, since the dispersion state of the microparticles 14 in the second dope 42 is substantially the same as the dispersion state of the microparticles 14 in the dispersion solution, the dispersion state of the microparticles 14 in the second dope 42 will be described later as used for preparation. The particles 14 of the second dope 42 have the same dispersion state in the dispersion.

在第2濃液42中，微粒14呈二次粒子的樣態而分散。二次粒徑r2為0.7μm以上的微粒14相對於第2濃液42中所包含之微粒14總數之含有比例N(0.7)[單位：%]為30%以上為較佳，含有比例N(0.7)為50%以上為更佳。藉由形成表層13之第2濃液42包含0.7μm以上的二次粒徑的微粒14，如上所述，表層13上會以所希望的突起密度D(H)、Dk(Hk)形成所希望的高度H、Hk的突起15。因此，關於使用這種第2濃液42製造之薄膜10，重疊薄膜10時的薄膜10彼此的貼附得以減少，且對其薄膜面10a賦予滑動性。 In the second dope 42, the fine particles 14 are dispersed as secondary particles. The content ratio N (0.7) [unit:%] of the fine particles 14 having a secondary particle diameter r2 of 0.7 μm or more to the total number of fine particles 14 contained in the second dope 42 is preferably 30% or more, and the content ratio N ( 0.7) is more preferably 50% or more. Since the second dope 42 forming the surface layer 13 contains fine particles 14 having a secondary particle diameter of 0.7 μm or more, as described above, the surface layer 13 is formed with the desired protrusion densities D (H) and Dk (Hk). Of the heights H, Hk of the protrusions 15. Therefore, with respect to the thin film 10 manufactured using such a second dope 42, the adhesion of the thin films 10 to each other when the thin films 10 are superimposed is reduced, and the film surface 10a is provided with sliding properties.

在此，如下定義表示微粒14的二次粒子的直徑之二次粒徑r2。當二次粒子的形狀為球形時將其直徑設為二次粒徑r2，當接近球形時將二次粒子近似於球形時的直徑設為二次粒徑r2。當二次粒子的形狀為橢圓體時，將長軸的長度設為二次粒徑r2，當接近橢圓體時，將二次粒子近似於橢圓體時的長軸的長度設為二次粒徑r2。如下求出第2濃液42所包含之微粒14的二次粒徑r2。在平面上使第2濃液42較薄地延伸，對於該平面，例如使用掃描型電子顯微鏡(Scanning Electron Microscope，SEM)放大至3000倍進行表面觀察，則可以得到各二次粒子的表面觀察圖像。對於該各二次粒子的表面觀察圖像，用圓近似或橢圓近似進行擬合。用圓近似擬合時，將直徑的值設為二次粒徑r2，用橢圓近似擬合時，將長軸的長度設為二次粒徑r2。 Here, the secondary particle diameter r2 that represents the diameter of the secondary particles of the fine particles 14 is defined as follows. When the shape of the secondary particles is spherical, the diameter is set as the secondary particle diameter r2, and when the shape is close to the spherical shape, the diameter when the secondary particles are approximately spherical is set as the secondary particle diameter r2. When the shape of the secondary particles is ellipsoid, the length of the long axis is set to the secondary particle diameter r2. When the shape of the secondary particles is close to the ellipsoid, the length of the long axis when the secondary particles approximate the ellipsoid is set to the secondary particle diameter. r2. The secondary particle diameter r2 of the fine particles 14 included in the second dope 42 is determined as follows. The second concentrated solution 42 is thinly extended on a plane, and for this plane, for example, a scanning electron microscope (Scanning Electron Microscope, SEM) is magnified to 3000 times for surface observation, and a surface observation image of each secondary particle can be obtained. . The surface observation image of each secondary particle is fitted using a circle approximation or an ellipse approximation. When the circle approximation is used, the value of the diameter is set to the secondary particle size r2, and when the ellipse approximation is used, the length of the major axis is set to the secondary particle size r2.

用於第1濃液41及第2濃液42中之溶劑53均為二氯甲烷、甲醇及丁醇的混合物。並且，雖然在本實施形態中使用了前述溶劑，但亦可以使用一般用於製造纖維素醯化物薄膜之溶液製膜中之其他任何溶劑。並且，不將薄膜主體12和表層13的各聚合物成份設為纖維素醯化物時，根據所使用之聚合物成份決定用於第1濃液41及第2濃液42中之溶劑53。 The solvent 53 used in the first dope 41 and the second dope 42 is a mixture of dichloromethane, methanol, and butanol. In addition, although the above-mentioned solvent is used in this embodiment, any other solvent that is generally used in the film formation of a solution of a cellulose halide film may be used. When the polymer components of the film main body 12 and the surface layer 13 are not made of cellulose halide, the solvent 53 used in the first dope 41 and the second dope 42 is determined based on the polymer components used.

製造薄膜10之溶液製膜例如在圖5的溶液製膜設備30中進行。溶液製膜設備30從上游側依次具備濃液調製裝置31、流延裝置32、拉幅機35、輥乾燥裝置36及捲取裝置37。 The solution film-making for manufacturing the thin film 10 is performed in the solution film-forming apparatus 30 of FIG. 5, for example. The solution film forming apparatus 30 includes a dope preparation device 31, a casting device 32, a tenter 35, a roll drying device 36, and a winding device 37 in this order from the upstream side.

濃液調製裝置31係用於製作前述第1濃液41和第2濃液42者。濃液調製裝置31可以設置於溶液製膜設備30的外部，而非溶液製膜設備30內。此時，製作出之第1濃液41和第2濃液42暫時保存於保存容器等中。濃液調製裝置31具備溶解部43、混合部46、分散部47及過濾部48、49。 The dope preparation device 31 is used to prepare the first dope 41 and the second dope 42 described above. The dope preparation device 31 may be provided outside the solution film forming apparatus 30 instead of inside the solution film forming apparatus 30. At this time, the produced first dope 41 and the second dope 42 are temporarily stored in a storage container or the like. The dope preparation device 31 includes a dissolving section 43, a mixing section 46, a dispersing section 47, and filtering sections 48 and 49.

若供給纖維素醯化物52和溶劑53，則溶解部43將該些混合並進行加熱和攪拌等。藉此，製作纖維素醯化物52溶解於溶劑53中之液態的原料濃液54(原料濃液調製製程)。若將原料濃液54的一部份和添加劑59混合供給，則過濾部48對其進行過濾來作成第1濃液41。 When the cellulose mash 52 and the solvent 53 are supplied, the dissolving section 43 mixes these and heats and stirs them. Thereby, a liquid raw material dope 54 (raw material dope preparation process) in which the cellulose mash 52 is dissolved in the solvent 53 is prepared. When a part of the raw material dope 54 and the additive 59 are mixed and supplied, the filtering unit 48 filters this to prepare a first dope 41.

若供給纖維素醯化物52、溶劑53及微粒14，則混合部46將該些混合並進行攪拌來得到液態的混合物(混合物調製製程)。分散部47配置於混合部46的下游，若從分散部47供給該液態的混合物，則對該混合物實施超音波，使微粒14在混合物中分散，從而得到微粒分散液58(微粒分散製程)。另外，分散部47中亦可以使用球磨機來代替實施超音波。若將藉由分散部47得到之微粒分散液58、原料濃液54的另一部份及添加劑59混合供給，則過濾部49將其混合(混合製程)，並進行過濾來作成第2濃液42(過濾製程)。 When the cellulose mash 52, the solvent 53, and the fine particles 14 are supplied, the mixing unit 46 mixes and stirs these to obtain a liquid mixture (mixture preparation process). The dispersion section 47 is disposed downstream of the mixing section 46. When the liquid mixture is supplied from the dispersion section 47, ultrasonic waves are applied to the mixture to disperse the fine particles 14 in the mixture to obtain a fine particle dispersion liquid 58 (a fine particle dispersion process). Alternatively, a ball mill may be used in the dispersion unit 47 instead of performing ultrasonic waves. When the particulate dispersion liquid 58 obtained from the dispersion portion 47, the other portion of the raw material concentrated liquid 54 and the additive 59 are mixed and supplied, the filtering portion 49 mixes them (mixing process) and performs filtration to prepare a second concentrated liquid. 42 (filtration process).

流延裝置32係用於由第1濃液41和第2濃液42形成薄膜10者。流延裝置32具備傳送帶62、第1輥63及第2輥64。傳送帶62為形成為環狀之循環流延支撐體，為SUS製。傳送帶62捲繞於第1輥63和第2輥64的周面。第1輥63和第2輥64中的至少一方具有驅動部(未圖示)，藉由驅動部沿周方向旋轉。藉由該旋轉，與周面接觸之傳送帶62被傳送，藉由該傳送，傳送帶62進行循環並沿長邊方向連續行走。 The casting device 32 is used to form the thin film 10 from the first dope 41 and the second dope 42. The casting device 32 includes a conveyor belt 62, a first roller 63, and a second roller 64. The conveyor belt 62 is a circular casting support body formed in a ring shape, and is made of SUS. The conveyor belt 62 is wound around the peripheral surfaces of the first roller 63 and the second roller 64. At least one of the first roller 63 and the second roller 64 has a driving portion (not shown), and the driving portion rotates in the circumferential direction. By this rotation, the conveyor belt 62 in contact with the peripheral surface is conveyed, and by this conveyance, the conveyor belt 62 circulates and continuously walks in the longitudinal direction.

