TWI822937B - Thin film manufacturing method and manufacturing device, and liquid crystal cured thin film manufacturing method - Google Patents
Thin film manufacturing method and manufacturing device, and liquid crystal cured thin film manufacturing method Download PDFInfo
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- TWI822937B TWI822937B TW108147979A TW108147979A TWI822937B TW I822937 B TWI822937 B TW I822937B TW 108147979 A TW108147979 A TW 108147979A TW 108147979 A TW108147979 A TW 108147979A TW I822937 B TWI822937 B TW I822937B
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- liquid crystal
- base material
- film
- manufacturing
- substrate
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- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
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Abstract
一種薄膜之製造方法，其係具備基材與形成於前述基材之表面S之液晶組成物層的薄膜之製造方法，包含：將前述基材沿運送路徑運送至塗布裝置的工序1，與藉由前述塗布裝置於前述表面S塗布液晶組成物以形成前述液晶組成物層的工序2，其中前述基材之運送係使用運送部件來進行，前述運送部件係以非接觸狀態支撐前述表面S的部件，前述運送係在進行前述工序2前維持前述運送部件與前述表面S的非接觸狀態來進行。A method for manufacturing a thin film including a base material and a liquid crystal composition layer formed on the surface S of the base material, including: a step 1 of conveying the base material to a coating device along a conveyance path, and The process 2 of coating the liquid crystal composition on the surface S by the coating device to form the liquid crystal composition layer, wherein the transportation of the substrate is performed using a transportation member, and the transportation unit is a member that supports the surface S in a non-contact state , the aforementioned transportation is performed while maintaining the non-contact state between the transportation member and the surface S before performing the aforementioned step 2.
Description
本發明係關於薄膜之製造方法及製造裝置以及液晶固化薄膜之製造方法。The present invention relates to a method and device for manufacturing a thin film, and a method for manufacturing a liquid crystal cured thin film.
作為光學薄膜的一種，使用液晶化合物製造之液晶固化薄膜已為人所知。液晶固化薄膜，舉例而言，可藉由於基材上塗布包含聚合性液晶化合物之組成物（液晶組成物）並將聚合性液晶化合物聚合來獲得（參照專利文獻1）。As a type of optical film, a liquid crystal cured film produced using a liquid crystal compound is known. A liquid crystal cured film can be obtained, for example, by coating a composition containing a polymerizable liquid crystal compound (liquid crystal composition) on a base material and polymerizing the polymerizable liquid crystal compound (see Patent Document 1).
『專利文獻』
《專利文獻1》：日本專利公開第2015-143786號公報（對應公報：美國專利申請公開第2015/218453號說明書）"Patent documents"
"
往基材上之液晶組成物的塗布，得將基材送出，往塗布裝置運送，在該塗布裝置中進行。在此種情況下，得在塗布裝置的附近進行將高張力施加於基材來提高平面性一事，以使液晶組成物之塗層厚度均勻。另一方面，若於運送基材時，於基材施加高張力，則可能發生基材的變形。於是，在送出時進行降低基材之張力，在塗布裝置附近，則進行提高基材之張力。Coating of the liquid crystal composition on the substrate can be carried out by feeding the substrate out and transporting it to a coating device, where it is performed. In this case, it is necessary to apply high tension to the substrate near the coating device to improve the flatness, so that the coating thickness of the liquid crystal composition can be uniform. On the other hand, if high tension is applied to the base material when the base material is transported, deformation of the base material may occur. Therefore, the tension of the base material is reduced when feeding out, and the tension of the base material is increased near the coating device.
若使用單一軋輥等裝置將送出時之張力提高至使塗層厚度均勻之張力為止，則在該裝置之前後，施加於基材之張力的變化會變大，藉此，基材之尺寸可能會大幅變化而產生傷痕。If a device such as a single roller is used to increase the tension at the time of delivery to a tension that makes the coating thickness uniform, the change in the tension applied to the substrate before and after the device will become larger, thereby causing the size of the substrate to change. Significant changes may cause scars.
為使施加於基材之張力的變化緩和，可想到使用多個運送輥來運送。然而，即使在運送輥前後之張力變化小，仍可能會發生基材的尺寸變化，故可能會發生基材的變形。若藉由多個運送輥往塗布裝置運送如此變形之基材，則可能因與運送輥的接觸而於基材產生傷痕。In order to alleviate the change in the tension applied to the base material, it is conceivable to use a plurality of conveyance rollers for conveyance. However, even if the change in tension before and after the transport roller is small, the dimensional change of the base material may still occur, and therefore the base material may be deformed. If the substrate deformed in this way is transported to the coating device by a plurality of transport rollers, scratches may occur on the substrate due to contact with the transport rollers.
若於產生了傷痕的基材塗布液晶組成物來製造液晶固化薄膜，則可能會發生問題。舉例而言，於進行液晶組成物的塗布前，有時會對基材進行賦予定向限制力之處理，但若使用產生了傷痕的基材來進行前述處理，則可能會產生定向缺陷。If a liquid crystal composition is coated on a scratched substrate to produce a liquid crystal cured film, problems may occur. For example, before coating the liquid crystal composition, the substrate may be subjected to a treatment to impart an orientation-restricting force. However, if a scratched substrate is used for the above-mentioned treatment, orientation defects may occur.
本發明係鑑於前述問題而首創者，其目的在於提供防止在塗布有液晶組成物之基材產生傷痕的薄膜之製造方法及製造裝置，以及液晶固化薄膜之製造方法。The present invention was initiated in view of the above-mentioned problems, and its object is to provide a method and apparatus for producing a film that prevents scratches on a substrate coated with a liquid crystal composition, and a method for producing a liquid crystal cured film.
本發明人為能解決前述問題而潛心研究。其結果發現：藉由至進行液晶組成物之塗布為止的期間，利用以非接觸狀態支撐基材之塗布有液晶組成物之面的運送部件，維持與該基材之塗布有液晶組成物之面的非接觸狀態，進行基材之運送，可解決前述問題，進而完成本發明。The inventors of the present invention have devoted themselves to research to solve the aforementioned problems. As a result, they found that by using a transport member that supports the surface of the substrate coated with the liquid crystal composition in a non-contact state until the liquid crystal composition is applied, the surface of the substrate coated with the liquid crystal composition can be maintained in contact with the surface of the substrate. The above problems can be solved by transporting the substrate in a non-contact state, thereby completing the present invention.
亦即，本發明包含下述內容。That is, the present invention includes the following contents.
［1］一種薄膜之製造方法，其係具備基材與形成於前述基材之表面S之液晶組成物層的薄膜之製造方法，包含：
將前述基材沿運送路徑運送至塗布裝置的工序1，與
藉由前述塗布裝置於前述表面S塗布液晶組成物以形成前述液晶組成物層的工序2，其中
前述基材之運送係使用運送部件來進行，
前述運送部件係以非接觸狀態支撐前述表面S的部件，前述運送係在進行前述工序2前維持前述運送部件與前述表面S的非接觸狀態來進行。[1] A method of manufacturing a thin film including a substrate and a liquid crystal composition layer formed on the surface S of the substrate, including:
The
［2］如［1］所記載之薄膜之製造方法，其包含對前述基材之前述表面S賦予定向限制力的工序A，其中
已進行前述工序A後至進行前述工序2為止的期間，維持前述表面S與其他部件的非接觸狀態來進行前述基材之運送。[2] The method for producing a film according to [1], which includes step A of imparting an orientation restricting force to the front surface S of the base material, wherein
After the process A is performed and the
［3］如［2］所記載之薄膜之製造方法，其中前述工序A係藉由選自摩擦處理、光定向處理及延伸處理的處理方法來進行。[3] The method for producing a film according to [2], wherein the step A is performed by a treatment method selected from the group consisting of rubbing treatment, photo-orientation treatment, and stretching treatment.
［4］如［1］～［3］之任一項所記載之薄膜之製造方法，其中在前述工序1中，前述基材係在做成具備前述基材與貼合於前述基材之前述表面S之保護薄膜的附保護薄膜之基材的狀態下運送。[4] The method for manufacturing a film according to any one of [1] to [3], wherein in the
［5］如［4］所記載之薄膜之製造方法，其包含於前述工序2前進行的工序B1及工序B2，其中
前述工序B1係自前述附保護薄膜之基材剝離前述保護薄膜以獲得前述表面S露出之前述基材的工序，
前述工序B2係將已進行前述工序B1後的前述基材之張力阻斷的工序。[5] The method for manufacturing a film according to [4], which includes step B1 and step B2 performed before
［6］如［1］～［5］之任一項所記載之薄膜之製造方法，其中前述基材係由能夠藉由延伸處理來控制定向限制力的材料而成。[6] The method for producing a film according to any one of [1] to [5], wherein the base material is made of a material capable of controlling the orientation restricting force by stretching treatment.
［7］如［1］～［6］之任一項所記載之薄膜之製造方法，其中前述運送部件與前述基材之前述表面S的間隔為1 mm以下。[7] The method for producing a film according to any one of [1] to [6], wherein the distance between the transport member and the front surface S of the base material is 1 mm or less.
［8］如［1］～［7］之任一項所記載之薄膜之製造方法，其中在前述運送路徑之較前述塗布裝置還要上游的前述基材之運送張力T1 為30 N/m以上且500 N/m以下。[8] The method for manufacturing a film according to any one of [1] to [7], wherein the conveyance tension T 1 of the substrate upstream of the coating device on the conveyance path is 30 N/m. Above and below 500 N/m.
［9］如［1］～［8］之任一項所記載之薄膜之製造方法，其中前述運送部件係具有將氣體噴出之孔的部件，所述氣體將前述基材保持於非接觸狀態， 前述氣體係壓力為0.05 MPa以上且0.7 MPa以下的高壓空氣。[9] The method for manufacturing a film according to any one of [1] to [8], wherein the conveying member has a hole for ejecting gas that keeps the base material in a non-contact state, The pressure of the aforementioned gas system is high-pressure air between 0.05 MPa and 0.7 MPa.
［10］如［1］～［9］之任一項所記載之薄膜之製造方法，其中前述運送部件係與運送方向平行之方向的截面具有弧狀之截面弧狀部的部件。[10] The method for manufacturing a film according to any one of [1] to [9], wherein the conveying member is a member having an arcuate cross-section in a direction parallel to the conveying direction.
［11］如［1］～［10］之任一項所記載之薄膜之製造方法，其中前述運送部件係由具有多個孔之多孔質材料而成的部件，前述孔之平均孔徑為10 μm以下。[11] The method for manufacturing a film according to any one of [1] to [10], wherein the conveying member is made of a porous material having a plurality of pores, and the average pore diameter of the pores is 10 μm. the following.
［12］如［1］～［11］之任一項所記載之薄膜之製造方法，其中在前述工序2中的前述基材之運送張力T2
為200 N/m以上，
在前述運送路徑之較前述塗布裝置還要上游的前述基材之運送張力T1
，較前述運送張力T2
還低，且前述運送張力T1
係以自前述基材之送出至進行前述工序2為止的期間階段性變高的方式設定。[12] The method for producing a film according to any one of [1] to [11], wherein the conveyance tension T 2 of the base material in the aforementioned step 2 is 200 N/m or more, and the conveyance path is The conveying tension T 1 of the substrate upstream of the coating device is lower than the conveying
［13］一種薄膜之製造裝置，其係在如［1］～［12］之任一項所記載之薄膜之製造方法中使用的薄膜之製造裝置，具備： 於前述基材之前述表面S塗布液晶組成物以形成前述液晶組成物之層體的塗布裝置，與 將前述基材運送至前述塗布裝置的運送部件，其中 前述運送部件係在以非接觸狀態支撐前述表面S的狀態下運送前述基材的運送部件。[13] A thin film manufacturing device used in the thin film manufacturing method described in any one of [1] to [12], including: A coating device for coating a liquid crystal composition on the front surface S of the base material to form a layer of the liquid crystal composition, and The aforementioned base material is transported to the transportation component of the aforementioned coating device, wherein The conveyance member is a conveyance member that conveys the base material while supporting the surface S in a non-contact state.
［14］一種液晶固化薄膜之製造方法，其係具備基材與形成於前述基材之表面S之液晶固化層的液晶固化薄膜之製造方法，包含：
藉由如［1］～［12］之任一項所記載之薄膜之製造方法來製造具備前述基材與形成於前述基材之前述表面S之前述液晶組成物層的薄膜的工序，以及
在前述運送路徑之較前述工序2還要下游進行的工序3A及工序3B，其中
前述工序3A係將前述液晶組成物層固化以於前述基材之前述表面S形成前述液晶固化層的工序，
前述工序3B係於前述液晶固化層之上進一步形成硬塗層的工序，
自前述工序2往前述工序3A之運送（2－3A）係使用運送部件（2－3A）來進行，前述運送部件（2－3A）係以非接觸狀態支撐前述薄膜之前述液晶組成物層側之面的運送部件，前述運送（2－3A）係自已進行前述工序2後至進行前述工序3A為止的期間維持前述運送部件（2－3A）與前述薄膜之前述液晶組成物層側之面的非接觸狀態來進行，且
自前述工序3A往前述工序3B之運送（3A－3B）係使用運送部件（3A－3B）來進行，前述運送部件（3A－3B）係以非接觸狀態支撐前述薄膜之前述液晶固化層側之面的運送部件，前述運送（3A－3B）係自已進行前述工序3A後至進行前述工序3B為止的期間維持前述運送部件（3A－3B）與前述薄膜之前述液晶固化層側之面的非接觸狀態來進行。[14] A method for manufacturing a liquid crystal cured film, which includes a substrate and a liquid crystal cured layer formed on the surface S of the substrate, including:
The process of producing a thin film including the base material and the liquid crystal composition layer formed on the front surface S of the base material by the thin film manufacturing method according to any one of [1] to [12], and
Processes 3A and 3B are performed downstream of the
根據本發明，可提供防止在塗布有液晶組成物之基材產生傷痕的薄膜之製造方法及製造裝置，以及液晶固化薄膜之製造方法。According to the present invention, it is possible to provide a method and apparatus for producing a film that prevents scratches on a substrate coated with a liquid crystal composition, and a method for producing a liquid crystal cured film.
以下揭示實施型態及示例物以詳細說明本發明。惟本發明並非受限於以下所揭示之實施型態及示例物者，在不脫離本發明之申請專利範圍及其均等之範圍的範圍內，得任意變更而實施。Embodiments and examples are disclosed below to explain the present invention in detail. However, the present invention is not limited to the embodiments and examples disclosed below, and may be arbitrarily modified and implemented without departing from the patentable scope of the present invention and its equivalent scope.
在以下說明中，所謂某層體之「面內方向」，除非另有註記，否則表示與層體平面平行的方向。In the following description, the so-called "in-plane direction" of a certain layer means the direction parallel to the plane of the layer unless otherwise noted.
在以下說明中，所謂某層體之「厚度方向」，除非另有註記，否則表示與層體平面垂直的方向。據此，除非另有註記，否則某層體之面內方向與厚度方向為垂直。In the following description, the so-called "thickness direction" of a certain layer means the direction perpendicular to the plane of the layer unless otherwise noted. Accordingly, unless otherwise noted, the in-plane direction and thickness direction of a certain layer are perpendicular.
在以下說明中，所謂「長條狀」之薄膜（該薄膜亦包含以下說明之「基材」），係謂相對於幅寬具有5倍以上之長度的薄膜，以具有10倍或其以上之長度為佳，具體上係謂具有可收捲成卷狀儲存或搬運之程度之長度的薄膜。長條狀之薄膜的長度之上限並無特別限制，得定為例如相對於幅寬為10萬倍以下。In the following description, the so-called "long strip" film (the film also includes the "substrate" described below) refers to a film with a length of 5 times or more relative to the width, and a film with a length of 10 times or more. The preferred length is, specifically, a film that is long enough to be rolled into a roll for storage or transportation. The upper limit of the length of the long film is not particularly limited, but may be, for example, 100,000 times or less relative to the width.
在本申請案中，所謂薄膜（該薄膜亦包含以下說明之「基材」）之MD方向，係在製造裝置或裁切裝置中所運送之長條狀之薄膜及將其切割而獲得之裁切後之薄膜所運送之方向，所謂TD方向，係垂直於MD方向且與薄膜之面平行之方向。MD方向與在製造裝置等中所運送之長條形狀之薄膜及裁切後之薄膜的長邊方向一致，TD方向與在製造裝置或裁切裝置中所運送之長條形狀之薄膜及裁切後之薄膜的幅寬方向一致。In this application, the so-called MD direction of the film (the film also includes the "substrate" explained below) refers to the long film conveyed in the manufacturing device or the cutting device and the cut obtained by cutting it. The direction in which the cut film is transported, the so-called TD direction, is the direction perpendicular to the MD direction and parallel to the surface of the film. The MD direction is consistent with the long side direction of the long-shaped film and the cut film conveyed in the manufacturing device, etc., and the TD direction is consistent with the long-side direction of the long-shaped film and cut film conveyed in the manufacturing device or cutting device. After that, the width direction of the film is consistent.
所謂縱向延伸，除非另有註記，否則表示將薄膜（亦包含延伸前之薄膜、延伸前之基材）沿薄膜之長邊方向延伸，所謂橫向延伸，除非另有註記，否則表示將薄膜沿其幅寬方向延伸。所謂斜向延伸，除非另有註記，否則表示將薄膜沿斜向延伸。所謂薄膜之斜向，除非另有註記，否則表示係為此薄膜之面內方向且與此薄膜之幅寬方向既不平行亦不垂直的方向。The so-called longitudinal extension, unless otherwise noted, means extending the film (including the film before stretching and the substrate before stretching) along the long side of the film. The so-called transverse extension, unless otherwise noted, means extending the film along its length. Extend across the width. The so-called diagonal extension means that the film is extended diagonally unless otherwise noted. The so-called oblique direction of the film, unless otherwise noted, means the in-plane direction of the film and the direction that is neither parallel nor perpendicular to the width direction of the film.
在以下說明中，某層體之面內相位差Re，除非另有註記，否則係由Re＝（nx－ny）×d所示之值。於此，nx表示係為與層體之厚度方向垂直之方向（面內方向）且賦予最大折射率之方向的折射率。ny表示係為層體之前述面內方向且與nx之方向正交之方向的折射率。d表示層體之厚度。相位差之量測波長，除非另有註記，否則為590 nm。面內相位差Re可使用相位差計（Axometrics公司製之「AxoScan」）來量測。In the following explanation, the in-plane phase difference Re of a certain layer is a value represented by Re=(nx-ny)×d, unless otherwise noted. Here, nx represents the refractive index in the direction perpendicular to the thickness direction of the layer (in-plane direction) and in the direction giving the maximum refractive index. ny represents the refractive index in the direction in the aforementioned in-plane direction of the layer and orthogonal to the direction of nx. d represents the thickness of the layer. The measurement wavelength of phase difference is 590 nm unless otherwise noted. The in-plane phase difference Re can be measured using a phase difference meter ("AxoScan" manufactured by Axometrics).
在以下說明中，所謂某層體之慢軸，除非另有註記，否則係謂面內方向之慢軸。In the following description, the so-called slow axis of a certain layer refers to the slow axis in the in-plane direction, unless otherwise noted.
在以下說明中，所謂構件之方向為「平行」及「垂直」，除非另有註記，否則在不損及本發明之效果的範圍內，亦可包含例如±4°──以±3°為佳，以±1°為較佳──之範圍內的誤差。In the following description, the so-called directions of components are "parallel" and "perpendicular". Unless otherwise noted, within the scope that does not impair the effect of the present invention, it may also include, for example, ±4°──with ±3° as the It is better to use ±1° as the error within the range.
在以下說明中，具有取代基之基的碳原子數，除非另有註記，否則不包含前述取代基的碳原子數。據此，舉例而言，「亦可具有取代基之碳原子數1～20的烷基」這樣的記載，表示不包含取代基之碳原子數之烷基自身的碳原子數為1～20。In the following description, the number of carbon atoms of a group having a substituent does not include the number of carbon atoms of the aforementioned substituent, unless otherwise noted. Accordingly, for example, the description "an alkyl group having 1 to 20 carbon atoms which may have a substituent" means that the alkyl group itself having 1 to 20 carbon atoms does not include a substituent.
在以下說明中，「偏光板」除非另有註記，否則作為包含樹脂薄膜等具有可撓性之薄膜及薄片之用語使用。In the following description, "polarizing plate" is used as a term including flexible films and sheets such as resin films, unless otherwise noted.
［本發明之薄膜之製造方法的概要］[Outline of the manufacturing method of the film of the present invention]
本發明之薄膜之製造方法，係具備基材與形成於基材之表面S之液晶組成物層的薄膜之製造方法。如於此所使用，「表面S」之用語，表示基材之成為液晶組成物之塗布對象的表面。本發明之薄膜之製造方法，包含：將基材沿運送路徑運送至塗布裝置的工序1，與藉由塗布裝置於基材之表面S塗布液晶組成物以形成液晶組成物層的工序2。在本發明之薄膜之製造方法中，基材之運送係使用運送部件來進行。運送部件係以非接觸狀態支撐基材之表面S的運送部件。基材之運送係在進行工序2前維持運送部件與基材之表面S的非接觸狀態來進行。在本發明中，所謂某表面與某部件的「非接觸狀態」，意謂該部件不與該表面「直接」接觸的狀態，包含該部件與成為對象之面間接性接觸。所謂「間接性」接觸，係謂該部件與成為對象之面中介位於此等之間的又另一部件而接觸。舉例而言，在係為於成為對象之面已貼合有保護薄膜等之狀態的情況下，貼合於成為對象之面的保護薄膜與運送部件直接接觸之情事，包含於成為對象之面與運送部件的「非接觸狀態」。The method of manufacturing a thin film of the present invention is a method of manufacturing a thin film including a base material and a liquid crystal composition layer formed on the surface S of the base material. As used here, the term "surface S" means the surface of the base material to which the liquid crystal composition is applied. The method for manufacturing a film of the present invention includes: a step of transporting a substrate to a coating device along a transport path; and a step of coating a liquid crystal composition on the surface S of the substrate by the coating device to form a liquid crystal composition layer. In the film manufacturing method of the present invention, the substrate is transported using a transport member. The conveying member is a conveying member that supports the surface S of the base material in a non-contact state. The substrate is transported while maintaining the non-contact state between the transport member and the surface S of the substrate before performing
［本發明之薄膜之製造裝置的概要］[Outline of the thin film manufacturing apparatus of the present invention]
本發明之薄膜之製造裝置，係在本發明之薄膜之製造方法使用的製造裝置，具備：於基材之表面S塗布液晶組成物以形成液晶組成物之層體的塗布裝置，與將基材運送至塗布裝置的運送部件。在本發明之薄膜之製造裝置中，運送部件除非另有註記，否則係在以非接觸狀態支撐基材之表面S的狀態下運送基材的運送部件。The thin film manufacturing apparatus of the present invention is a manufacturing apparatus used in the thin film manufacturing method of the present invention, and includes: a coating device for applying a liquid crystal composition to the surface S of a base material to form a layer of the liquid crystal composition; Transport components to the coating unit. In the film manufacturing apparatus of the present invention, unless otherwise noted, the transport member is a transport member that transports the substrate while supporting the surface S of the substrate in a non-contact state.