在傳送帶62的上方具備吐出第1濃液41和第2濃液42之流延模65。藉由從流延模65向傳送狀態之傳送帶62連續吐出第1濃液41 和第2濃液42，第1濃液41和第2濃液42以相互重疊之狀態在傳送帶62上流延，從而形成流延膜66。另外，第1濃液41以被夾在第2濃液42之態樣從流延模65的吐出口65a吐出。 A casting die 65 for discharging the first dope 41 and the second dope 42 is provided above the conveyor 62. The first dope 41 is continuously ejected from the casting die 65 to the conveying belt 62 in the conveying state. And the second dope 42, the first dope 41 and the second dope 42 are cast on the conveyor belt 62 in a state of overlapping with each other, thereby forming a casting film 66. In addition, the first dope 41 is discharged from the discharge port 65 a of the casting die 65 while being sandwiched by the second dope 42.

第1輥63和第2輥64分別具備控制周面溫度之溫度控制器(未圖示)。藉由控制第1輥63和第2輥的各周面溫度來調整傳送帶62的溫度。 The first roller 63 and the second roller 64 are each provided with a temperature controller (not shown) that controls the temperature of the peripheral surface. The temperature of the conveyor belt 62 is adjusted by controlling the temperatures of the peripheral surfaces of the first roller 63 and the second roller.

關於從流延模65至傳送帶62之第1濃液41及第2濃液42亦即所謂的液珠，在傳送帶62的行走方向上之上游具備減壓腔室(未圖示)。該減壓腔室吸引所吐出之第1濃液41及第2濃液42的上游側區域的氣氛而對前述區域進行減壓。 The first dope 41 and the second dope 42 which are the so-called liquid beads from the casting die 65 to the conveyor 62 are provided with a decompression chamber (not shown) upstream in the running direction of the conveyor 62. The decompression chamber sucks the atmosphere in the region on the upstream side of the discharged first dope 41 and second dope 42 and decompresses the aforementioned region.

使流延膜66硬化至能夠向拉幅機35傳送的程度之後，以包含溶劑53之狀態從傳送帶62剝下。就剝取而言，乾燥流延方式時以10質量%以上100質量%以下的範圍內的溶劑含有率進行，冷卻流延方式時以100質量%以上300質量%以下的範圍內的溶劑含有率進行。乾燥流延方式為主要藉由乾燥使流延膜66硬化之方式，冷卻流延方式為主要藉由冷卻使流延膜66凝膠化而硬化之方式。另外，本說明書中之溶劑含有率為將處於潤濕狀態之薄膜10的質量設為X將該薄膜10乾燥之後的質量設為Y時，由{(X-Y)/Y}×100求出之所謂的乾量基準的值。 After the casting film 66 is cured to such an extent that it can be conveyed to the tenter 35, it is peeled from the conveyor belt 62 in a state containing the solvent 53. In terms of peeling, the solvent content rate in the range of 10% by mass to 100% by mass in the dry casting method is performed, and the solvent content rate in the range of 100% by mass to 300% by mass in the cooling cast method. get on. The dry casting method is a method in which the casting film 66 is hardened mainly by drying, and the cooling casting method is a method in which the casting film 66 is gelatinized and hardened mainly by cooling. In addition, when the solvent content rate in this specification is the mass of the thin film 10 in the wet state as X, when the mass of the film 10 after drying is Y, the so-called is obtained from {(XY) / Y} × 100 The value of the dry basis.

在剝取時，用剝取用的輥(以下稱為剝取輥)70支撐薄膜10，固定保持從傳送帶62剝下流延膜66之剝取位置。若傳送帶62進行循環而從剝取位置返回至流延第1濃液41及第2濃液42之流延位置，則再次流延新的第1濃液41及第2濃液42。 When peeling, the film 10 is supported by a peeling roller (hereinafter referred to as a peeling roller) 70, and the peeling position at which the casting film 66 is peeled from the conveyor belt 62 is fixedly held. When the conveyor belt 62 circulates and returns from the stripping position to the casting position where the first dope 41 and the second dope 42 are cast, the new first dope 41 and the second dope 42 are cast again.

亦可以以與傳送帶62的形成流延膜66之流延面相對向之方式設置供氣導管(未圖示)。該供氣導管排出氣體，促進所通過之流延膜66的乾燥。 An air supply duct (not shown) may be provided so as to face the casting surface of the casting film 66 forming the conveyor belt 62. The air supply duct exhausts gas, and promotes the drying of the casting film 66 passing therethrough.

用剝取輥70剝取之流延膜66亦即薄膜10被導引至拉幅機35。拉幅機35用保持構件71保持薄膜10的各側部，同時促進薄膜10的乾燥。作為拉幅機35的保持構件71，使用夾子和銷等。夾子藉由夾持薄 膜10，銷藉由沿厚度方向貫穿薄膜10來分別保持薄膜10。 The casting film 66 that is peeled by the peeling roller 70, that is, the film 10 is guided to the tenter 35. The tenter 35 holds each side portion of the film 10 with a holding member 71 and promotes drying of the film 10 at the same time. As the holding member 71 of the tenter 35, a clip, a pin, or the like is used. Clip by holding thin The film 10 and the pin respectively hold the film 10 by penetrating the film 10 in the thickness direction.

拉幅機35用保持構件71保持薄膜10並沿長邊方向進行傳送，同時賦予寬度方向上的張力，擴大薄膜10的寬度。該拉幅機35具備使乾燥氣體流向薄膜10的附近來進行供給之導管72。薄膜10被傳送，同時藉由來自導管72之乾燥氣體促進乾燥，並且藉由保持構件71在既定的時刻改變寬度。 The tenter 35 holds the film 10 with a holding member 71 and conveys the film 10 in the longitudinal direction, while applying tension in the width direction to expand the width of the film 10. The tenter 35 is provided with a duct 72 for supplying a dry gas to the vicinity of the film 10 and supplying it. The film 10 is conveyed while drying is promoted by the drying gas from the duct 72, and the width is changed by the holding member 71 at a predetermined timing.

輥乾燥裝置36係用於乾燥傳送狀態之薄膜10者。輥乾燥裝置36具備沿薄膜10的傳送方向排列有複數個之複數個輥73、空調機(未圖示)及腔室(未圖示)。在複數個輥73中有沿周方向旋轉之驅動輥，薄膜10藉由該驅動輥的旋轉而傳送至下游。空調機吸引腔室內部的氣氛，調節所吸引之氣體的濕度和溫度等之後將該氣體再次送入腔室內部。藉此，腔室內部的溫度和濕度等保持為恆定。捲取裝置37將從輥乾燥裝置36供給而來之薄膜10捲取成卷狀。另外，可以在輥乾燥裝置36與捲取裝置37之間設置冷卻室(未圖示)。該冷卻室在捲取通過內部之薄膜10之前將其冷卻至室溫。 The roller drying device 36 is used for drying the film 10 in a conveyed state. The roller drying device 36 includes a plurality of rollers 73, an air conditioner (not shown), and a chamber (not shown) arranged in the conveyance direction of the film 10. The plurality of rollers 73 include a driving roller that rotates in the circumferential direction, and the film 10 is conveyed downstream by the rotation of the driving roller. The air conditioner attracts the atmosphere inside the chamber, adjusts the humidity and temperature of the attracted gas, and sends the gas into the chamber again. Thereby, the temperature, humidity, and the like inside the chamber are kept constant. The winding device 37 winds the film 10 supplied from the roll drying device 36 into a roll shape. A cooling chamber (not shown) may be provided between the roll drying device 36 and the winding device 37. The cooling chamber cools the film 10 to room temperature before winding it through the inside film 10.

溶液製膜設備30為本發明的實施形態的一例，亦可以為其他溶液製膜設備。例如，作為流延支撐體，亦可以係沿周方向旋轉之滾筒(未圖示)來代替傳送帶62。冷卻流延方式時，將滾筒用作流延支撐體之情況較多。並且，亦可以在拉幅機35與輥乾燥裝置36之間設置具有與拉幅機35相同構成之拉幅機(未圖示)。 The solution film forming equipment 30 is an example of the embodiment of the present invention, and may be other solution film forming equipment. For example, instead of the conveyor belt 62, a roller (not shown) that rotates in the circumferential direction may be used as the casting support. In the cooling casting method, a roller is often used as a casting support. A tenter (not shown) having the same configuration as the tenter 35 may be provided between the tenter 35 and the roll drying device 36.

對上述構成的作用進行說明。若纖維素醯化物52和溶劑53被送至溶解部43，則進行混合並藉由加熱和攪拌等來作成原料濃液54(原料濃液調製製程)。原料濃液54的一部份在被導引至過濾部48之前，加入添加劑59，以與添加劑59混合之狀態，藉由過濾部48進行過濾而成為第1濃液41。 The effect of the above configuration will be described. When the cellulose mash 52 and the solvent 53 are sent to the dissolving section 43, they are mixed, and a raw material dope 54 is prepared by heating, stirring, or the like (raw material dope preparation process). A part of the raw material concentrated solution 54 is added to the filtering portion 48 before being added to the mixed portion 59 with the additive 59, and filtered by the filtering portion 48 to become the first concentrated solution 41.

若微粒14、纖維素醯化物52及溶劑53被導引至混合部46，則藉由混合部46混合並進行攪拌，從而得到液態的混合物(混合物調製製程)。在此，關於第2濃液42中所包含之微粒14的含有比例N(0.7)為 30%以上為較佳。該混合物從混合部46被送至分散部47。該混合物中的微粒14藉由分散部47分散於混合物中，從而得到微粒分散液58(微粒分散製程)。在原料濃液54的另一部份中加入微粒分散液58，再加入添加劑，並被導引至過濾部49進行混合(混合製程)，藉由過濾部49進行過濾而作成第2濃液42(過濾製程)。 When the fine particles 14, the cellulose halide 52, and the solvent 53 are guided to the mixing section 46, the mixing section 46 is mixed and stirred to obtain a liquid mixture (mixture preparation process). Here, the content ratio N (0.7) of the fine particles 14 contained in the second dope 42 is Above 30% is better. This mixture is sent from the mixing section 46 to the dispersion section 47. The fine particles 14 in the mixture are dispersed in the mixture by the dispersion portion 47 to obtain a fine particle dispersion liquid 58 (a fine particle dispersion process). The fine particle dispersion liquid 58 is added to the other part of the raw material concentrated liquid 54, and then additives are added, which are guided to the filtering section 49 for mixing (mixing process), and filtered by the filtering section 49 to prepare a second concentrated solution 42. (Filtration process).