［本發明之液晶固化薄膜之製造方法的概要］[Outline of the manufacturing method of the liquid crystal cured film of the present invention]
本發明之液晶固化薄膜之製造方法，係使藉由本發明之薄膜之製造方法獲得的薄膜之液晶組成物層固化而成的液晶固化薄膜之製造方法。亦即，本發明之液晶固化薄膜之製造方法，係具備基材與形成於基材之表面S之液晶固化層的液晶固化薄膜之製造方法，包含：藉由本發明之薄膜之製造方法來製造具備基材與形成於基材之表面S之液晶組成物層的薄膜的工序，以及在運送路徑之較工序2還要下游進行的工序3A及工序3B。工序3A係將液晶組成物層固化以於基材之表面S形成液晶固化層的工序，工序3B係於液晶固化層之上進一步形成硬塗層的工序。使用運送部件（下面有為了區別於其他工序使用之運送部件而將於此工序使用之運送部件稱作「運送部件（2－3A）」的情形）進行自工序2往工序3A的運送（下面有將此特定之運送稱作「運送（2－3A）」的情形）。運送部件（2－3A）係以非接觸狀態支撐薄膜之液晶組成物層側之面的運送部件。運送（2－3A）係自已進行工序2後至進行工序3A為止的期間維持運送部件（2－3A）與薄膜之液晶組成物層側之面的非接觸狀態來進行。使用運送部件（下面有將於此工序使用之運送部件稱作「運送部件（3A－3B）」的情形）進行自工序3A往工序3B的運送（下面有將此特定之運送稱作「運送（3A－3B）」的情形）。運送部件（3A－3B）係以非接觸狀態支撐薄膜之液晶固化層側之面的運送部件。運送（3A－3B）係自已進行工序3A後至進行工序3B為止的期間維持運送部件（3A－3B）與薄膜之液晶固化層側之面的非接觸狀態來進行。The method for producing a liquid crystal cured film of the present invention is a method for producing a liquid crystal cured film obtained by solidifying the liquid crystal composition layer of the film obtained by the method for producing the film of the present invention. That is, the method of manufacturing a liquid crystal cured film of the present invention is a method of manufacturing a liquid crystal cured film that includes a base material and a liquid crystal cured layer formed on the surface S of the base material, including: manufacturing a liquid crystal cured film having The steps of forming a thin film of a liquid crystal composition layer on a substrate and a surface S of the substrate, and steps 3A and 3B that are performed downstream of
［實施型態1］[Implementation type 1]
以下參照圖1～4，同時說明本發明相關的實施型態1之薄膜之製造方法及製造裝置，以及使用藉由前述薄膜之製造方法獲得之薄膜的液晶固化薄膜之製造方法。圖1係繪示於實施型態1相關的薄膜之製造方法使用之裝置的側視示意圖。圖2係繪示在實施型態1相關的薄膜之製造方法中所獲得之薄膜的剖面示意圖。圖3係繪示附保護薄膜之基材的剖面示意圖。圖4係繪示運送部件的剖面示意圖。1 to 4 , a method for manufacturing a film and a manufacturing apparatus according to
［1.薄膜之製造方法］[1. Film manufacturing method]
本實施型態之薄膜之製造方法，包含：將藉由送出裝置101送出之基材1運送至塗布裝置110的工序1，與藉由塗布裝置110於基材1A之表面S塗布液晶組成物以形成液晶組成物層的工序2。本實施型態之薄膜之製造方法係使用圖1所示之薄膜之製造裝置100來進行。The method of manufacturing a film according to this embodiment includes the
在本實施型態之薄膜之製造方法中，將藉由送出裝置101送出之基材1沿圖示右方向（A1所示之方向）運送，在裝置102中，對基材1之表面S（在圖1中為下側面）賦予定向限制力（工序A）。已進行此工序A後，於基材（經賦予定向限制力之基材1A，以下亦簡稱作「基材1A」）之表面S貼合保護薄膜2，做成附保護薄膜之基材20，運送該附保護薄膜之基材20。本實施型態之薄膜之製造方法於運送至塗布裝置110前（工序2之前），包含：自附保護薄膜之基材20剝離保護薄膜2以獲得基材1A的工序B1，與將已進行工序B1後獲得之基材1A的張力阻斷的工序B2。藉由以非接觸狀態支撐基材1A之表面S（在圖1中之下側面）的運送部件121&122，將已進行工序B2後之基材1A運送至塗布裝置110。然後，進行藉由塗布裝置110於基材1A之表面S塗布液晶組成物以形成液晶組成物層5的工序2。藉此，可獲得如圖2所示具備基材1A與形成於基材1A之表面S之液晶組成物層5的薄膜10。在本發明中，工序A、工序B1、工序B2係任意工序，進行此等任意工序一事及進行工序的時機，不受限於在本實施型態說明的態樣。以下說明各工序。In the film manufacturing method of this embodiment, the
［1.1.工序1］[1.1. Process 1]
工序1係將基材1運送至塗布裝置110的工序。
在工序1中，使用運送部件121&122，將自送出裝置101送出的基材1運送至塗布裝置110。In
［基材］[Substrate]
作為基材，通常得使用樹脂薄膜或玻璃板。作為基材，以使用長條狀之樹脂薄膜為佳。作為基材，以由能夠藉由延伸處理來控制定向限制力的材料而成者為佳。As a base material, a resin film or a glass plate is usually used. As the base material, a long resin film is preferably used. As the base material, it is preferable to use a material that can control the orientation restricting force by stretching treatment.
作為用作基材的樹脂薄膜，可列舉例如：包含含脂環結構聚合物的樹脂薄膜、聚對酞酸乙二酯（PET）薄膜、聚萘二甲酸乙二酯（PEN）薄膜、丙烯酸薄膜、聚乙烯（PE）薄膜、聚丙烯（PP、OPP）薄膜、聚碳酸酯（PC）薄膜、聚苯乙烯（PS）薄膜、三乙酸纖維素（TAC）薄膜、聚氯乙烯（PVC）薄膜、聚醯亞胺（PI）薄膜等塑膠之薄膜，以及聚苯硫醚（PPS）薄膜、聚四氟乙烯（PTFE）薄膜、聚醚醚酮（PEEK）薄膜、聚醚碸（PES）薄膜、聚芳醯胺薄膜等超級工程塑膠之薄膜。Examples of the resin film used as the base material include a resin film containing an alicyclic structure-containing polymer, a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, and an acrylic film. , polyethylene (PE) film, polypropylene (PP, OPP) film, polycarbonate (PC) film, polystyrene (PS) film, triacetate cellulose (TAC) film, polyvinyl chloride (PVC) film, Polyimide (PI) film and other plastic films, as well as polyphenylene sulfide (PPS) film, polytetrafluoroethylene (PTFE) film, polyether ether ketone (PEEK) film, polyether styrene (PES) film, poly Films of super engineering plastics such as arylamide films.
得用作基材的樹脂薄膜由熱塑性樹脂而成，熱塑性樹脂包含聚合物。作為該聚合物，可列舉：含脂環結構聚合物、聚對酞酸乙二酯、聚萘二甲酸乙二酯、丙烯酸聚合物、甲基丙烯酸聚合物、聚乙烯、聚丙烯、聚碳酸酯、聚苯乙烯、三乙酸纖維素、聚氯乙烯、聚醯亞胺、聚苯硫醚、聚四氟乙烯、聚醚醚酮、聚醚碸、聚芳醯胺及此等的組合。就係為能夠藉由延伸處理來控制定向限制力之材料的觀點而言，以含脂環結構聚合物為佳。The resin film used as the base material is made of thermoplastic resin, which contains a polymer. Examples of the polymer include alicyclic structure-containing polymers, polyethylene terephthalate, polyethylene naphthalate, acrylic polymers, methacrylic acid polymers, polyethylene, polypropylene, and polycarbonate. , polystyrene, cellulose triacetate, polyvinyl chloride, polyimide, polyphenylene sulfide, polytetrafluoroethylene, polyetheretherketone, polyetherether, polyarylamide and combinations thereof. From the viewpoint of being a material that can control the orientation restriction force by stretching treatment, an alicyclic structure-containing polymer is preferred.
含脂環結構聚合物係於重複單元中具有脂環結構的非晶性之聚合物，使用於主鏈中含有脂環結構的聚合物及於側鏈含有脂環結構的聚合物之任一者皆可。The alicyclic structure-containing polymer is an amorphous polymer having an alicyclic structure in the repeating unit. It is used for both polymers containing an alicyclic structure in the main chain and polymers containing an alicyclic structure in the side chain. Either way.
作為脂環結構雖可列舉例如：環烷結構、環烯結構等，但就熱穩定性等的觀點而言，以環烷結構為佳。Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure. However, from the viewpoint of thermal stability and the like, a cycloalkane structure is preferred.
1個脂環結構之構成重複單元的碳數雖無特別限制，但通常為4個～30個，以5個～20個為佳，以6個～15個為較佳。Although the number of carbon atoms constituting the repeating unit of one alicyclic structure is not particularly limited, it is usually 4 to 30, preferably 5 to 20, and more preferably 6 to 15.
含脂環結構聚合物中之具有脂環結構之重複單元的比例，係因應使用目的而適當選擇，但通常為50重量%以上，以70重量%以上為佳，以90重量%以上為較佳。藉由如此增加具有脂環結構的重複單元，可提高樹脂薄膜的耐熱性。The proportion of repeating units having an alicyclic structure in the alicyclic structure-containing polymer is appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, and preferably 90% by weight or more. . By increasing the repeating units having an alicyclic structure in this way, the heat resistance of the resin film can be improved.
含脂環結構聚合物具體上可列舉：（1）降𦯉烯聚合物、（2）單環的環烯烴聚合物、（3）環狀共軛二烯聚合物、（4）乙烯脂環烴聚合物，及此等的氫化物等。此等之中，就透明性及成形性的觀點而言，以降𦯉烯聚合物及此等的氫化物為較佳。Specifically, polymers containing alicyclic structures can be listed as follows: (1) norphene polymers, (2) monocyclic cycloolefin polymers, (3) cyclic conjugated diene polymers, (4) ethylene alicyclic hydrocarbons Polymers, and their hydrides, etc. Among these, from the viewpoint of transparency and formability, norphene polymers and these hydrides are preferred.
作為降𦯉烯聚合物，可列舉例如：降𦯉烯單體的開環聚合物、降𦯉烯單體與能夠開環共聚合之其他單體的開環共聚物及此等的氫化物；降𦯉烯單體的加成聚合物、降𦯉烯單體與能夠共聚合之其他單體的加成共聚物等。此等之中，就透明性的觀點而言，以降𦯉烯單體的開環聚合物氫化物為尤佳。Examples of norvinyl polymers include ring-opened polymers of nordecene monomers, ring-opened copolymers of nordecene monomers and other monomers capable of ring-opening copolymerization, and hydrogenated products thereof; Addition polymers of olefin monomers, addition copolymers of olefin monomers and other monomers that can be copolymerized, etc. Among these, from the viewpoint of transparency, the ring-opened polymer hydrogenated product of norphene monomer is particularly preferred.
上述含脂環結構聚合物可選自例如日本專利公開第2002-321302號公報所揭露的聚合物。The alicyclic structure-containing polymer may be selected from polymers disclosed in Japanese Patent Publication No. 2002-321302, for example.
含脂環結構聚合物，其玻璃轉移溫度以80℃以上為佳，以100℃～250℃為較佳。玻璃轉移溫度位於此種範圍的含脂環結構聚合物，在高溫下之使用時的變形及應力不易產生，耐久性優異。For polymers containing alicyclic structures, the glass transition temperature is preferably above 80°C, and preferably between 100°C and 250°C. Polymers containing an alicyclic structure with a glass transition temperature in this range are less prone to deformation and stress when used at high temperatures and have excellent durability.
含脂環結構聚合物的分子量，以藉由使用環己烷作為溶媒（在樹脂不溶解的情況下為甲苯）的凝膠滲透層析法（以下簡稱作「GPC」。）來量測之聚異戊二烯換算（溶媒為甲苯時係聚苯乙烯換算）的重量平均分子量（Mw）計，通常為10,000～100,000，以25,000～80,000為佳，以25,000～50,000為較佳。重量平均分子量位於此種範圍時，樹脂薄膜之機械性強度及成形加工性取得高度平衡。The molecular weight of a polymer containing an alicyclic structure is measured by gel permeation chromatography (hereinafter referred to as "GPC") using cyclohexane as a solvent (toluene if the resin is not dissolved). The weight average molecular weight (Mw) in terms of isoprene conversion (polystyrene conversion when the solvent is toluene) is usually 10,000 to 100,000, preferably 25,000 to 80,000, and more preferably 25,000 to 50,000. When the weight average molecular weight is within this range, the mechanical strength and molding processability of the resin film are highly balanced.
含脂環結構聚合物之分子量分布（重量平均分子量（Mw）／數量平均分子量（Mn））通常為1～10，以1～4為佳，以1.2～3.5為較佳。The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the alicyclic structure-containing polymer is usually 1 to 10, preferably 1 to 4, and preferably 1.2 to 3.5.
包含含脂環結構聚合物的樹脂，其分子量2,000以下之樹脂成分（亦即寡聚物成分）的含量，以5重量%以下為佳，以3重量%以下為較佳，以2重量%以下為更佳。若寡聚物成分之量位於前述範圍內，則在表面S之微細的凸部之產生會減少，厚度之參差會變小，表面精細度會上升。寡聚物成分之量的減低，得藉由適切設定聚合觸媒及氫化觸媒的選擇；聚合、氫化等的反應條件；在將樹脂做成成形用材料而顆粒化之工序中的溫度條件；等條件來進行。For resins containing polymers with alicyclic structures, the content of resin components (i.e. oligomer components) with a molecular weight of 2,000 or less is preferably 5 wt% or less, preferably 3 wt% or less, and 2 wt% or less. For the better. If the amount of the oligomer component is within the above range, the occurrence of fine protrusions on the surface S will be reduced, the thickness variation will be smaller, and the surface fineness will be improved. The amount of oligomer components can be reduced by appropriately setting the selection of polymerization catalyst and hydrogenation catalyst; the reaction conditions of polymerization, hydrogenation, etc.; and the temperature conditions in the process of making the resin into a molding material and granulating it; Wait for the conditions to proceed.
寡聚物之成分量，可藉由前述GPC來量測。The content of oligomers can be measured by the aforementioned GPC.
包含含脂環結構聚合物的樹脂雖可僅由含脂環結構聚合物而成，但只要不顯著損及本發明之效果，亦可包含任意摻合劑。包含含脂環結構聚合物的樹脂中之含脂環結構聚合物的比例，以70重量%以上為佳，以80重量%以上為較佳。Although the resin containing the alicyclic structure-containing polymer may be composed solely of the alicyclic structure-containing polymer, any blending agent may be included as long as the effect of the present invention is not significantly impaired. The proportion of the alicyclic structure-containing polymer in the resin containing the alicyclic structure-containing polymer is preferably 70% by weight or more, and more preferably 80% by weight or more.
作為包含含脂環結構聚合物的樹脂之合適的具體例，得舉出日本瑞翁公司製之「ZEONOR」。As a suitable specific example of the resin containing an alicyclic structure-containing polymer, "ZEONOR" manufactured by Japan Zeon Corporation can be cited.
樹脂除了上述聚合物以外，還得包含任意成分。作為任意成分，可列舉例如：酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑等抗氧化劑；受阻胺系光穩定劑等光穩定劑；石油系蠟、費托蠟、聚伸烷蠟等蠟；山梨醇系化合物、有機磷酸之金屬鹽、有機羧酸之金屬鹽、高嶺土及滑石等成核劑；二胺基二苯乙烯衍生物、香豆素衍生物、唑系衍生物（例如苯并㗁唑衍生物、苯并***衍生物、苯并咪唑衍生物及苯并噻唑衍生物）、咔唑衍生物、吡啶衍生物、萘二甲酸衍生物及咪唑酮衍生物等螢光增白劑；二苯甲酮系紫外線吸收劑、水楊酸系紫外線吸收劑、苯并***系紫外線吸收劑等紫外線吸收劑；滑石、矽石、碳酸鈣、玻璃纖維等無機填充材；著色劑；阻燃劑；阻燃助劑；抗靜電劑；塑化劑；近紅外線吸收劑；滑劑；填料及軟質聚合物等含脂環結構聚合物以外的任意聚合物；等。並且，任意成分可單獨使用1種，亦可以任意比率組合2種以上使用。The resin must contain optional components in addition to the above-mentioned polymers. Examples of optional components include: antioxidants such as phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants; light stabilizers such as hindered amine-based light stabilizers; petroleum-based waxes, Fischer-Tropsch waxes, polyalkylene waxes, etc. Wax; nucleating agents such as sorbitol compounds, metal salts of organic phosphoric acids, metal salts of organic carboxylic acids, kaolin and talc; diaminostilbene derivatives, coumarin derivatives, azole derivatives (such as benzene Fluorescent whitening such as tetrazole derivatives, benzotriazole derivatives, benzimidazole derivatives and benzothiazole derivatives), carbazole derivatives, pyridine derivatives, naphthalenedicarboxylic acid derivatives and imidazolone derivatives Agents; UV absorbers such as benzophenone-based UV absorbers, salicylic acid-based UV absorbers, and benzotriazole-based UV absorbers; inorganic fillers such as talc, silica, calcium carbonate, and glass fiber; colorants; Flame retardants; flame retardant additives; antistatic agents; plasticizers; near-infrared absorbers; lubricants; fillers and soft polymers and other polymers other than polymers containing alicyclic structures; etc. Moreover, any component may be used individually by 1 type, and may be used in combination of 2 or more types in arbitrary ratios.
［工序A］[Process A]
基材以於進行液晶組成物之塗布前已賦予定向限制力為佳。本實施型態之薄膜之製造方法，包含對基材1之表面S（在圖1中之下側面）賦予定向限制力的工序A。在圖1中，102為賦予定向限制力之裝置。It is preferable that the base material has been provided with orientation restricting force before coating of the liquid crystal composition. The method of manufacturing a thin film according to this embodiment includes a step A of imparting an orientation restricting force to the surface S (the lower side in FIG. 1 ) of the
工序A係對基材1之表面S賦予定向限制力的工序。藉由進行工序A，得對基材之表面S賦予定向限制力，促進在液晶組成物層中之液晶化合物的定向。所謂定向限制力，係謂可使液晶組成物所包含之液晶化合物等液晶化合物定向的「面之性質」。Step A is a step of imparting an orientation regulating force to the surface S of the
工序A，得藉由選自摩擦處理、光定向處理及延伸處理的處理方法來進行。此等處理方法之中，就製造效率優異的觀點而言，以延伸處理為佳。Step A can be performed by a treatment method selected from the group consisting of rubbing treatment, photo-orientation treatment, and stretching treatment. Among these treatment methods, stretching treatment is preferred from the viewpoint of excellent manufacturing efficiency.
在進行延伸處理的情況下，延伸之方向得因應薄膜所需之期望的定向方向而適當設定。延伸處理可僅為斜向延伸，亦可將斜向延伸與縱向延伸（往基材之長邊方向的延伸）及／或橫向延伸（往基材之幅寬方向的延伸）組合而進行。延伸倍率得以基材之雙折射成為期望之範圍的方式來適當設定。延伸處理得使用拉幅延伸機等已知的延伸機來進行。In the case of stretching processing, the direction of stretching can be appropriately set according to the desired orientation direction required for the film. The stretching treatment can be only diagonal extension, or can be performed by combining diagonal extension with longitudinal extension (extension in the long side direction of the substrate) and/or transverse extension (extension in the width direction of the substrate). The stretching ratio is appropriately set so that the birefringence of the base material falls within a desired range. The stretching treatment is performed using a known stretching machine such as a tenter stretching machine.
已進行工序A後至進行工序2為止的期間，維持相當於已進行工序A後之基材1A之表面S的表面1A1與其他部件的非接觸狀態，運送該基材1A。From after step A is carried out until
［附保護薄膜之基材］[Substrate with protective film]
在本實施型態，於工序1中，基材在做成具備基材與貼合於基材之表面S之保護薄膜的附保護薄膜之基材的狀態下運送。具體而言，運送於經賦予定向限制力之基材1A之表面1A1（亦即基材1A之表面S）之上貼合保護薄膜2而成的附保護薄膜之基材20。簡言之，已進行工序A後獲得之經賦予定向限制力之基材1A，會做成於表面1A1貼合保護薄膜2的狀態（附保護薄膜之基材20）運送。藉此，可維持基材1A之表面1A1與保護薄膜2以外之其他部件的非接觸狀態，防止在基材1A之表面1A1之傷痕的產生，或落塵等往該面的附著。In this embodiment, in
往經賦予定向限制力之基材1A之保護薄膜2的貼合（保護薄膜貼合工序），得藉由將自送出裝置103送出的保護薄膜2重疊於基材1A之下側面並利用2支軋輥105A&105B抵壓來進行。The
附保護薄膜之基材20，如圖3所示，於經賦予定向限制力之基材1A之表面1A1之上具備保護薄膜2。As shown in FIG. 3 , the
作為保護薄膜雖無特別限定，但可舉出樹脂製的薄膜。就可藉由輥對輥法有效率製造的觀點而言，以長條狀之樹脂製的薄膜為佳。作為構成保護薄膜的樹脂，可舉出包含例如：含脂環結構聚合物、聚對酞酸乙二酯、聚乙烯、聚對酞酸丁二酯、聚丙烯、聚四氟乙烯等聚合物的樹脂。並且，作為此種樹脂薄膜，亦可使用例如於表面已施以利用適切的離型劑之離型處理的薄膜，或於表面已施以利用適切的黏合劑之黏合處理的薄膜。The protective film is not particularly limited, but a resin film may be used. From the viewpoint of efficient production by the roll-to-roll method, a long resin film is preferred. Examples of the resin constituting the protective film include polymers such as alicyclic structure-containing polymers, polyethylene terephthalate, polyethylene, polybutylene terephthalate, polypropylene, and polytetrafluoroethylene. resin. Furthermore, as such a resin film, for example, a film whose surface has been subjected to a release treatment using an appropriate release agent, or a film whose surface has been subjected to an adhesive treatment using an appropriate adhesive.
保護薄膜得對於基材1A直接或中介黏合劑等而貼合。The protective film must be bonded to the
［工序B1及工序B2］[Process B1 and Process B2]
本實施型態之薄膜之製造方法，包含：於工序2之前進行之自附保護薄膜之基材剝離保護薄膜以獲得表面S露出之基材的工序（工序B1），與將已進行工序B1後的基材之張力阻斷的工序（工序B2）。The manufacturing method of the film of this embodiment includes: a step of peeling off the protective film from the base material attached with the protective film before step 2 (step B1) to obtain the base material with the surface S exposed; and removing the protective film after step B1. The process of breaking the tension of the base material (process B2).
藉由進行工序B1，保護基材的保護薄膜被剝離，基材之表面S露出，而能夠往表面S塗布液晶組成物。在工序B1中，附保護薄膜之基材20的保護薄膜2，於通過軋輥106A&106B後剝離，藉由收捲裝置104收捲。自附保護薄膜之基材20將保護薄膜2剝離後（工序B1之後）獲得的基材1A，沿圖示右方向運送，對於此基材1A進行將基材之張力阻斷的工序B2。By performing step B1, the protective film protecting the substrate is peeled off, the surface S of the substrate is exposed, and the liquid crystal composition can be applied to the surface S. In step B1, the
若進行工序B1，在基材1A中可能會發生由剝離保護薄膜所導致之張力的追逐（hunting）等，但藉由進行工序B2得調整基材之張力，防止張力的追逐。工序B2，得藉由使僅接觸於與基材1A之表面1A1為相反側之面（在圖1中之上側之面）的吸輥等張力截斷裝置（107&108）接觸於該面來進行。在已進行工序B1後，基材1A之表面1A1雖呈露出狀態，但在工序B2中，由於使用僅接觸於與基材1A之表面1A1為相反側之面的部件將張力阻斷，故在工序B2中亦得維持基材1A之表面1A1與其他部件的非接觸狀態。If step B1 is performed, tension hunting due to peeling of the protective film may occur in the
［運送部件］[Shipping Parts]
已進行工序B2後的基材1A，係藉由以非接觸狀態支撐基材1A之表面1A1的運送部件121&122來運送至塗布裝置110。藉此，工序1得在至進行工序2為止的期間維持與基材1A之表面1A1的非接觸狀態來進行。The
在本實施型態使用之運送部件121，係圓筒形的部件，如圖4所示，係與運送方向平行之方向的截面呈圓形的部件，外周部分的全部區域為截面弧狀部121R。在本發明中，所謂「與運送方向平行之方向的截面」，係謂以相對於運送基材之方向平行之面切割時的截面。在本實施型態中，「與運送方向平行之方向的截面」，係以與運送方向A1（圖1之左右方向）平行之面切割運送部件121時的截面。The conveying
運送部件121與基材1A之表面1A1，在全部區域中為非接觸，基材1A配置於沿運送部件121之外周部分的一部分接近的位置（參照圖4）。在本發明中，所謂「接近的位置」，係謂截面弧狀部與樹脂薄膜的間隔X為1 mm以下的部分。The conveying
運送部件121與基材1A之表面1A1的間隔X，以保持在1 mm以下為佳，以0.3 mm以下為較佳。藉由將運送部件121與基材1A的間隔定為上限值以下，可穩定運送基材1A。間隔X的下限，得定為例如10 μm以上。The distance X between the conveying
在本實施型態，運送部件122由於與運送部件121相同形狀相同大小，故省略運送部件122的說明。2個運送部件的配置位置可適當設定。In this embodiment, since the
在本實施型態中，運送部件121&122得做成具有將氣體噴出之孔的部件，所述氣體將基材1A保持於非接觸狀態。作為運送部件，以由具有將氣體噴出之孔的材料而成者為佳，以由多孔質材料而成的部件為較佳。作為此種多孔質材料，可列舉：多孔碳、多孔氧化鋁等。若使用由此種多孔質材料而成的運送部件，則可藉由自運送部件噴出之氣體的壓力使基材漂浮，故可防止基材之表面S與運送部件121&122的接觸，在薄膜之製造工序中，更有效抑制傷痕的產生。In this embodiment, the
在運送部件121&122係由多孔質材料而成的部件之情況下，運送部件成為於其表面具有多個孔。其平均孔徑以10 μm以下為佳，以2 μm以下為較佳。在孔徑過大的情況下，有時會發生一部分的孔阻塞，而氣體自其他孔洩漏之情事，但若將孔徑做成上限值以下，則即使一部分的孔阻塞，仍可防止氣體洩漏，基材1A得於運送部件121&122以均勻的力受支撐。此事推測為由以下機制所致者。在孔徑過大的情況下，一部分的孔由基材所覆蓋以使之漂浮時，壓力的變動會經由運送部件121&122的內部結構傳遞，大量的空氣會自基材未覆蓋的部分漏出，有時會變得無法使基材充分漂浮。若將孔徑做成上限值以下，即使於一部分的孔由基材所覆蓋以使之漂浮時，壓力的變動不易經由運送部件的內部結構傳遞，可抑制大量的空氣往基材未覆蓋的部分洩漏，基材1A得於運送部件121&122以均勻的力受支撐。多孔質材料之平均孔徑的下限得做成例如10 nm以上。When the conveying
在運送部件121&122為具有將氣體噴出之孔的部件之情況下，該氣體以高壓空氣為佳。在氣體為高壓空氣的情況下，其壓力以0.05 MPa以上為佳，以0.2 MPa以上為較佳，且以0.7 MPa以下為佳，以0.5 MPa以下為較佳。此種壓力係在運送部件之孔的內部且氣體往運送部件之外部噴出前之時刻的壓力。若運送部件121&122為此種態樣，則得在保持與基材之非接觸狀態的狀態下進行基材的運送。When the
［1.2.工序2］[1.2. Process 2]
工序2係藉由塗布裝置110，於係為對應基材1A之表面S之表面的表面1A1塗布液晶組成物以形成液晶組成物層5的工序。藉由進行工序2，可獲得具備基材1A與液晶組成物層5的薄膜10（參照圖2）。
作為塗布液晶組成物的方法，可列舉例如：簾塗法、擠製塗法、輥塗法、旋塗法、浸塗法、棒塗法、噴塗法、斜板式塗法、印刷塗法、凹版塗法、模具塗法、間隙塗法及浸漬法。Examples of methods for coating the liquid crystal composition include curtain coating, extrusion coating, roll coating, spin coating, dip coating, rod coating, spray coating, swash plate coating, printing coating, and gravure coating. Coating method, mold coating method, gap coating method and dipping method.