第1濃液41和第2濃液42連續被導引至流延模65，從吐出口65a連續被吐出。以第2濃液42、第1濃液41、第2濃液42的順序重疊之狀態在傳送帶62上流延，從而形成流延膜66。形成於行走中之傳送帶62上之流延膜66在具備自支撐性之後，以包含溶劑53之狀態從傳送帶62被剝取，從而作成薄膜10。 The first dope 41 and the second dope 42 are continuously guided to the casting die 65 and continuously discharged from the discharge port 65a. The second dope 42, the first dope 41, and the second dope 42 are sequentially stacked on the conveyor 62 to form a casting film 66. After the casting film 66 formed on the running conveyor 62 has self-supporting properties, the casting film 66 is peeled from the conveyor 62 in a state containing a solvent 53 to form a film 10.

薄膜10被送至拉幅機35，以藉由保持構件71限制寬度之狀態，在從導管72供給之乾燥氣體的氣氛中通過。藉此，促進薄膜10的乾燥。出自拉幅機35之薄膜10被導引至輥乾燥裝置36，在通過該輥乾燥裝置36的腔室(未圖示)內部期間被乾燥。經乾燥之薄膜10被導引至捲取裝置37，捲取成卷狀。 The film 10 is sent to the tenter 35, and passes through the atmosphere of the dry gas supplied from the duct 72 in a state where the width is restricted by the holding member 71. Thereby, drying of the film 10 is promoted. The film 10 from the tenter 35 is guided to a roll drying device 36 and is dried while passing through the inside of a chamber (not shown) of the roll drying device 36. The dried film 10 is guided to a winding device 37 and wound into a roll shape.

在第2濃液42中微粒14相對於纖維素醯化物52之質量比例Wp[單位：質量%]及關於微粒14之含有比例N(0.7)、與薄膜面10a上之突起密度D(3o)[單位：個/mm2]之間具有相關性。突起密度D(30)隨著質量比例Wp和含有比例N(0.7)的增加而增加。在此，質量比例Wp係用(添加至濃液中之微粒的總質量)/(用於濃液中之纖維素醯化物的總質量)定義之比例。另外，藉由後述實施例中記載之測定方法分別求出含有比例N(0.7)及突起密度D(30)。並且，關於突起密度Dk(30)、突起密度D(40)、突起密度Dk(40)等，亦與突起密度D(30)同樣，具有隨著質量比例Wp和含有比例N(0.7)的增加而增加之傾向。 The mass ratio Wp [unit: mass%] of the fine particles 14 to the cellulose halide 52 in the second dope 42 and the content ratio N (0.7) of the fine particles 14 and the projection density D (3o) on the film surface 10a There is a correlation between [unit: pcs / mm 2 ]. The protrusion density D (30) increases as the mass ratio Wp and the content ratio N (0.7) increase. Here, the mass ratio Wp is a ratio defined by (total mass of fine particles added to the dope) / (total mass of cellulose trioxide used in the dope). The content ratio N (0.7) and the protrusion density D (30) were determined by the measurement methods described in the examples described later. Also, the protrusion density Dk (30), the protrusion density D (40), the protrusion density Dk (40), and the like have the same increase as the protrusion density D (30) with the mass ratio Wp and the content ratio N (0.7). And the tendency to increase.

作為一例，若將質量比例Wp設在0.1質量%以上0.3質量%以下的範圍內將粒子的一次粒徑r1設在12nm以上20nm以下的範圍內，則如圖6所示，可知突起密度D(30)隨著含有比例N(0.7)的增加而大致增加。在圖6中示出表示含有比例N(0.7)與突起密度D(30)之間的 相關性之直線U1。另外，若減小質量比例Wp，則在圖6中直線U1向下側(突起密度D(30)減少之一側)偏移，若提高質量比例Wp，則在圖6中直線U1向上側(突起密度D(30)增加之一側)偏移。並且，並不限於突起密度D(30)，關於突起密度D(40)及突起密度D(50)，亦隨著質量比例Wp和含有比例N(0.7)的增加而增加。 As an example, if the mass ratio Wp is set within the range of 0.1% by mass to 0.3% by mass, and the primary particle diameter r1 of the particles is set within the range of 12 nm to 20 nm, as shown in FIG. 6, it can be seen that the protrusion density D ( 30) As the content ratio N (0.7) increases, it increases approximately. FIG. 6 shows the ratio between the content ratio N (0.7) and the protrusion density D (30). Correlation line U1. In addition, if the mass ratio Wp is decreased, the straight line U1 is shifted downward (one side where the protrusion density D (30) is reduced) in FIG. 6. One side where the protrusion density D (30) increases) shifts. In addition, it is not limited to the protrusion density D (30), and the protrusion density D (40) and the protrusion density D (50) also increase as the mass ratio Wp and the content ratio N (0.7) increase.

然而，當使用含有增塑劑之第2濃液42時，即表層13中含有增塑劑時，因實施皂化處理，有時會在皂化處理後的薄膜10的薄膜面10a(參閱圖1、圖2)上產生發黏感(黏著性)。尤其在較弱的皂化條件下進行皂化處理時，具有產生該發黏感之傾向。皂化條件越強，增塑劑越容易被分解，當為前述較強的皂化條件時，在皂化處理中被分解而從薄膜面10a中去除。但是，當為前述較弱的皂化條件時，增塑劑的分解進程達不到從薄膜面10a中去除的程度，因此認為是以分解中途之狀態殘留之增塑劑成為發黏感的原因。 However, when the second dope 42 containing a plasticizer is used, that is, when the plasticizer is contained in the surface layer 13, the film surface 10a (see FIG. 1) of the film 10 after the saponification treatment may be applied due to the saponification treatment. Fig. 2) A sticky feeling (adhesiveness) is produced. In particular, when the saponification treatment is performed under a weak saponification condition, the sticky feeling tends to be generated. The stronger the saponification condition, the more easily the plasticizer is decomposed. When it is the aforementioned strong saponification condition, it is decomposed during the saponification treatment and removed from the film surface 10a. However, under the aforementioned weak saponification conditions, the decomposition process of the plasticizer is not sufficiently removed from the film surface 10a. Therefore, it is considered that the plasticizer remaining in a state of being decomposed causes the stickiness.

因此，當提供給前述較弱的皂化條件時，同時使用一次粒徑r1相互不同之第1微粒14和第2微粒14更為佳。具體而言，同時使用一次粒徑r1在16nm以上30nm以下的範圍內之第1微粒14和一次粒徑r1小於第1微粒14且在5nm以上15nm以下的範圍內之第2微粒14。藉此，能夠制造在圖2中之薄膜面10a形成有具有30nm以上高度H之突起15a、15b、以及具有10nm以上30nm以下範圍內的高度H之突起之薄膜(未圖示)。另外，此時在第2濃液42中，第1微粒14相對於纖維素醯化物52之質量比例Wp1設在0.10質量%以上0.30質量%以下的範圍內，第2微粒14相對於纖維素醯化物52之質量比例Wp2設在0.03質量%以上0.30質量%以下的範圍內為較佳。藉由還形成具有10nm以上30nm以下範圍內的高度H之突起，較弱的皂化條件下的皂化處理後的薄膜的貼附進一步可靠地得到抑制。並且，即使還形成具有10nm以上30nm以下範圍內的高度H之突起，由於該突起較小，因此霧度的上升亦會得到抑制。第1微粒14的一次粒徑r1在16nm以上30nm以下的範圍內為較佳，在16nm以上20nm以下的範圍內為進一步較佳。第2微粒14的一次粒徑r1在5nm以上15nm 以下的範圍內為較佳，在7nm以上12nm以下的範圍內為進一步較佳。不僅在第2濃液42中，而且在第1濃液41中亦可以同時使用一次粒徑r1相互不同之第1微粒14和第2微粒14。 Therefore, when the aforementioned weaker saponification conditions are provided, it is more preferable to use the first particles 14 and the second particles 14 having different primary particle diameters r1 from each other. Specifically, the first particles 14 having a primary particle diameter r1 in a range of 16 nm to 30 nm and the second particles 14 having a primary particle diameter r1 smaller than the first particles 14 and in a range of 5 nm to 15 nm are simultaneously used. As a result, a thin film (not shown) having protrusions 15a and 15b having a height H of 30 nm or more and protrusions H having a height H in a range of 10 nm to 30 nm can be manufactured on the thin film surface 10a in FIG. 2. At this time, in the second dope 42, the mass ratio Wp1 of the first fine particles 14 to the cellulose tritide 52 is set within a range of 0.10% by mass to 0.30% by mass, and the second fine particles 14 are relative to the cellulose The mass ratio Wp2 of the compound 52 is preferably set to be in a range of 0.03% by mass to 0.30% by mass. By further forming protrusions having a height H in a range of 10 nm to 30 nm, adhesion of the film after saponification treatment under weak saponification conditions is further reliably suppressed. In addition, even if protrusions having a height H in a range of 10 nm to 30 nm are formed, since the protrusions are small, an increase in haze is suppressed. The primary particle diameter r1 of the first fine particles 14 is preferably in a range of 16 nm to 30 nm, and more preferably in a range of 16 nm to 20 nm. The primary particle diameter r1 of the second fine particles 14 is 5 nm or more and 15 nm The following range is preferable, and the range of 7 nm to 12 nm is more preferable. Not only in the second dope 42 but also in the first dope 41, the first particles 14 and the second particles 14 having different primary particle diameters r1 may be used at the same time.

在本實施形態中，製造三層這種複數層構造的薄膜10，但如上所述，本發明對單層構造的薄膜亦具有效果。並且，在本實施形態中，製造由薄膜主體12和一對表層13構成之三層構造的薄膜10，但藉由本發明得到之薄膜並不限於此。例如，亦可以藉由複數層流延和塗佈等設為四層以上。另外，製造單層構造的薄膜時亦同樣，關於微粒14的含有比例N(0.7)為30%以上為較佳。並且，所製造之薄膜的薄膜面10a的突起密度D(30)在104個/mm2以上106個/mm2以下的範圍內，進行皂化處理之後的薄膜面10a的突起密度Dk(30)亦與皂化處理前同樣地在104個/mm2以上106個/mm2以下的範圍內。 In this embodiment, three layers of the thin film 10 having such a multiple-layer structure are manufactured. However, as described above, the present invention is also effective for a thin film having a single-layer structure. Furthermore, in this embodiment, a thin film 10 having a three-layer structure composed of a thin film main body 12 and a pair of surface layers 13 is manufactured, but the thin film obtained by the present invention is not limited to this. For example, it may be set to four or more layers by plural layers of casting, coating, and the like. The same applies to the production of a thin film having a single-layer structure, and the content ratio N (0.7) of the fine particles 14 is preferably 30% or more. In addition, the protrusion density D (30) of the film surface 10a of the produced film is in a range of 10 4 / mm 2 or more and 10 6 / mm 2 or less. The protrusion density Dk of the film surface 10a after saponification treatment (30 ) Is also in the range of 10 4 / mm 2 or more and 10 6 / mm 2 or less as before the saponification treatment.

以下，舉出4個與本發明有關之實施例。 Hereinafter, four examples related to the present invention will be listed.

[實施例1] [Example 1]

作為實施例1，進行17種實驗1-A~1-Q。在該實施例1中使用商品名分別為R972、NX90S、RX200(均為Nippon Aerosil Co.,Ltd.製造)之3種微粒14的分散液。在此，關於該3種微粒14的分散液，總結在以下的表1中。在表1的“分散液”的各欄所記載之各個商品名的分散液中，分別在“微粒”欄中示出構成微粒14之物質，在“分散劑”欄中示出構成分散劑之物質，在“微粒濃度”欄中示出分散劑中的微粒14的濃度[單位：質量%]，在“一次粒徑”欄中示出微粒14的一次粒徑r1的平均值[單位：nm]，在“二次粒徑平均值”欄中示出微粒14的二次粒徑r2的平均值[單位：μm]，在“含有比例N(0.7)”欄中示出關於微粒14的含有比例N(0.7)[單位：%]。另外，“微粒”和“分散劑”在3種分散液中相同，因此將表1中的欄分別合併在一起。“分散劑”欄中的CH2Cl2：CH3OH的比率係以質量計的比率。 As Example 1, 17 kinds of experiments 1-A to 1-Q were performed. In this Example 1, a dispersion liquid of three kinds of fine particles 14 each having a trade name of R972, NX90S, and RX200 (all manufactured by Nippon Aerosil Co., Ltd.) was used. Here, the dispersion liquid of these three kinds of fine particles 14 is summarized in Table 1 below. In the dispersion liquids of the respective trade names described in the columns of the "dispersion liquid" in Table 1, substances constituting the microparticles 14 are shown in the "fine particle" column, and those constituting the dispersant are shown in the "dispersant" column. For the substance, the concentration [unit: mass%] of the microparticles 14 in the dispersant is shown in the "particle concentration" column, and the average value [unit: nm] of the primary particle diameter r1 of the microparticles 14 is shown in the "primary particle diameter" column. ], An average value [unit: μm] of the secondary particle diameter r2 of the microparticles 14 is shown in the "secondary particle average value" column, and the content of the microparticles 14 is shown in the "content ratio N (0.7)" column Proportion N (0.7) [Unit:%]. In addition, since "microparticles" and "dispersant" are the same in the three dispersion liquids, the columns in Table 1 are combined together. The ratio of CH 2 Cl 2 : CH 3 OH in the “dispersant” column is a ratio by mass.

在此，微粒14的二次粒徑r2係基於上述實施形態所記載之定義者，如上所述，使用SEM放大至3000倍進行表面觀察，藉此針對每個微粒14求出二次粒徑。依據針對每個微粒14求出之二次粒徑r2的結果而求出微粒14的粒徑分佈，依據該粒徑分佈求出中位粒徑，將該中位粒徑設為二次粒徑r2的平均值。並且，依據微粒14的粒度分佈求出關於微粒14的含有比例N(0.7)。另外，在此求出之關於微粒14的含有比例N(0.7)為添加至濃液之後之含有比例N(0.7)。 Here, the secondary particle diameter r2 of the microparticles 14 is based on the definition described in the above embodiment, and as described above, the secondary particle diameter is obtained for each microparticle 14 by using SEM to magnify the surface to 3000 times. The particle size distribution of the particles 14 is obtained based on the result of the secondary particle diameter r2 obtained for each particle 14, and the median particle diameter is obtained based on the particle size distribution. The average value of r2. The content ratio N (0.7) of the fine particles 14 was obtained from the particle size distribution of the fine particles 14. The content ratio N (0.7) of the fine particles 14 obtained here is the content ratio N (0.7) after being added to the dope.

將各實驗中使用之微粒14的分散液的商品名示於表2的各例的欄中之“微粒”的“分散液”欄中。並且，將微粒14相對於纖維素醯化物52之質量比例Wp示於表2的各實驗中之“微粒”的“質量比例”欄中。另外，實驗1-L係相對於本發明之比較實驗，對於該實驗1-L未添加分散液，因此表2的“分散液”欄中表示為“-”。 The trade name of the dispersion liquid of the fine particles 14 used in each experiment is shown in the "dispersion liquid" column of "fine particles" in each column of Table 2. In addition, the mass ratio Wp of the microparticles 14 with respect to the cellulose halide 52 is shown in the "mass ratio" column of "microparticles" in each experiment of Table 2. In addition, Experiment 1-L is a comparative experiment with respect to the present invention. For this Experiment 1-L, no dispersion liquid was added. Therefore, the column "Dispersion liquid" in Table 2 is represented as "-".

並且，用於各實驗之濃液中所包含之微粒14以外的固形物設為以下固形物A~C中的任意一個。在任一實驗中，在所有三層的濃液中均使用相同種類的固形物。將各實驗中使用之微粒14以外的固形物示於表2的各實驗中之“固形物種類”欄中。另外，在此，以質量份單位表示之比例為將上述實施形態中源自原料濃液54之固形物和源自微粒分散液58之微粒14以外的固形物加在一起時的整體的比例。 The solid matter other than the fine particles 14 included in the dope used in each experiment was set to any one of the following solid matters A to C. In either experiment, the same kinds of solids were used in all three layers of dope. The solid matter other than the fine particles 14 used in each experiment is shown in the "solid type" column in each experiment of Table 2. Here, the ratio expressed in parts by mass is the overall ratio when the solid matter derived from the raw material dope 54 and the solid matter other than the fine particles 14 derived from the fine particle dispersion liquid 58 in the above embodiment are added together.

固形物A由以下所示之成份構成。使用固形物A製造之薄膜10的長度方向及寬度方向的平均彈性模量為4.5GPa。 The solid A is composed of the components shown below. The average elastic modulus in the longitudinal direction and the width direction of the film 10 manufactured using the solid A was 4.5 GPa.

〔固形物A〕 〔Solid A〕

三醋酸纤维素(TAC) 100.0質量份 100.0 parts by mass of cellulose triacetate (TAC)

苯甲酸蔗糖酯 7.5質量份 7.5 parts by mass of sucrose benzoate

乙酸異丁酸蔗糖酯 2.5質量份 2.5 parts by mass of sucrose isobutyrate

紫外線吸收劑TINUVIN(登錄商標)928(BASF Japan Ltd.製造)2.0質量份 2.0 parts by mass of UV absorber TINUVIN (registered trademark) 928 (manufactured by BASF Japan Ltd.)

在此，上述三醋酸纖維素係乙醯基取代度為2.86、黏度平均聚合度為306、含水率為0.2質量%、二氯甲烷溶液中的6質量%的黏度為310mPa．s的粉體。苯甲酸蔗糖酯及乙酸異丁酸蔗糖酯係增塑劑。並且，TINUVIN(登錄商標)928以2-(2H-苯並***-2-基)-6-(1-甲基-1-苯乙基)-4-(1,1,3,3-四甲基丁基)苯酚為主成份。 Here, the above cellulose triacetate-based acetamyl substitution degree is 2.86, the average viscosity polymerization degree is 306, the water content is 0.2% by mass, and the viscosity of 6% by mass in the dichloromethane solution is 310 mPa. s powder. Sucrose benzoate and sucrose acetate isobutyrate are plasticizers. In addition, TINUVIN (registered trademark) 928 uses 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenethyl) -4- (1,1,3,3- Tetramethylbutyl) phenol is the main ingredient.

固形物B由以下所示之成份構成。使用固形物B製造之薄膜10的長度方向及寬度方向的平均彈性模量為3.0GPa。 The solid B is composed of the components shown below. The average elastic modulus in the longitudinal direction and the width direction of the film 10 manufactured using the solid B was 3.0 GPa.

〔固形物B〕 [Solid B]

三醋酸纖維素(TAC) 100.0質量份 100.0 parts by mass of cellulose triacetate (TAC)

聚酯增塑劑 25.0質量份 Polyester plasticizer 25.0 parts by mass

紫外線吸收劑TINUVIN(登錄商標)928(BASF Japan Ltd.製造)2.0質量份 2.0 parts by mass of UV absorber TINUVIN (registered trademark) 928 (manufactured by BASF Japan Ltd.)