［液晶組成物］[Liquid crystal composition]
在工序2使用之液晶組成物，係包含液晶化合物的組成物。此液晶組成物不僅包含含有2種以上之成分的材料，亦包含僅含有1種液晶化合物的材料。The liquid crystal composition used in
液晶化合物由於具有液晶性，故通常在使該液晶化合物定向的情況下可呈現液晶相。Since a liquid crystal compound has liquid crystallinity, it usually exhibits a liquid crystal phase when the liquid crystal compound is oriented.
液晶化合物以具有聚合性為佳。據此，液晶化合物以此分子包含丙烯醯基、甲基丙烯醯基及環氧基等聚合性基為佳。液晶化合物之每1分子之聚合性基的數量亦可為1個，但以2個以上為佳。具有聚合性的液晶化合物，可在呈現液晶相的狀態下聚合，以不使在液晶相中之分子的折射率橢球上表現最大之折射率的方向變化的方式成為聚合物。據此，能夠在液晶固化層中將液晶化合物的定向狀態固定，或提高液晶化合物的聚合度而提高液晶固化層的機械性強度。The liquid crystal compound is preferably polymerizable. Accordingly, it is preferable that the liquid crystal compound contains polymerizable groups such as acrylic group, methacrylic group, and epoxy group in its molecule. The number of polymerizable groups per molecule of the liquid crystal compound may be one, but is preferably two or more. A polymerizable liquid crystal compound can be polymerized in a state of exhibiting a liquid crystal phase, and becomes a polymer in a manner that does not change the direction of the maximum refractive index on the refractive index ellipsoid of molecules in the liquid crystal phase. According to this, the orientation state of the liquid crystal compound can be fixed in the liquid crystal solidified layer, or the polymerization degree of the liquid crystal compound can be increased to improve the mechanical strength of the liquid crystal solidified layer.
液晶化合物之分子量以300以上為佳，以500以上為較佳，以800以上為尤佳，且以2000以下為佳，以1700以下為較佳，以1500以下為尤佳。在使用具有此種範圍之分子量的液晶化合物之情況下，尤可優化液晶組成物的塗覆性。The molecular weight of the liquid crystal compound is preferably 300 or more, more preferably 500 or more, particularly preferably 800 or more, and preferably 2,000 or less, preferably 1,700 or less, and particularly preferably 1,500 or less. In the case of using a liquid crystal compound having a molecular weight in such a range, the coatability of the liquid crystal composition can be optimized.
在量測波長590 nm之液晶化合物的雙折射Δn，以0.01以上為佳，以0.03以上為較佳，且以0.15以下為佳，以0.10以下為較佳。在使用具有此種範圍之雙折射Δn的液晶化合物之情況下，容易獲得定向缺陷少的液晶固化層。When measuring the birefringence Δn of the liquid crystal compound at a wavelength of 590 nm, it is preferably above 0.01, preferably above 0.03, preferably below 0.15, and preferably below 0.10. When a liquid crystal compound having birefringence Δn in such a range is used, a liquid crystal solidified layer with few alignment defects can be easily obtained.
液晶化合物的雙折射，可藉由例如下述方法來量測。The birefringence of a liquid crystal compound can be measured, for example, by the following method.
製作液晶化合物之層體，使此層體所包含之液晶化合物均勻定向。之後，量測此層體之面內相位差。然後，自「（層體之面內相位差）÷（層體之厚度）」可求出液晶化合物的雙折射。此時，為了使面內相位差及厚度的量測變得容易，亦可使已均勻定向的液晶化合物之層體固化。A layer of liquid crystal compound is produced so that the liquid crystal compound contained in the layer is uniformly oriented. Afterwards, the in-plane phase difference of this layer is measured. Then, the birefringence of the liquid crystal compound can be obtained from "(in-plane phase difference of the layer) ÷ (thickness of the layer)". At this time, in order to facilitate the measurement of the in-plane phase difference and thickness, the uniformly oriented layer of the liquid crystal compound may also be solidified.
液晶化合物可單獨使用1種，亦可以任意比率組合2種以上使用。One type of liquid crystal compound may be used alone, or two or more types may be used in combination at any ratio.
作為液晶化合物之例，可列舉：由下述式（I）所示之液晶化合物。Examples of the liquid crystal compound include a liquid crystal compound represented by the following formula (I).
『化1』（I）"
在式（I）中，Ar表示具有芳雜環、雜環及芳烴環之至少1個且亦可經取代之碳原子數6～67的2價有機基。作為芳雜環，可列舉例如：1H-異吲哚-1,3(2H)-二酮環、1-苯并呋喃環、2-苯并呋喃環、吖啶環、異喹啉環、咪唑環、吲哚環、㗁二唑環、㗁唑環、㗁唑并吡𠯤環、㗁唑并吡啶環、㗁唑并嗒𠯤環、㗁唑并嘧啶環、喹唑啉環、喹㗁啉環、喹啉環、㖕啉環、噻二唑環、噻唑環、噻唑并吡𠯤環、噻唑并吡啶環、噻唑并嗒𠯤環、噻唑并嘧啶環、噻吩環、三𠯤環、***環、㖠啶環、吡𠯤環、吡唑環、哌喃酮環、哌喃環、吡啶環、嗒𠯤環、嘧啶環、吡咯環、啡啶環、呔𠯤環、呋喃環、苯[c]噻吩環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、苯并㗁二唑環、苯并㗁唑環、苯并噻二唑環、苯并噻唑環、苯并噻吩環、苯并三𠯤環、苯并***環、苯并吡唑環、苯并哌喃酮環等。作為雜環，可列舉例如：1,3-二噻𠷬環、吡咯啶、哌𠯤等。作為芳烴環，可列舉例如：苯環、萘環等。In formula (I), Ar represents an optionally substituted divalent organic group having 6 to 67 carbon atoms, which has at least one of an aromatic heterocyclic ring, a heterocyclic ring, and an aromatic hydrocarbon ring. Examples of the aromatic heterocyclic ring include: 1H-isoindole-1,3(2H)-dione ring, 1-benzofuran ring, 2-benzofuran ring, acridine ring, isoquinoline ring, and imidazole ring, indole ring, 㗁oxadiazole ring, 㗁azole ring, 㗁azolopyridine ring, 㗁azolopyridine ring, 㗁azolopyridine ring, 㗁azolopyrimidine ring, quinazoline ring, quinoline ring , quinoline ring, Ζline ring, thiadiazole ring, thiazole ring, thiazolopyridine ring, thiazolopyridine ring, thiazoloda𠯤 ring, thiazolopyrimidine ring, thiophene ring, three 𠯤 ring, triazole ring,㖠Dine ring, pyrrole ring, pyrazole ring, piperanone ring, piperan ring, pyridine ring, pyridine ring, pyrimidine ring, pyrrole ring, phenanthridine ring, pyridine ring, furan ring, benzene[c]thiophene Ring, benzisothiazole ring, benzisothiazole ring, benzimidazole ring, benzodiazole ring, benzothiazole ring, benzothiadiazole ring, benzothiazole ring, benzothiophene ring, Benzotriazole ring, benzotriazole ring, benzopyrazole ring, benzopyranone ring, etc. Examples of the heterocyclic ring include 1,3-dithiane ring, pyrrolidine, piperazine, and the like. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and the like.
在式（I）中，Z1 及Z2 分別獨立表示選自由單鍵、－O－、－O－CH2 －、－CH2 －O－、－O－CH2 －CH2 －、－CH2 －CH2 －O－、－C(＝O)－O－、－O－C(＝O)－、－C(＝O)－S－、－S－C(＝O)－、－NR21 －C(＝O)－、－C(＝O)－NR21 －、－CF2 －O－、－O－CF2 －、－CH2 －CH2 －、－CF2 －CF2 －、－O－CH2 －CH2 －O－、－CH＝CH－C(＝O)－O－、－O－C(＝O)－CH＝CH－、－CH2 －C(＝O)－O－、－O－C(＝O)－CH2 －、－CH2 －O－C(＝O)－、－C(＝O)－O－CH2 －、－CH2 －CH2 －C(＝O)－O－、－O－C(＝O)－CH2 －CH2 －、－CH2 －CH2 －O－C(＝O)－、－C(＝O)－O－CH2 －CH2 －、－CH＝CH－、－N＝CH－、－CH＝N－、－N＝C(CH3 )－、－C(CH3 )＝N－、－N＝N－及－C≡C－而成之群組之任一者。R21 分別獨立表示氫原子或碳原子數1～6的烷基。In formula (I), Z 1 and Z 2 independently represent a group selected from a single bond, -O-, -O-CH 2 -, -CH 2 -O-, -O- CH 2 -CH 2 -, -CH 2 -CH 2 -O-, -C(=O)-O-, -O-C(=O)-, -C(=O)-S-, -S-C(=O)-, -NR 21 -C(=O)-, -C(=O)-NR 21 -, -CF 2 -O-, -O-CF 2 -, -CH 2 -CH 2 -, -CF 2 -CF 2 -, -O-CH 2 -CH 2 -O-, -CH＝CH-C(＝O)-O-, -O-C(＝O)-CH＝CH-, -CH 2 -C(＝O)- O-, -O-C(=O)-CH 2 -, -CH 2 -O-C(=O)-, -C(=O)-O-CH 2 -, -CH 2 -CH 2 -C (＝O)-O-, -O-C(＝O)-CH 2 -CH 2 -, -CH 2 -CH 2 -O-C(＝O)-, -C(＝O)-O-CH 2 -CH 2 -, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH 3 )-, -C(CH 3 )=N-, -N=N- and Any one of the groups formed by -C≡C-. R 21 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
在式（I）中，A1 、A2 、B1 及B2 分別獨立表示選自由亦可具有取代基之脂環基及亦可具有取代基之芳基而成之群組之基。A1 、A2 、B1 及B2 所表示之基的碳原子數（包含取代基的碳原子數。）分別獨立，通常為3～100。其中，A1 、A2 、B1 及B2 分別獨立，以亦可具有取代基之碳原子數5～20的脂環基或亦可具有取代基之碳原子數2～20的芳基為佳。In formula (I), A 1 , A 2 , B 1 and B 2 each independently represent a group selected from the group consisting of an alicyclic group which may have a substituent and an aryl group which may have a substituent. The number of carbon atoms (including the number of carbon atoms of the substituent) of the groups represented by A 1 , A 2 , B 1 and B 2 are independent of each other, and are usually 3 to 100. Among them, A 1 , A 2 , B 1 and B 2 are each independently an alicyclic group having 5 to 20 carbon atoms which may have a substituent or an aryl group having 2 to 20 carbon atoms which may have a substituent. good.