固形物C由以下所示之成份構成。使用固形物C製造之薄膜10的長度方向及寬度方向的平均彈性模量為3.0GPa。 The solid C is composed of the components shown below. The average elastic modulus in the longitudinal direction and the width direction of the film 10 manufactured using the solid C was 3.0 GPa.

〔固形物C〕 〔Solid C〕

丙烯酸聚合物 100.0質量份 100.0 parts by mass of acrylic polymer

並且，在各實驗的濃液中所包含之溶劑中使用以下所示之溶劑。 The solvents shown below were used as the solvents contained in the dope of each experiment.

〔溶劑〕 [Solvent]

二氯甲烷 330.0質量份 330.0 parts by mass of methylene chloride

甲醇 64.0質量份 64.0 parts by mass of methanol

丁醇 3.0質量份 3.0 parts by mass of butanol

在任一實驗中，濃液均使用上述圖5所示之濃液調製裝置31進行製造。在此，對於後述添加有微粒14之濃液，利用與第2濃液42相同的方法進行製造，對於未添加微粒14之濃液，利用與第1濃液41相 同的方法進行製造。並且，在任一實驗中，將形成薄膜主體12之濃液的固形物的濃度設為22%將形成表層13之濃液的固形物濃度設為19%。並且，在任一實驗中，藉由與上述圖5所示者相同的流延裝置32形成流延膜66。形成薄膜主體12之濃液被夾在形成表層13之濃液中，從而以三層重疊之狀態形成流延膜66。而且，剝取該流延膜66來形成薄膜10。之後，在圖5的溶液製膜設備30中，藉由設置於流延裝置32之下游的各裝置進行與上述實施形態相同的處理。 In each experiment, the dope was produced using the dope preparation device 31 shown in FIG. 5 described above. Here, a dope to which the fine particles 14 are added, which will be described later, is manufactured by the same method as the second dope 42, and a dope without the fine particles 14 is produced in the same phase as the first dope 41. The manufacturing method is the same. In each experiment, the concentration of the solid matter of the dope forming the thin film body 12 was set to 22%, and the concentration of the solid matter of the dope forming the surface layer 13 was set to 19%. In any experiment, a casting film 66 was formed by the same casting device 32 as that shown in FIG. 5 described above. The dope forming the film main body 12 is sandwiched in the dope forming the surface layer 13 to form a casting film 66 in a state of three layers overlapping. Then, the casting film 66 is peeled to form the thin film 10. Thereafter, in the solution film forming apparatus 30 shown in FIG. 5, the same processing as that of the above-mentioned embodiment is performed by each device provided downstream of the casting device 32.

在此，關於實驗1-A~1-E、1-J~1-Q，在所有三層的濃液中均添加微粒14。另一方面，關於實驗1-F~1-I，僅在形成表層13之濃液中添加微粒14。將各實驗中添加有微粒之濃液的層示於表2的各實驗中之“微粒”的“添加層”欄中。在此，對於在所有三層的濃液中添加有微粒14之例子，表示為“全層”，對於僅在形成表層13之濃液中添加有微粒14之例子，表示為“表層”。 Here, regarding experiments 1-A to 1-E and 1-J to 1-Q, fine particles 14 were added to the dope of all three layers. On the other hand, in Experiments 1-F to 1-I, the fine particles 14 were added only to the dope forming the surface layer 13. The layers of the dope-added dope in each experiment are shown in the "Additive layer" column of "microparticles" in each experiment in Table 2. Here, an example in which the fine particles 14 are added to the dope of all three layers is referred to as “full layer”, and an example in which the fine particles 14 are added to only the dope that forms the surface layer 13 is referred to as “surface layer”.

對於所製造之各薄膜10，藉由以下方法求出薄膜面10a上之突起15的總密度(總突起密度D[單位：個/mm2])、及分別進行皂化前後之高度為30nm以上的突起15的密度(突起密度D(30)[單位：個/mm2]、Dk(30)[單位：個/mm2])。皂化處理設為較強的皂化處理，其條件為前述第1皂化條件。 For each manufactured film 10, the total density of the protrusions 15 on the film surface 10a (total protrusion density D [unit: pcs / mm 2 ]) and the heights of 30 nm or more before and after saponification were determined by the following methods. The density of the protrusions 15 (the protrusion density D (30) [unit: pieces / mm 2 ], Dk (30) [unit: pieces / mm 2 ]). The saponification treatment is a strong saponification treatment, and the conditions are the aforementioned first saponification conditions.

從與所製造之各薄膜10(第1皂化條件下的皂化處理前)的薄膜面10a大致垂直的方向進行觀察，獲取該觀察的圖像。該觀察使用掃描型探針顯微鏡(SPA400，SII Nano Technology Inc.製造)，在AFM(Atomic Force Microscope，原子力顯微鏡)模式下，在100μm×100μm的範圍進行。以下，將在此所得到之觀察圖像稱為AFM圖像。在AFM圖像中，按照在觀察到之部位上從薄膜面10a的表面突出之高度，較高地顯示出與該部位對應之像素的亮度。作為AFM圖像的一例，將與實驗1-D中製造之薄膜10有關之AFM圖像示於圖7。 An observed image was obtained from a direction substantially perpendicular to the film surface 10a of each of the manufactured films 10 (before the saponification treatment under the first saponification condition). This observation was performed using a scanning probe microscope (SPA400, manufactured by SII Nano Technology Inc.) in an AFM (Atomic Force Microscope) mode in a range of 100 μm × 100 μm. Hereinafter, the observation image obtained here is called an AFM image. In the AFM image, the brightness of the pixel corresponding to the portion is displayed at a high level in accordance with the height protruding from the surface of the film surface 10a at the observed portion. As an example of the AFM image, an AFM image related to the thin film 10 produced in Experiment 1-D is shown in FIG. 7.

若依據亮度隨著突出高度而變高之AFM圖像的性質，在AFM圖像中將既定的亮度設定為閾值來進行二值化處理，則能夠從薄膜面 10a的表面分離提取既定的高度以上的部位。利用此，針對各AFM圖像，進行將從薄膜面10a的表面突出10nm以上之部份設為明亮度並將除此以外的部份設為暗亮度而分離之二值化處理。在此將對實驗1-D中得到之AFM圖像進行該二值化處理之圖像的一例示於圖8。 According to the nature of the AFM image whose brightness increases with the height of the projection, if the predetermined brightness is set as a threshold in the AFM image to perform the binarization process, the film surface can be viewed from the film surface. The surface separation of 10a extracts a part above a predetermined height. With this, for each AFM image, a binarization process is performed in which a portion protruding from the surface of the thin film surface 10a by 10 nm or more is set to brightness and the other portions are set to dark brightness. An example of an image obtained by performing the binarization processing on the AFM image obtained in Experiment 1-D is shown in FIG. 8.

在將高度為10nm時的亮度作為閾值進行二值化處理之後的圖像中，將成為明亮度之各部份(例如，圖8中之各灰色的島)分別識別為高度為10nm以上的突起而進行檢測。藉由對成為該明亮度之部份的數量進行計數來求出高度為10nm以上的突起的數量。而且，將該突起的數量乘以100並換算為每1mm2的突起的數量的數作為獲取該AFM圖像之區域中之局部的總突起密度D1。在各實驗中，獲取複數個AFM圖像，並求出複數個局部的總突起密度D1，將該些的算術平均設為各實驗中之總突起密度D。將該總突起密度D示於表3的各實驗中之“總突起密度D”欄中。另外，在“總突起密度D”欄中示出有效數字為兩位之值。 In an image after binarizing the brightness at a height of 10 nm as a threshold value, each portion that becomes the brightness (for example, each gray island in FIG. 8) is recognized as a protrusion having a height of 10 nm or more. And test. The number of protrusions having a height of 10 nm or more was obtained by counting the number of portions that became the brightness. Furthermore, the number of times the number of protrusions is multiplied by 100 and converted into the number of protrusions per 1 mm 2 is taken as the total protrusion density D1 of a part in the area where the AFM image is acquired. In each experiment, a plurality of AFM images were acquired, and a plurality of local total protrusion densities D1 were obtained, and the arithmetic average of these was taken as the total protrusion density D in each experiment. This total protrusion density D is shown in the "Total protrusion density D" column in each experiment of Table 3. In addition, the column of "total protrusion density D" shows that a significant figure is a two-digit value.

將上述總突起密度D的求法中進行二值化處理時的閾值變更為從薄膜面10a的表面突出30nm以上時的亮度，其他則利用與求出總突起密度D相同的方法來求出各實驗中之突起密度D(30)。在此，在圖9中示出對於實驗1-D中所得到之AFM圖像，將高度為30nm時的亮度作為閾值來進行二值化處理之圖像的一例。將該突起密度D(30)示於表3的各實驗中之“突起密度D(30)”欄中。另外，在“突起密度D(30)”欄中示出有效數字為3位之值。 The threshold value when the binarization process was performed in the above-mentioned method of obtaining the total protrusion density D was changed to the brightness when protruding from the surface of the thin film surface 10a by 30 nm or more, and other experiments were performed by the same method as the total protrusion density D. The protrusion density D (30). Here, FIG. 9 shows an example of an image obtained by binarizing the AFM image obtained in Experiment 1-D with the brightness at a height of 30 nm as a threshold. This protrusion density D (30) is shown in the "protrusion density D (30)" column in each experiment of Table 3. In addition, in the column of "protrusion density D (30)", a significant figure is a value of 3 digits.