作為A1 、A2 、B1 及B2 中之脂環基，可列舉例如：環戊烷-1,3-二基、環己烷-1,4-二基、環庚烷-1,4-二基、環辛烷-1,5-二基等碳原子數5～20的環烷二基；十氫萘-1,5-二基、十氫萘-2,6-二基等碳原子數5～20的雙環烷二基；等。其中，以亦可經取代之碳原子數5～20的環烷二基為佳，以環己烷二基為較佳，以環己烷-1,4-二基為尤佳。脂環基可為反式體，可為順式體，亦可為順式體與反式體的混合物。其中，以反式體為較佳。Examples of the alicyclic group in A 1 , A 2 , B 1 and B 2 include: cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cycloheptane-1, 4-diyl, cyclooctane-1,5-diyl and other cycloalkanediyl groups with 5 to 20 carbon atoms; decalin-1,5-diyl, decalin-2,6-diyl, etc. Bicycloalkanediyl with 5 to 20 carbon atoms; etc. Among them, a cycloalkanediyl group having 5 to 20 carbon atoms which may be substituted is preferred, a cyclohexanediyl group is preferred, and a cyclohexane-1,4-diyl radical is particularly preferred. The alicyclic group may be a trans form, a cis form, or a mixture of the cis form and the trans form. Among them, the trans form is preferred.
作為A1 、A2 、B1 及B2 中之脂環基得具有之取代基，可列舉例如：鹵素原子、碳原子數1～6的烷基、碳原子數1～5的烷氧基、硝基、氰基等。取代基之數量可為一個，亦可為多個。並且，多個取代基可彼此相同，亦可相異。Examples of substituents that the alicyclic groups in A 1 , A 2 , B 1 and B 2 have include: halogen atoms, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms. , nitro, cyano, etc. The number of substituents may be one or multiple. In addition, the plurality of substituents may be the same as each other or different.
作為A1 、A2 、B1 及B2 中之芳基，可列舉例如：1,2-伸苯基、1,3-伸苯基、1,4-伸苯基、1,4-伸萘基、1,5-伸萘基、2,6-伸萘基、4,4’-伸聯苯基等碳原子數6～20的芳烴環基；呋喃-2,5-二基、噻吩-2,5-二基、吡啶-2,5-二基、吡𠯤-2,5-二基等碳原子數2～20的芳雜環基；等。其中，以碳原子數6～20的芳烴環基為佳，以伸苯基為更佳，以1,4-伸苯基為尤佳。Examples of the aryl group in A 1 , A 2 , B 1 and B 2 include: 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-phenylene group Naphthyl, 1,5-naphthyl, 2,6-naphthyl, 4,4'-biphenyl and other aromatic hydrocarbon ring groups with 6 to 20 carbon atoms; furan-2,5-diyl, thiophene -2,5-diyl, pyridine-2,5-diyl, pyridine-2,5-diyl and other aromatic heterocyclic groups with 2 to 20 carbon atoms; etc. Among them, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms is preferred, a phenylene group is more preferred, and a 1,4-phenylene group is particularly preferred.
作為A1 、A2 、B1 及B2 中之芳基得具有之取代基，可列舉例如與A1 、A2 、B1 及B2 中之脂環基得具有之取代基相同之例。取代基之數量可為一個，亦可為多個。並且，多個取代基可彼此相同，亦可相異。Examples of the substituents that the aryl groups in A 1 , A 2 , B 1 and B 2 have include the same substituents as those that the alicyclic groups in A 1 , A 2 , B 1 and B 2 have. . The number of substituents may be one or multiple. In addition, the plurality of substituents may be the same as each other or different.
在式（I）中，Y1 ～Y4 分別獨立表示選自由單鍵、－O－、－C(＝O)－、－C(＝O)－O－、－O－C(＝O)－、－NR22 －C(＝O)－、－C(＝O)－NR22 －、－O－C(＝O)－O－、－NR22 －C(＝O)－O－、－O－C(＝O)－NR22 －及－NR22 －C(＝O)－NR23 －而成之群組之任一者。R22 及R23 分別獨立表示氫原子或碳原子數1～6的烷基。In formula (I), Y 1 to Y 4 independently represent a group selected from a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O) -, -NR 22 -C(＝O)-, -C(＝O)-NR 22 -, -O-C(＝O)-O-, -NR 22 -C(＝O)-O-, - Any one of the group consisting of O-C(＝O)-NR 22 - and -NR 22- C(＝O)-NR 23- . R 22 and R 23 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
在式（I）中，G1 及G2 分別獨立表示選自由碳原子數1～20的脂族烴基；以及碳原子數3～20的脂族烴基所包含之亞甲基（－CH2 －）之1個以上經－O－或－C(＝O)－取代之基；而成之群組的有機基。G1 及G2 之前述有機基所包含之氫原子，亦可被碳原子數1～5的烷基、碳原子數1～5的烷氧基或鹵素原子取代。惟G1 及G2 之兩末端的亞甲基（－CH2 －）不被－O－或－C(＝O)－取代。In formula (I), G 1 and G 2 each independently represent a methylene group (-CH 2 -) selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and an aliphatic hydrocarbon group having 3 to 20 carbon atoms. ) is an organic group consisting of one or more groups substituted by -O- or -C(=O)-; The hydrogen atoms contained in the aforementioned organic groups of G 1 and G 2 may also be substituted by an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. However, the methylene groups (-CH 2 -) at both ends of G 1 and G 2 are not replaced by -O- or -C(=O)-.
作為G1 及G2 中之碳原子數1～20的脂族烴基之具體例，可列舉碳原子數1～20伸烷基。Specific examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in G 1 and G 2 include an alkylene group having 1 to 20 carbon atoms.
作為G1 及G2 中之碳原子數3～20的脂族烴基之具體例，可列舉碳原子數3～20的伸烷基。Specific examples of the aliphatic hydrocarbon group having 3 to 20 carbon atoms in G 1 and G 2 include an alkylene group having 3 to 20 carbon atoms.
在式（I）中，P1 及P2 分別獨立表示聚合性基。作為P1 及P2 中之聚合性基，可列舉例如：丙烯醯氧基、甲基丙烯醯氧基等由CH2 ＝CR31 －C(＝O)－O－所示之基；乙烯基；乙烯醚基；對二苯乙烯基；丙烯醯基；甲基丙烯醯基；羧基；甲基羰基；羥基；醯胺基；碳原子數1～4的烷基胺基；胺基；環氧基；氧呾基；醛基；異氰酸酯基；硫異氰酸酯基；等。R31 表示氫原子、甲基或氯原子。其中，以由CH2 ＝CR31 －C(＝O)－O－所示之基為佳，以CH2 ＝CH－C(＝O)－O－（丙烯醯氧基）、CH2 ＝C(CH3 )－C(＝O)－O－（甲基丙烯醯氧基）為較佳，以丙烯醯氧基為尤佳。In formula (I), P 1 and P 2 each independently represent a polymerizable group. Examples of the polymerizable group in P 1 and P 2 include: acryloyloxy group, methacryloyloxy group and other groups represented by CH 2 =CR 31 -C(=O)-O-; vinyl group ; Vinyl ether group; p-distyryl group; acrylyl group; methacrylyl group; carboxyl group; methylcarbonyl group; hydroxyl; amide group; alkylamino group with 1 to 4 carbon atoms; amine group; epoxy group; oxyethyl group; aldehyde group; isocyanate group; thiisocyanate group; etc. R 31 represents a hydrogen atom, a methyl group or a chlorine atom. Among them, the group represented by CH 2 =CR 31 -C(=O)-O- is preferred, and CH 2 =CH-C(=O)-O- (acrylyloxy group), CH 2 =C (CH 3 )-C(=O)-O- (methacryloxy group) is preferred, and acryloyloxy group is particularly preferred.
在式（I）中，p及q分別獨立表示0或1。In formula (I), p and q independently represent 0 or 1.
由式（I）所示之液晶化合物，得藉由例如國際專利公開第2012/147904號所記載之肼化合物與羰化合物的反應來製造。The liquid crystal compound represented by formula (I) can be produced by the reaction of a hydrazine compound and a carbonyl compound described in International Patent Publication No. 2012/147904, for example.
作為由式（I）所示之液晶化合物，具體而言，可列舉例如由下述式所示之化合物。Specific examples of the liquid crystal compound represented by formula (I) include compounds represented by the following formula.
『化2』（A-1）（A-2）（A-3）（A-4）（A-5）（A-6）（A-7）（A-8）（A-9）"
液晶組成物亦可視需求更包含任意成分組合至液晶化合物。任意成分可單獨使用1種，亦可以任意比率組合2種以上使用。The liquid crystal composition may also contain any combination of ingredients into the liquid crystal compound as required. Any component may be used individually by 1 type, or in combination of 2 or more types at arbitrary ratios.
舉例而言，為了促進液晶化合物的聚合，液晶組成物亦可包含聚合起始劑作為任意成分。作為聚合起始劑，熱聚合起始劑及光聚合起始劑之任一者皆可使用。其中，在顯著獲得本發明之期望之效果的觀點上，以使用光聚合起始劑為佳。For example, in order to promote the polymerization of the liquid crystal compound, the liquid crystal composition may also include a polymerization initiator as an optional component. As the polymerization initiator, any of a thermal polymerization initiator and a photopolymerization initiator can be used. Among them, from the viewpoint of significantly obtaining the desired effects of the present invention, it is preferable to use a photopolymerization initiator.
並且，聚合起始劑的種類，得因應液晶組成物所包含的聚合性之化合物的種類來選擇。舉例而言，若聚合性之化合物為自由基聚合性，即得使用自由基聚合起始劑。並且，若聚合性之化合物為陰離子聚合性，即得使用陰離子聚合起始劑。再者，若聚合性之化合物為陽離子聚合性，即得使用陽離子聚合起始劑。聚合起始劑可單獨使用1種，亦可以任意比率組合2種以上使用。In addition, the type of polymerization initiator must be selected according to the type of polymerizable compound contained in the liquid crystal composition. For example, if the polymerizable compound is radically polymerizable, a radical polymerization initiator may be used. Furthermore, if the polymerizable compound is anionically polymerizable, an anionic polymerization initiator may be used. Furthermore, if the polymerizable compound is cationically polymerizable, a cationic polymerization initiator may be used. One type of polymerization initiator may be used alone, or two or more types may be used in combination at any ratio.
作為聚合起始劑，以自由基聚合起始劑為佳，以肟酯系聚合起始劑為較佳。所謂肟酯系聚合起始劑，係含有肟酯基的聚合起始劑。藉由使用肟酯系聚合起始劑，可有效提高液晶組成物之固化物的耐溶解性。As the polymerization initiator, a radical polymerization initiator is preferred, and an oxime ester polymerization initiator is preferred. The oxime ester polymerization initiator is a polymerization initiator containing an oxime ester group. By using an oxime ester polymerization initiator, the dissolution resistance of the cured product of the liquid crystal composition can be effectively improved.
作為聚合起始劑之具體例，作為肟酯系聚合起始劑，可列舉例如：1,2-辛二酮-1-[4-(苯硫基)苯基]-2-(O-苯甲醯肟)、乙酮-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(O-乙醯肟)、日本專利公開第2001-233842號公報所記載之肟酯系聚合起始劑等。並且，若要以商品名舉出肟酯系聚合起始劑之例，可列舉：BASF公司製之IrgacureOXE01、IrgacureOXE02、IrgacureOXE04；ADEKA公司製之ADEKA ARKLS N-1919T、ADEKA ARKLS NCI730；等。Specific examples of the polymerization initiator include, for example, oxime ester-based polymerization initiator: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-phenyl) Methyl oxime), ethanone-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), Japan The oxime ester polymerization initiator described in Patent Publication No. 2001-233842, etc. Furthermore, examples of oxime ester-based polymerization initiators by trade names include: IrgacureOXE01, IrgacureOXE02, and IrgacureOXE04 manufactured by BASF; ADEKA ARKLS N-1919T and ADEKA ARKLS NCI730 manufactured by ADEKA; etc.
聚合起始劑之量相對於液晶化合物100重量份，以0.1重量份以上為佳，以0.5重量份以上為較佳，且以30重量份以下為佳，以10重量份以下為較佳。在聚合起始劑之量落於前述範圍的情況下，可使聚合有效率進行。The amount of the polymerization initiator is preferably not less than 0.1 parts by weight, more preferably not less than 0.5 parts by weight, preferably not more than 30 parts by weight, and preferably not more than 10 parts by weight based on 100 parts by weight of the liquid crystal compound. When the amount of the polymerization initiator falls within the aforementioned range, polymerization can be efficiently performed.
舉例而言，液晶組成物亦可包含界面活性劑作為任意成分。尤其就穩定獲得定向性優異之液晶固化層的觀點而言，作為界面活性劑，以分子中包含氟原子的界面活性劑為佳。在以下說明中，適時將分子中包含氟原子的界面活性劑稱作「氟系界面活性劑」。For example, the liquid crystal composition may also include a surfactant as an optional component. In particular, from the viewpoint of stably obtaining a liquid crystal solidified layer excellent in orientation, a surfactant containing a fluorine atom in the molecule is preferred as the surfactant. In the following description, surfactants containing fluorine atoms in their molecules will be appropriately referred to as "fluorine-based surfactants".
界面活性劑以非離子系界面活性劑為佳。在界面活性劑為不包含離子性基的非離子系界面活性劑之情況下，尤可優化液晶固化層之表面狀態及定向性。The surfactant is preferably a nonionic surfactant. When the surfactant is a non-ionic surfactant that does not contain ionic groups, the surface state and orientation of the liquid crystal solidified layer can be optimized.
作為界面活性劑，可列舉例如：AGC Seimi Chemical Co., Ltd.製之SURFLON系列（S242、S386、S420等）、DIC公司製之MEGAFAC系列（F251、F554、F556、F562、RS-75、RS-76-E等）、NEOS公司製之FTERGENT系列（FTX601AD、FTX602A、FTX601ADH2、FTX650A、209F等）等。並且，界面活性劑可單獨使用1種，亦可以任意比率組合2種以上使用。Examples of surfactants include: SURFLON series (S242, S386, S420, etc.) manufactured by AGC Seimi Chemical Co., Ltd., MEGAFAC series (F251, F554, F556, F562, RS-75, RS) manufactured by DIC Corporation -76-E, etc.), FTERGENT series manufactured by NEOS (FTX601AD, FTX602A, FTX601ADH2, FTX650A, 209F, etc.), etc. In addition, one type of surfactant may be used alone, or two or more types may be used in combination at any ratio.
界面活性劑之量相對於液晶化合物100重量份，以0.005重量份以上為佳，以0.010重量份以上為較佳，且以1.00重量份以下為佳，以0.50重量份以下為較佳。在界面活性劑之量位於前述範圍的情況下，可優化液晶固化層之表面狀態，或抑制液晶固化層之定向缺陷的產生。The amount of the surfactant is preferably at least 0.005 parts by weight, preferably at least 0.010 parts by weight, preferably at most 1.00 parts by weight, and preferably at most 0.50 parts by weight based on 100 parts by weight of the liquid crystal compound. When the amount of the surfactant is within the aforementioned range, the surface state of the liquid crystal solidified layer can be optimized or the occurrence of orientation defects in the liquid crystal solidified layer can be suppressed.
舉例而言，液晶組成物亦可包含抗氧化劑作為任意成分。藉由使用抗氧化劑，可抑制液晶組成物的膠化，故可延長液晶組成物的適用期。抗氧化劑可單獨使用1種，亦可以任意比率組合2種以上使用。For example, the liquid crystal composition may also contain an antioxidant as an optional component. By using antioxidants, the gelation of the liquid crystal composition can be inhibited, so the pot life of the liquid crystal composition can be extended. One type of antioxidant may be used alone, or two or more types may be used in combination at any ratio.
抗氧化劑之量相對於液晶化合物100重量份，以0.001重量份以上為佳，以0.005重量份以上為較佳，以0.010重量份以上為尤佳，且以5重量份以下為佳，以2重量份以下為較佳，以1重量份以下為尤佳。在抗氧化劑之量位於前述範圍的情況下，可有效延長液晶組成物的適用期。The amount of the antioxidant is preferably at least 0.001 parts by weight, preferably at least 0.005 parts by weight, particularly preferably at least 0.010 parts by weight, and preferably at most 5 parts by weight, based on 100 parts by weight of the liquid crystal compound. Parts or less are preferred, and 1 part by weight or less is particularly preferred. When the amount of antioxidant is within the aforementioned range, the pot life of the liquid crystal composition can be effectively extended.
液晶組成物亦可包含溶媒作為任意成分。作為溶媒，以可溶解液晶化合物者為佳。作為此種溶媒，通常使用有機溶媒。作為有機溶媒之例，可列舉：環戊酮、環己酮、甲基乙基酮、丙酮、甲基異丁基酮等酮溶媒；乙酸丁酯、乙酸戊酯等乙酸酯溶媒；氯仿、二氯甲烷、二氯乙烷等鹵化烴溶媒；1,4-二氧𠮿、環戊基甲基醚、四氫呋喃、四氫哌喃、1,3-二氧𠷬、1,2-二甲氧基乙烷等醚溶媒；以及甲苯、二甲苯、1,3,5-三甲苯等芳烴溶媒。並且，溶媒可單獨使用1種，亦可以任意比率組合2種以上使用。The liquid crystal composition may also contain a solvent as an optional component. As a solvent, one capable of dissolving a liquid crystal compound is preferred. As such a solvent, an organic solvent is usually used. Examples of organic solvents include ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, and methyl isobutyl ketone; acetate solvents such as butyl acetate and amyl acetate; chloroform, Dichloromethane, dichloroethane and other halogenated hydrocarbon solvents; 1,4-dioxan, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxan, 1,2-dimethoxy Ether solvents such as ethane; and aromatic hydrocarbon solvents such as toluene, xylene, and 1,3,5-trimethylbenzene. In addition, one type of solvent may be used alone, or two or more types may be used in combination at any ratio.
溶媒之沸點就操作性優異的觀點而言，以60℃～250℃為佳，以60℃～150℃為較佳。From the viewpoint of excellent operability, the boiling point of the solvent is preferably 60°C to 250°C, and more preferably 60°C to 150°C.
溶媒之量相對於液晶化合物100重量份，以200重量份以上為佳，以250重量份以上為較佳，以300重量份以上為尤佳，且以650重量份以下為佳，以600重量份以下為較佳，以500重量份以下為尤佳。在溶媒之量為前述範圍之下限值以上的情況下，可抑制異物產生。並且，在溶媒之量為前述範圍之上限值以下的情況下，可減低乾燥負荷。The amount of the solvent is preferably at least 200 parts by weight, preferably at least 250 parts by weight, and especially at least 300 parts by weight, based on 100 parts by weight of the liquid crystal compound, and is preferably at most 650 parts by weight, with 600 parts by weight being preferred. The following is preferred, and the content of 500 parts by weight or less is particularly preferred. When the amount of the solvent is more than the lower limit of the aforementioned range, the generation of foreign matter can be suppressed. In addition, when the amount of the solvent is less than the upper limit of the aforementioned range, the drying load can be reduced.
作為液晶組成物得包含之任意其他成分，可列舉例如：金屬；金屬錯合物；氧化鈦等金屬氧化物；染料、顏料等著色劑；螢光材料、磷光材料等發光材料；均染劑；觸變劑；膠化劑；多醣類；紫外線吸收劑；紅外線吸收劑；抗氧化劑；離子交換樹脂；等。此等成分之量相對於液晶化合物之合計100重量份，得各自定為0.1重量份～20重量份。Examples of any other components that may be included in the liquid crystal composition include: metals; metal complexes; metal oxides such as titanium oxide; colorants such as dyes and pigments; luminescent materials such as fluorescent materials and phosphorescent materials; leveling agents; Thixotropic agents; gelling agents; polysaccharides; ultraviolet absorbers; infrared absorbers; antioxidants; ion exchange resins; etc. The amounts of these components are each determined to be 0.1 to 20 parts by weight relative to 100 parts by weight of the liquid crystal compound in total.
［1.3.基材之運送張力］[1.3. Transport tension of substrate]
在本實施型態之薄膜之製造方法中的基材之運送張力得如下設定。In the film manufacturing method of this embodiment, the conveyance tension of the base material is set as follows.
在運送路徑之較塗布裝置110還要上游的基材1（基材1A）之運送張力T1
，以30 N/m以上為佳，以50 N/m以上為較佳，且以500 N/m以下為佳，以200 N/m以下為較佳。藉由將運送路徑之較塗布裝置110還要上游──即在工序1中──的基材1（基材1A）之運送張力T1
定為前述上限值以下，可防止由運送張力所導致之基材1（基材1A）的變形。藉由將運送張力T1
定為前述下限值以上，可減小與在工序2中之運送張力的差，抑制由張力差所導致之基材的尺寸變化。The conveyance tension T 1 of the substrate 1 (
在工序2中的基材1A之運送張力T2
以200 N/m以上為佳，以250 N/m以上為較佳，且以500 N/m以下為佳，以400 N/m以下為較佳。藉由將在工序2中的運送張力定為前述下限值以上，可提高在工序2中之基材的平坦性，使液晶組成物之塗層厚度均勻。藉由將運送張力T2
定為前述上限值以下，得防止已塗布液晶組成物的基材之變形。The conveyance tension T 2 of the
運送張力T1
以較運送張力T2
還低且於自基材之送出至進行工序2為止的期間設定成階段性變高者為佳。藉由將運送張力T1
及運送張力T2
定為此種態樣，可抑制運送張力的驟升，藉此可抑制基材的尺寸變化，防止由尺寸變化所導致之傷痕的產生。階段性的運送張力之上升，得藉由於在工序1中之運送路徑內設置多個吸輥及／或軋輥，以運送張力在各自的下游較上游高的方式，調整此等的驅動速度來達成。It is preferable that the conveyance tension T 1 is lower than the conveyance tension T 2 and is set to become higher in steps from the delivery of the base material to the execution of the
［2.薄膜之製造裝置］[2. Film manufacturing equipment]
在於上已述之本實施型態之薄膜之製造方法使用之製造裝置100，具備：於基材1之表面S塗布液晶組成物以形成液晶組成物層5的塗布裝置110，與將基材1（基材1A）運送至塗布裝置110的運送部件121&122。在本實施型態之薄膜之製造裝置中，運送部件121&122係在以非接觸狀態支撐基材1之表面1A1（亦即基材1之表面S）的狀態下運送基材的運送部件。The
薄膜之製造裝置100，於運送部件121&122及塗布裝置110以外，還具備將基材1送出的送出裝置101、對基材1賦予定向限制力之裝置102、將保護薄膜2送出的送出裝置103、將自附保護薄膜之基材20剝離之保護薄膜2收捲的收捲裝置104、吸輥107&108、軋輥105A&105B&106A&106B。The
［3.作用、效果］[3. Function, effect]
以下說明本實施型態之薄膜之製造方法及製造裝置的作用及效果。The following describes the functions and effects of the thin film manufacturing method and the manufacturing device according to this embodiment.