在第1皂化條件下對所製造之各薄膜10進行皂化處理之後，關於AFM圖像的獲取處理，二值化處理及求出突起的數量之前的處理，利用與上述相同的方法求出各實驗中之突起密度Dk(30)。將該突起密度Dk(30)示於表3的各實驗中之“突起密度Dk(30)”欄中。另外，在“突起密度Dk(30)”欄中示出有效數字為3位之值。 After the saponification treatment was performed on each of the manufactured films 10 under the first saponification condition, the respective experiments were performed by the same method as described above regarding the AFM image acquisition processing, the binarization processing, and the processing before the number of protrusions was obtained. The protrusion density Dk (30) in. This protrusion density Dk (30) is shown in the "protrusion density Dk (30)" column in each experiment of Table 3. In addition, in the column of "protrusion density Dk (30)", it is shown that a significant figure has a value of 3 digits.

對於各實驗中之第1皂化條件下的皂化處理前後的各個薄膜10，如下評價貼附得以減少之程度。首先，重疊3片將各薄膜10切割為7cm×7cm的正方形者。接著，以重疊3片各薄膜10之狀態，在溫度25℃、濕度50%之條件下進行24小時調濕之後，以重疊3片之狀態置於溫度40℃、濕度20%之環境下。而且，在3片重疊之各薄膜10之上載置5kg的砝 碼並放置24小時之後，求出薄膜10的貼附面積相對於薄膜10的接觸面積的比例S[單位：%]。用以下A~D的4個階段，對所求出之貼附面積的比例S進行評價。將該評價結果示於表3的各實驗中之“貼附評價”欄中。分別在“皂化處理前”欄中示出皂化處理前的評價，在“皂化處理後”欄中示出皂化處理後的評價。若該貼附評價在A、B、C之中，則為實用上容許的範圍內的薄膜10。 For each film 10 before and after the saponification treatment under the first saponification condition in each experiment, the extent to which the adhesion was reduced was evaluated as follows. First, three sheets were stacked to cut each film 10 into 7 cm × 7 cm squares. Next, the three films 10 were superimposed for 24 hours under the conditions of a temperature of 25 ° C and a humidity of 50%, and then placed in an environment of a temperature of 40 ° C and a humidity of 20% in a state of three overlaps. Then, a weight of 5 kg was placed on each of the three overlapping films 10. After the code was left for 24 hours, the ratio S [unit:%] of the attached area of the film 10 to the contact area of the film 10 was obtained. The following four steps A to D were used to evaluate the ratio S of the obtained attachment area. The evaluation results are shown in the "attachment evaluation" column in each experiment in Table 3. The evaluation before the saponification treatment is shown in the “before the saponification treatment” column, and the evaluation after the saponification treatment is shown in the “after the saponification treatment” column. When this adhesion evaluation is among A, B, and C, it is the film 10 in the range which is practically permissible.

A：小於20% A: less than 20%

B：20%以上且小於30% B: 20% or more and less than 30%

C：30%以上且小於40% C: 30% or more and less than 40%

D：40%以上 D: 40% or more

針對各實驗中之皂化處理前的各個薄膜10，使用霧度計(NDH-5000，Nippon Denshoku Industries Co.Ltd.)，依照JIS-K-7105測定霧度。將霧度的測定結果示於表3的各實驗中之“霧度”欄中。 For each film 10 before the saponification treatment in each experiment, a haze meter (NDH-5000, Nippon Denshoku Industries Co. Ltd.) was used to measure the haze in accordance with JIS-K-7105. The measurement results of the haze are shown in the "haze" column of each experiment in Table 3.

由表2及表3可知以下。觀察到如下傾向：雖然產生了一些偏差，但突起密度D(30)隨著分散液的含有比例N(0.7)及質量比例Wp 的增加而大致增加。並且可知：與添加有微粒14之層係全層時相比，前述層係表層時，將所製造之薄膜的霧度抑制得更低。 Tables 2 and 3 show the following. The following tendency was observed: Although some deviations occurred, the protrusion density D (30) changed with the content ratio N (0.7) and the mass ratio Wp of the dispersion. Increase. In addition, it can be seen that the haze of the produced thin film is suppressed to be lower when the above-mentioned layer-based surface layer is compared with the case where the layer-based entire layer to which the fine particles 14 are added.

並且，總突起密度D與皂化處理前之貼附評價的結果之間未觀察到相關性。例如，在實驗1-C、1-F、1-N、1-P、1-Q中，總突起密度D均為90000個/mm2，但皂化處理前之貼附評價分別為A、A、B、C、C，產生了較大差異。另一方面，突起密度D(30)與皂化處理前之貼附評價的結果之間觀察到了相關性。在突起密度D(30)為20000個/mm2以上之實驗1-A~1-K中，皂化處理前之貼附評價均為A。在突起密度D(30)在16000個/mm2以上且小於20000個/mm2的範圍內之實驗1-O中，皂化處理前之貼附評價為B。在突起密度D(30)為10000個/mm2以上且小於16000個/mm2的範圍內之實驗1-M、1-N、1-P、1-Q中，皂化處理前之貼附評價分別為C、B、C、C。並且，在突起密度D(30)小於10000個/mm2之實驗1-L中，皂化處理前之貼附評價為D。 Moreover, no correlation was observed between the total protrusion density D and the result of the adhesion evaluation before the saponification treatment. For example, in experiments 1-C, 1-F, 1-N, 1-P, and 1-Q, the total protrusion density D was 90,000 pieces / mm 2 , but the evaluation of the adhesion before the saponification treatment was A and A, respectively. , B, C, C, have made a big difference. On the other hand, a correlation was observed between the protrusion density D (30) and the result of the adhesion evaluation before the saponification treatment. In the experiments 1-A to 1-K in which the protrusion density D (30) was 20,000 pieces / mm 2 or more, the evaluation of the adhesion before the saponification treatment was A. In Experiment 1-O in which the protrusion density D (30) was in the range of 16,000 pieces / mm 2 or more and less than 20,000 pieces / mm 2 , the adhesion evaluation before the saponification treatment was B. In the experiments 1-M, 1-N, 1-P, 1-Q in which the protrusion density D (30) was in the range of 10,000 pieces / mm 2 or more and less than 16,000 pieces / mm 2 , the evaluation of the adhesion before the saponification treatment They are C, B, C, and C, respectively. Furthermore, in Experiment 1-L where the protrusion density D (30) was less than 10,000 pieces / mm 2 , the adhesion evaluation before the saponification treatment was D.

並且，突起密度Dk(30)與皂化處理後之貼附評價的結果之間觀察到了相關性。在突起密度Dk(30)為20000個/mm2以上之實驗1-D、1-E、1-G~1-K中，皂化處理後之貼附評價均為A。在突起密度Dk(30)在10000個/mm2以上且小於20000個/mm2的範圍內之實驗1-B、1-C、1-F中，皂化處理後之貼附評價為B。在突起密度Dk(30)為小於10000個/mm2之實驗1-A、1-L~1-Q中，皂化處理後之貼附評價為D。 Furthermore, a correlation was observed between the protrusion density Dk (30) and the result of the adhesion evaluation after the saponification treatment. In the experiments 1-D, 1-E, 1-G ~ 1-K in which the protrusion density Dk (30) was 20,000 pieces / mm 2 or more, the evaluation of the adhesion after the saponification treatment was A. In Experiments 1-B, 1-C, and 1-F in which the protrusion density Dk (30) was in the range of 10,000 pieces / mm 2 or more and less than 20,000 pieces / mm 2 , the adhesion evaluation after the saponification treatment was B. In Experiments 1-A, 1-L ~ 1-Q in which the protrusion density Dk (30) was less than 10,000 pieces / mm 2 , the adhesion evaluation after the saponification treatment was D.

並且，在除固形物以外設為相同條件之實驗1-N、1-P、1-Q中，在使用薄膜彈性模量較低的固形物B和C之實驗1-P、1-Q中，皂化處理前之貼附評價為C，為比使用固形物A之實驗1-N的貼附評價B更低的評價。另一方面，在同樣將固形物以外保持相同條件而提高突起密度D(30)之實驗1-G、1-J、1-K中，在使用固形物B和C之實驗1-J、1-K中，貼附評價為A，為與使用固形物A之實驗1-G的貼附評價A相同的結果。藉此可知：與使用固形物A之薄膜相比，使用彈性模量較低的固形物B和C之薄膜藉由提高突起密度D(30)而得到之減少貼附之效果更大。 In addition, in Experiments 1-N, 1-P, and 1-Q, which were set to the same conditions except for the solids, and in Experiments 1-P and 1-Q, in which the solids B and C with low elastic modulus of the film were used, The adhesion evaluation before the saponification treatment is C, which is a lower evaluation than the adhesion evaluation B of Experiment 1-N using the solid A. On the other hand, in Experiments 1-G, 1-J, and 1-K in which the protrusion density D (30) was increased while maintaining the same conditions other than the solids, Experiments 1-J and 1 in which the solids B and C were used In -K, the adhesion evaluation was A, which is the same result as the adhesion evaluation A of Experiment 1-G using the solid A. From this, it can be seen that, compared with the film using the solid A, the film using the solids B and C having a lower elastic modulus has a greater effect of reducing adhesion by increasing the protrusion density D (30).

並且，對於分別在實施例1-D、1-J、1-K中製造之厚度為20μm、40μm的各薄膜10，確認分別在第1皂化條件下的皂化處理前後是否因捲取成卷狀而產生凹部、折皺及黏連(捲取性)，結果均未產生凹部、 折皺及黏連(捲取性良好)。並且，其中，對厚度為40μm的各薄膜10進行透明塗佈之後確認捲取成卷狀之捲取性，結果捲取性均良好。 In addition, for each film 10 having a thickness of 20 μm and 40 μm manufactured in each of Examples 1-D, 1-J, and 1-K, it was confirmed whether or not each of the films 10 was wound into a roll shape before and after the saponification treatment under the first saponification condition. However, dents, wrinkles, and adhesions were generated (winding properties). As a result, no dents, Wrinkling and adhesion (good take-up). In addition, after each film 10 having a thickness of 40 μm was transparently coated, the rewindability was confirmed to be rolled into a roll shape, and as a result, the rewindability was good.

在此，透明塗佈係指在上述薄膜的表面進行塗佈來設置透明硬塗層。作為透明硬塗層，使用光化射線硬化性樹脂或熱硬化樹脂為較佳。光化射線硬化性樹脂是指以藉由紫外線和電子射線等光化射線的照射發生交聯反應而硬化之樹脂為主成份之層。作為光化射線硬化性樹脂，有紫外線硬化性樹脂和電子射線硬化性樹脂等，亦可以係藉由紫外線和電子射線等以外的光化射線的照射而硬化之樹脂。作為紫外線硬化性樹脂，例如可以舉出紫外線硬化型丙烯酸聚氨酯系樹脂、紫外線硬化型聚酯丙烯酸酯系樹脂、紫外線硬化型環氧丙烯酸酯系樹脂等。 Here, the term “transparent coating” refers to applying a transparent hard coat layer on the surface of the film. As the transparent hard coat layer, an actinic ray-curable resin or a thermosetting resin is preferably used. Actinic ray curable resin refers to a layer whose main component is a resin that is cured by a crosslinking reaction upon irradiation with actinic rays such as ultraviolet rays and electron rays. Examples of actinic ray-curable resins include ultraviolet-curable resins and electron-ray-curable resins. The resins may be cured by irradiation with actinic rays other than ultraviolet rays and electron rays. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, and the like.

[實施例2] [Example 2]

本發明的實施例2係使用上述固形物A，將微粒14的一次粒徑r1和其添加量設為變量來製造7種薄膜10，並確認對減少貼附有效之突起高度H者。7種薄膜中隨機選擇在上述貼附評價的方法中貼附面積的比例S為0%~50%者。 In Example 2 of the present invention, seven kinds of films 10 were manufactured using the solid material A described above with the primary particle diameter r1 of the fine particles 14 and the addition amount thereof as variables, and it was confirmed that the protrusion height H effective for reducing the adhesion was reduced. Among the 7 kinds of films, the ratio S of the attachment area in the above-mentioned method of attachment evaluation was randomly selected from 0% to 50%.

對於該7種薄膜10，分別求出高度為10nm以上的突起的密度(突起密度D(10)[單位：個/mm2])、高度為20nm以上的突起的密度(突起密度D(20)[單位：個/mm2])、高度為30nm以上的突起的密度(突起密度D(30)[單位：個/mm2])、高度為40nm以上的突起的密度(突起密度D(40)[單位：個/mm2])、高度為50nm以上的突起的密度(突起密度D(50)[單位：個/mm2])。該些突起的密度均藉由如下求出：將與各個突起的高度相對應之亮度設定為閾值來對上面說明之AFM圖像進行二值化處理，對明亮度的塊數進行計數並按每1mm2進行換算。 For these 7 kinds of films 10, the density of protrusions having a height of 10 nm or more (protrusion density D (10) [unit: pcs / mm 2 ]) and the density of protrusions having a height of 20 nm or more (protrusion density D (20)) were obtained. [Unit: pcs / mm 2 ]), Density of protrusions with a height of 30 nm or more (protrusion density D (30) [Unit: pcs / mm 2 ]), Density of protrusions with a height of 40 nm or more (Protrusion density D (40) [Unit: pcs / mm 2 ]) and the density of the protrusions having a height of 50 nm or more (protrusion density D (50) [unit: pcs / mm 2 ]). The densities of these protrusions are obtained by setting the brightness corresponding to the height of each protrusion as a threshold to binarize the AFM image described above, counting the number of blocks of brightness and 1mm 2 for conversion.

關於該7種薄膜10，在橫軸取突起密度D(10)、縱軸取貼附面積的比例S之曲線圖中進行標繪，結果得到了圖10所示之曲線圖。橫軸取突起密度D(30)並進行同樣的標繪，結果得到了圖11所示之曲線圖。橫軸取突起密度D(40)並進行同樣的標繪，結果得到了圖12所示之曲線圖。並且，橫軸取突起密度D(50)並進行同樣的標繪，結果得到了圖13所示之曲線圖。 The seven types of films 10 were plotted on a graph in which the projection density D (10) was taken on the horizontal axis and the ratio S of the attached area was taken on the vertical axis. As a result, the graph shown in FIG. 10 was obtained. Taking the projection density D (30) on the horizontal axis and performing the same plot, the graph shown in FIG. 11 was obtained. Taking the projection density D (40) on the horizontal axis and performing the same plot, the graph shown in FIG. 12 was obtained. Furthermore, the projection density D (50) was taken on the horizontal axis and the same plot was performed. As a result, a graph shown in FIG. 13 was obtained.

由圖10的曲線圖可知：突起密度D(10)係對貼附面積的 比例S幾乎沒有影響的因子。另一方面，由第11、12、13圖的曲線圖可知：突起密度D(30)、突起密度D(40)及突起密度D(50)均係對貼附面積的比例S具有較強的相關性之因子。可知突起密度D(30)、突起密度D(40)及突起密度D(50)越大，貼附面積的比例S越小。 It can be seen from the graph of FIG. 10 that the protrusion density D (10) is a function of the area of attachment. The ratio S has little effect on the factor. On the other hand, from the graphs in Figures 11, 12, and 13, it can be seen that the protrusion density D (30), the protrusion density D (40), and the protrusion density D (50) all have a stronger ratio S to the area of attachment. Correlation factor. It can be seen that the larger the projection density D (30), the projection density D (40), and the projection density D (50), the smaller the ratio S of the attachment area.

除了第10~13圖以外，關於該7種薄膜10，還製作出在橫軸取突起密度D(20)、縱軸取貼附面積的比例S之曲線圖中進行標繪者(省略圖)。對於該5個曲線圖求出貢獻率(多重決定係數)R2。關於求出該貢獻率R2之結果，在橫軸取前述5個曲線圖中成為閾值之突起高度H[單位：nm]、縱軸取貢獻率R2之曲線圖中進行標繪，結果得到圖14所示之曲線圖。由該曲線圖可知：高度為30nm以上的突起有助於減小貼附面積的比例S，其中，高度為40nm以上的突起更加有助於減小貼附面積的比例S，其中，高度為50nm以上的突起進一步有助於減小貼附面積的比例S。 In addition to Figures 10 to 13, for the seven kinds of films 10, the graphs are plotted on the graph of the projection density D (20) on the horizontal axis and the ratio S of the attached area on the vertical axis (omitted) . The contribution rate (multiple determination coefficient) R 2 was obtained for these five graphs. The results obtained on the contribution rate of R 2, become the 5 graph the horizontal axis represents the threshold of the protrusion height H [unit: nm], the vertical axis represents the contribution rate R 2 of the graph is plotted, the result obtained The graph shown in FIG. 14. From this graph, it can be seen that protrusions having a height of 30 nm or more contribute to reducing the proportion S of the attachment area. Among them, protrusions having a height of 40 nm or more contribute to reducing the proportion S of the attachment area. The height is 50 nm. The above protrusions further contribute to reducing the ratio S of the attachment area.

[實施例3] [Example 3]

本實施例3係使用藉由與上述實施例1、2相同的方法製作之10種薄膜10，確認有效地減少貼附之突起包含哪種微粒者。10種薄膜隨機選擇在上述貼附評價的方法中貼附面積的比例S為0%~50%者。 In Example 3, ten types of films 10 produced by the same method as in Examples 1 and 2 were used, and it was confirmed that what kind of fine particles are included in the protrusions to be effectively attached. Ten kinds of films were randomly selected in the method of the above-mentioned attachment evaluation, and the ratio S of the attachment area was 0% to 50%.

從與該10種薄膜10的薄膜面10a大致垂直的方向，用SEM(Scanning Electron Microscope，掃描型電子顯微鏡)進行觀察，調查各薄膜10的薄膜面10a上存在之微粒的二次粒徑r2的分佈。關於該10種薄膜10，在橫軸取關於微粒14的含有比例N(0.7)[單位：%]、縱軸取貼附面積的比例S之曲線圖中進行標繪，結果得到了圖15所示之曲線圖。由圖15可知：若含有比例N(0.7)成為30%以上，則貼附面積的比例S小於20%，若含有比例N(0.7)成為50%以上，則貼附面積的比例小於10%。藉此能夠確認：為了減少重疊之薄膜之間的貼附，重要的是將形成薄膜之濃液中之含有比例N(0.7)設為較高。 The SEM (Scanning Electron Microscope) was observed from a direction substantially perpendicular to the film surface 10a of the ten types of films 10, and the secondary particle diameter r2 of the fine particles existing on the film surface 10a of each film 10 was investigated. distributed. With regard to the ten kinds of films 10, the content ratio N (0.7) [unit:%] of the fine particles 14 on the horizontal axis and the ratio S of the attachment area on the vertical axis were plotted, and the result was obtained as shown in FIG. 15. The graph shown. As can be seen from FIG. 15, if the content ratio N (0.7) is 30% or more, the proportion S of the attachment area is less than 20%, and if the content ratio N (0.7) is 50% or more, the proportion of the attachment area is less than 10%. From this, it can be confirmed that, in order to reduce the adhesion between overlapping films, it is important to set the content ratio N (0.7) in the dope forming the film to be high.

[實施例4] [Example 4]

同時使用兩種微粒14的分散液並由與實施例1相同的方法分別製作3層構造的3種薄膜10，針對該3種薄膜10和實施例1的實驗1-D、1-E、1-O中得到之各薄膜10，如下評價減少貼附之效果並求出霧度。將關於同時使用兩種分散液來製作之薄膜10的實驗設為實驗4-R、4-S、4-T，將關 於實施例1的實驗1-D、1-E、1-O中得到之各薄膜10的實驗設為實驗4-D、4-E、4-O。 Using two dispersions of two kinds of fine particles 14 at the same time, three types of thin films 10 having a three-layer structure were produced by the same method as in Example 1. For the three types of films 10 and experiments 1-D, 1-E, and 1 of Example 1, Each of the films 10 obtained in -O was evaluated for the effect of reducing adhesion and the haze was determined as follows. The experiment on the thin film 10 made by using two kinds of dispersion liquids at the same time is set as Experiment 4-R, 4-S, 4-T. The experiments of each thin film 10 obtained in Experiments 1-D, 1-E, and 1-O of Example 1 were set as Experiments 4-D, 4-E, and 4-O.

同時使用之分散液為前述NX90S和RX200，在表4中，將NX90S記為第1成份將RX200記為第2成份。預先混合NX90S和RX200，將由該混合而得到之混合分散液用作第1濃液41和第2濃液42的各原料。表4中之“微粒”的“質量比例”欄中，按每一分散液示出微粒14相對於纖維素醯化物52之質量比例Wp。在表4中，當未使用NX90S時在“第1成份”的“分散液”欄中記為“-”，當未使用RX200時在“第2成份”的“分散液”欄中記為“-”。關於在各實驗中添加有微粒之濃液的層，表4的“微粒”的“添加層”和“固形物種類”分別設為與表2中之“添加層”欄、“固形物種類”欄相同的表示方法。 The dispersions used at the same time are the aforementioned NX90S and RX200. In Table 4, NX90S is described as the first component and RX200 is described as the second component. NX90S and RX200 are mixed in advance, and the mixed dispersion liquid obtained by the mixing is used as each raw material of the first dope 41 and the second dope 42. In the “mass ratio” column of “fine particles” in Table 4, the mass ratio Wp of the fine particles 14 to the cellulose tritide 52 is shown for each dispersion liquid. In Table 4, when the NX90S is not used, it is described as "-" in the "dispersion" column of "the first component", and when the RX200 is not used, it is described as "-" in the "dispersion" column of the "second component" -". Regarding the layers to which the microparticles are added in each experiment, the "additive layer" and "solid type" of the "particles" in Table 4 are set to be the same as those in the "additive layer" column and "solid type" in Table 2. The same way as the column.

在該實施例4中，針對各薄膜10進行前述的基於第2皂化條件之較強的皂化處理和前述的基於第3皂化條件之較弱的皂化處理，並針對各皂化處理後的薄膜10評價減少貼附之效果並求出霧度。減少貼附之效果的評價方法及評價基準和霧度的求法係與實施例1中者相同。結果示於表4。 In Example 4, each of the films 10 was subjected to the aforementioned strong saponification treatment based on the second saponification condition and the aforementioned weaker saponification treatment based on the third saponification condition, and evaluated for each of the saponified films 10 Reduce the effect of attachment and find the haze. The method of evaluating the effect of reducing the adhesion, the evaluation criterion, and the method of obtaining the haze are the same as those in Example 1. The results are shown in Table 4.

Claims (7)

一種薄膜，其具備以下：薄膜面，由聚合物形成；及突起，形成於前述薄膜面上且高度為30nm以上，前述突起包含微粒，並且在前述薄膜面上每1mm2面積內，以104個以上106個以下的範圍形成有前述突起，在前述薄膜面上每1mm2面積內，以15000個以上106個以下的範圍形成有將前述薄膜面皂化處理之後的前述突起，前述聚合物為纖維素醯化物，前述微粒為二氧化矽，且為Nippon Aerosil Co.,Ltd製造的NX90S。A film comprising the following: a film surface formed of a polymer; and protrusions formed on the film surface and having a height of 30 nm or more, the protrusions including fine particles, and the surface of the film surface is 10 4 per 1 mm 2 area. the range of 106 or more or less formed with the projections, the area per 1mm 2 in the film surface in the range of more or less 15 000 106, there is formed the thin film surface after the saponification projection, the polymer It is a cellulose halide, and the aforementioned fine particles are silica, and it is NX90S manufactured by Nippon Aerosil Co., Ltd. 如申請專利範圍第1項之薄膜，其中，將偏光膜黏接於皂化處理之後的前述薄膜面來進行使用。For example, the thin film of the scope of application for the first item, wherein the polarizing film is adhered to the aforementioned film surface after the saponification treatment and used. 一種濃液組成物，其具備以下：聚合物；溶劑，溶解前述聚合物；及微粒，以二次粒子的狀態分散，二次粒徑為0.7μm以上的前述微粒相對於前述微粒總數之含有比例至少為30%，前述聚合物為纖維素醯化物，前述微粒為二氧化矽，且為Nippon Aerosil Co.,Ltd製造的NX90S，前述溶劑為二氯甲烷、甲醇及丁醇的混合物。A dope composition comprising: a polymer; a solvent, dissolving the polymer; and fine particles dispersed in a state of secondary particles, and a content ratio of the fine particles having a secondary particle size of 0.7 μm or more to the total number of the fine particles. At least 30%, the polymer is a cellulose halide, the fine particles are silica, and NX90S manufactured by Nippon Aerosil Co., Ltd., and the solvent is a mixture of dichloromethane, methanol, and butanol. 一種濃液組成物的製造方法，其具備以下步驟：(A)將聚合物和溶劑進行混合，並藉由加熱和攪拌中的至少一方，將前述聚合物溶解於前述溶劑來製作原料濃液；(B)將與前述聚合物及前述溶劑相同成份之聚合物及溶劑和微粒進行混合並攪拌來得到液態的混合物；(C)在前述混合物中，使前述微粒作為二次粒子而分散，從而得到微粒分散液，前述微粒分散液中，0.7μm以上的二次粒徑的前述微粒相對於前述微粒總數之含有比例至少為30%；及(D)將前述原料濃液和前述微粒分散液進行混合來得到濃液組成物，前述聚合物為纖維素醯化物，前述微粒為二氧化矽，且為Nippon Aerosil Co.,Ltd製造的NX90S，前述溶劑為二氯甲烷、甲醇及丁醇的混合物。A method for producing a dope composition, comprising the following steps: (A) mixing a polymer and a solvent, and dissolving the polymer in the solvent by at least one of heating and stirring to prepare a raw material dope; (B) mixing and stirring a polymer, a solvent, and fine particles having the same composition as the polymer and the solvent to obtain a liquid mixture; (C) dispersing the fine particles as secondary particles in the mixture to obtain A microparticle dispersion liquid, in which the content ratio of the microparticles having a secondary particle size of 0.7 μm or more to the total number of microparticles is at least 30%; and (D) mixing the raw material concentrate and the microparticle dispersion To obtain a dope composition, the polymer is a cellulose halide, the fine particles are silica, and NX90S manufactured by Nippon Aerosil Co., Ltd., and the solvent is a mixture of dichloromethane, methanol, and butanol. 如申請專利範圍第4項之濃液組成物的製造方法，其中，在前述C步驟中，藉由對前述混合物施加超音波來使前述微粒在前述混合物中作為二次粒子而分散。For example, in the method for manufacturing a dope composition according to item 4 of the patent application, in the step C, the particles are dispersed as secondary particles in the mixture by applying an ultrasonic wave to the mixture. 如申請專利範圍第4項之濃液組成物的製造方法，其中，在前述C步驟中，藉由使用球磨機來使前述微粒在前述混合物中作為二次粒子而分散。For example, in the method for manufacturing a dope composition according to item 4 of the patent application, in the step C, the fine particles are dispersed as secondary particles in the mixture by using a ball mill. 一種溶液製膜方法，其具備以下步驟：(A)將聚合物和溶劑進行混合，並藉由加熱和攪拌中的至少一方，將前述聚合物溶解於前述溶劑來製作原料濃液；(B)將與前述聚合物及前述溶劑相同成份之聚合物及溶劑和微粒進行混合並攪拌來得到液態的混合物；(C)使前述微粒在前述混合物中作為二次粒子而分散，從而得到微粒分散液，在前述微粒分散液中，0.7μm以上的二次粒徑的前述微粒相對於前述微粒總數之含有比例至少為30%；(D)將前述原料濃液和前述微粒分散液進行混合來得到濃液組成物；(E)藉由從流延模向連續行走之支撐體上連續吐出前述濃液組成物來在前述支撐體上形成流延膜；及(F)藉由從前述支撐體剝下前述流延膜並進行乾燥來得到薄膜，前述聚合物為纖維素醯化物，前述微粒為二氧化矽，且為Nippon Aerosil Co.,Ltd製造的NX90S，前述溶劑為二氯甲烷、甲醇及丁醇的混合物。A solution film forming method comprising the following steps: (A) mixing a polymer and a solvent, and dissolving the polymer in the solvent by at least one of heating and stirring to prepare a raw material concentrate; (B) Mixing and stirring a polymer, a solvent, and fine particles having the same components as the polymer and the solvent to obtain a liquid mixture; (C) dispersing the fine particles as secondary particles in the mixture to obtain a fine particle dispersion, In the fine particle dispersion liquid, a content ratio of the fine particles having a secondary particle diameter of 0.7 μm or more to the total number of the fine particles is at least 30%; (D) mixing the raw material concentrate and the fine particle dispersion to obtain a concentrate A composition; (E) forming a casting film on the support by continuously ejecting the dope composition from a casting die to a continuous walking support; and (F) peeling the foregoing from the support The film was cast and dried to obtain a thin film. The polymer was a cellulose halide, the particles were silica, and NX90S manufactured by Nippon Aerosil Co., Ltd., and the solvent was dichloromethane, Alcohol and a mixture of butanol.
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