在本實施型態之薄膜之製造方法中，將自送出裝置101送出的基材1沿A1所示之方向運送，在賦予定向限制力之裝置102中，對基材1之表面S賦予定向限制力（工序A）。藉由進行工序A，可獲得經賦予定向限制力之基材1A。In the film manufacturing method of this embodiment, the
已進行工序A後之基材（基材1A），係於其表面1A1貼合自送出裝置103送出的保護薄膜2，在附保護薄膜之基材20的狀態下運送。藉此，可防止基材之表面1A1與保護薄膜2以外之其他部件的直接接觸，故基材1A可在維持基材1A之表面1A1與其他部件之非接觸狀態的狀態下運送。The base material (
具備保護薄膜2之態樣（附保護薄膜之基材20之狀態）的基材1A，可於運送至塗布裝置110前，自其表面1A1將保護薄膜2（工序B1）剝離。使吸輥107接觸於與已進行工序B1後獲得之基材1A之表面1A1為相反側之面，以阻斷基材1A的張力（工序B2）。藉此，得在將保護薄膜2剝離後之基材1A中調整張力，防止張力之追逐的發生。The
藉由在以非接觸狀態支撐基材1A之表面1A1的狀態下運送的運送部件121&122，將已進行工序B2後獲得之基材1A運送至塗布裝置110。在本實施型態，已進行利用運送部件121&122的運送後，經過吸輥108，運送至塗布裝置110。吸輥108係接觸於與基材1A之表面1A1為相反側之面以調整基材之張力的部件。因此，至進行工序2為止的期間，可維持與基材1A之表面1A1的非接觸狀態來進行已進行工序B2後之基材1A的運送。The
其次，進行於已運送至塗布裝置110的基材1A之表面1A1塗布液晶組成物以形成液晶組成物層5的工序2。藉此，可獲得如圖2所示具備基材1A與形成於基材1A之表面1A1之液晶組成物層5的薄膜10。Next, the
在本實施型態之薄膜之製造方法中，藉由以非接觸狀態支撐基材1（基材1A）之表面1A1的運送部件121&122，至進行工序2為止的期間，維持與基材1（1A）之表面1A1的非接觸狀態來進行基材1（基材1A）的運送。In the film manufacturing method of this embodiment, the
並且，根據本實施型態，已進行工序A後之基材1A由於在貼合有保護薄膜的狀態下運送，故可防止基材1A之表面1A1與保護薄膜以外之其他部件的直接接觸。其結果，基材1A得於工序A之後至進行工序2為止的期間，在維持基材1A之表面1A1與其他部件之非接觸狀態的狀態下運送。Furthermore, according to this embodiment, since the
其結果，根據本實施型態之薄膜之製造方法，可提供防止在塗布有液晶組成物之基材中產生傷痕的薄膜之製造方法及製造裝置。As a result, according to the thin film manufacturing method of this embodiment, it is possible to provide a thin film manufacturing method and a manufacturing apparatus that prevent scratches from occurring on a base material coated with a liquid crystal composition.
［4.液晶固化薄膜之製造方法］[4. Manufacturing method of liquid crystal cured film]
茲說明使用藉由上述薄膜之製造方法獲得之薄膜（具備基材與液晶組成物層的薄膜）的液晶固化薄膜之製造方法。Hereinafter, a method for producing a liquid crystal cured film using a film (a film having a base material and a liquid crystal composition layer) obtained by the above-mentioned film production method will be described.
液晶固化薄膜之製造方法，係使藉由上述本實施型態之薄膜之製造方法獲得之薄膜的液晶組成物層固化而成的液晶固化薄膜之製造方法。The method for producing a liquid crystal cured film is a method for producing a liquid crystal cured film obtained by solidifying the liquid crystal composition layer of the film obtained by the film producing method of this embodiment.
亦即，本實施型態之液晶固化薄膜之製造方法，係具備基材與形成於基材之表面S之液晶固化層的液晶固化薄膜之製造方法，包含：藉由本發明之薄膜之製造方法製造具備基材與形成於基材之表面S之液晶組成物層的薄膜的工序，以及在運送路徑之較上述工序2還要下游進行的工序3A及工序3B。That is, the method of manufacturing a liquid crystal cured film of this embodiment is a method of manufacturing a liquid crystal cured film including a base material and a liquid crystal cured layer formed on the surface S of the base material, including manufacturing by the method of manufacturing a film of the present invention. The process of including a substrate and a thin film of a liquid crystal composition layer formed on the surface S of the substrate, and processes 3A and 3B that are performed downstream of the above-mentioned
工序3A係將液晶組成物層固化以於基材之表面S形成液晶固化層的工序，工序3B係於液晶固化層之上進一步形成硬塗層的工序。在本發明中，工序3B係任意工序，進行此任意工序一事及進行工序之時機，不受限於在本實施型態說明的態樣。Step 3A is a step of solidifying the liquid crystal composition layer to form a liquid crystal solidified layer on the surface S of the substrate, and step 3B is a step of further forming a hard coat layer on the liquid crystal solidified layer. In the present invention, step 3B is an arbitrary step, and the fact that this arbitrary step is performed and the timing of performing the step are not limited to the aspects described in this embodiment.
自工序2往工序3A之運送（2－3A），藉由以非接觸狀態支撐薄膜之液晶組成物層側之面的運送部件（2－3A），自已進行工序2後至進行工序3A為止的期間，維持運送部件（2－3A）與薄膜之液晶組成物層側之面的非接觸狀態來進行。The transportation from
在自工序2往工序3A之運送（2－3A）中使用之運送部件（2－3A），得使用如同在基材1A之運送中使用之運送部件121&122的構造者。The conveyance member (2-3A) used for conveyance (2-3A) from
在液晶組成物為液體且運送部件（2－3A）為漂浮運送部件（亦即，於上已述之自表面將氣體噴出之部件）的情況下，液晶組成物有因自漂浮運送部件之氣體之吹拂而飛散的可能性。惟此種飛散可藉由調整製造方法之實施的諸條件來減低或防止。作為此種調整之例，可列舉：提高液晶組成物之黏度、將液晶組成物做成容易乾燥者、薄化液晶組成物之層體的厚度、將薄膜於工序2之結束後至到達最初之漂浮運送部件為止的時間延長、在薄膜於工序2之結束後至到達最初之漂浮運送部件為止的期間設置適切的乾燥手段，以及將自漂浮運送部件之氣體的噴出做成緩和者等調整。When the liquid crystal composition is a liquid and the transport member (2-3A) is a floating transport member (that is, a member that ejects gas from the surface as described above), the liquid crystal composition has gas from the floating transport member. The possibility of being blown away. However, this kind of scattering can be reduced or prevented by adjusting the conditions for the implementation of the manufacturing method. Examples of such adjustments include: increasing the viscosity of the liquid crystal composition, making the liquid crystal composition easy to dry, thinning the thickness of the layer of the liquid crystal composition, and adjusting the film to the initial thickness after the end of
［工序3A］[Process 3A]
在工序3A，通常藉由液晶組成物所包含之聚合性之化合物的聚合，使液晶組成物之層體固化。據此，在液晶化合物具有聚合性的情況下，此液晶化合物通常會聚合。由於會因固化而失去固化前的流動性，故通常在所獲得之液晶固化層，液晶化合物之定向狀態受到固定。In step 3A, the layer of the liquid crystal composition is usually solidified by polymerization of a polymerizable compound contained in the liquid crystal composition. According to this, when a liquid crystal compound has polymerizability, the liquid crystal compound usually polymerizes. Since the fluidity before solidification is lost due to solidification, the orientation state of the liquid crystal compound is usually fixed in the obtained solidified liquid crystal layer.
作為聚合方法，得選擇適合於液晶組成物所包含之成分之性質的方法。作為聚合方法，可列舉例如：照射活性能量線的方法及熱聚合法。其中，由於不需加熱而可使聚合反應在室溫下進行，故以照射活性能量線的方法為佳。於此，所照射之活性能量線，得包含：可見光、紫外線及紅外線等光線，以及電子束等任意能量線。As a polymerization method, a method suitable for the properties of the components contained in the liquid crystal composition must be selected. Examples of the polymerization method include a method of irradiating active energy rays and a thermal polymerization method. Among them, the method of irradiating active energy rays is preferred because the polymerization reaction can proceed at room temperature without heating. Here, the irradiated active energy rays may include: visible light, ultraviolet rays, infrared rays and other rays, as well as any energy rays such as electron beams.
自工序3A往工序3B之運送（3A－3B），藉由以非接觸狀態支撐薄膜之液晶固化層側之面的運送部件（3A－3B），自已進行工序3A後至進行工序3B為止的期間，維持與薄膜之液晶固化層側之面的非接觸狀態來進行。為便於說明，係為包含基材及液晶固化層的多層物且供於硬塗層之形成者，如同於上已述之本發明之薄膜（包含基材及液晶組成物層的多層物）稱作「薄膜」。During the transportation from step 3A to step 3B (3A-3B), the transportation member (3A-3B) that supports the liquid crystal solidified layer side of the film in a non-contact state, the period from step 3A to step 3B , while maintaining the non-contact state with the liquid crystal solidified layer side of the film. For convenience of explanation, it is a multi-layered material including a base material and a liquid crystal solidified layer and is used for the formation of a hard coat layer. It is called the thin film of the present invention (a multi-layered material including a base material and a liquid crystal composition layer) as described above. As "film".
在自工序3A往工序3B之運送（3A－3B）中使用之運送部件（3A－3B），得使用如同在基材1A之運送中使用之運送部件121&122的構造者。The conveying member (3A-3B) used for conveying (3A-3B) from step 3A to step 3B may have the same structure as the conveying
［工序3B］[Process 3B]
工序3B係於液晶固化層之上進一步形成硬塗層的工序。硬塗層得藉由將形成硬塗層之組成物塗布於液晶固化層之上並使之固化來形成。Step 3B is a step of further forming a hard coat layer on the liquid crystal solidified layer. The hard coat layer is formed by applying a composition for forming the hard coat layer on the liquid crystal solidified layer and solidifying it.
作為形成硬塗層之組成物，可舉出例如得藉由活性能量線固化之包含活性能量線固化型樹脂與微粒子的組成物。作為活性能量線，可列舉：紫外線、電子束等。Examples of the composition for forming the hard coat layer include a composition containing an active energy ray-curable resin and fine particles that are cured by active energy rays. Examples of active energy rays include ultraviolet rays, electron beams, etc.
作為活性能量線固化型樹脂，以於固化後在JIS K5600-5-4所規定之鉛筆硬度試驗表現「HB」以上之硬度的樹脂為佳。As the active energy ray-curable resin, a resin that exhibits a hardness of “HB” or higher in the pencil hardness test specified in JIS K5600-5-4 after curing is preferred.
作為活性能量線固化型樹脂，可列舉例如：有機矽系、三聚氰胺系、環氧系、丙烯酸系、胺甲酸酯丙烯酸酯系、多官能丙烯酸酯系之活性能量線固化型樹脂。其中，就接合力良好、強韌性及生產性優異的觀點而言，以胺甲酸酯丙烯酸酯系紫外線固化型樹脂及／或多官能丙烯酸酯系紫外線固化型樹脂為佳。Examples of active energy ray-curable resins include silicone-based, melamine-based, epoxy-based, acrylic-based, urethane acrylate-based, and multifunctional acrylate-based active energy ray-curable resins. Among them, urethane acrylate ultraviolet curable resin and/or polyfunctional acrylate ultraviolet curable resin are preferred from the viewpoint of good bonding strength, strength, toughness, and productivity.
微粒子可為由有機物構成之有機微粒子，亦可為由無機物構成之無機微粒子。微粒子以無機微粒子為佳，以無機氧化物的微粒子為較佳。作為得構成微粒子的無機氧化物，可列舉例如：矽石、鈦白（氧化鈦）、鋯土（氧化鋯）、氧化鋅、氧化錫、氧化鈰、五氧化二銻、二氧化鈦、摻錫的氧化銦（ITO）、摻銻的氧化錫（ATO）、摻磷的氧化錫（PTO）、摻鋅的氧化銦（IZO）、摻鋁的氧化鋅（AZO）及摻氟的氧化錫（FTO）。The microparticles may be organic microparticles composed of organic substances or inorganic microparticles composed of inorganic substances. As the fine particles, inorganic fine particles are preferred, and inorganic oxide fine particles are more preferred. Examples of inorganic oxides constituting fine particles include silica, titanium dioxide (titanium oxide), zirconium oxide (zirconium oxide), zinc oxide, tin oxide, cerium oxide, antimony pentoxide, titanium dioxide, and tin-doped oxide. Indium (ITO), antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), zinc-doped indium oxide (IZO), aluminum-doped zinc oxide (AZO) and fluorine-doped tin oxide (FTO).
作為微粒子，由於與作為形成硬塗層之黏結劑之樹脂的密合性及透明性達成優異平衡，可輕易調整硬塗層之折射率，故以矽石微粒子為佳。As fine particles, silica fine particles are preferred because they have an excellent balance of adhesion and transparency with the resin used as a binder for forming the hard coat layer and can easily adjust the refractive index of the hard coat layer.
用以形成硬塗層之組成物，可單獨包含1種微粒子，亦可以2種以上之組合來包含微粒子。The composition used to form the hard coat layer may contain one type of microparticles alone, or may contain two or more types of microparticles in combination.
微粒子之數量平均粒徑以1 nm以上且1000 nm以下為佳，以1 nm以上且500 nm以下為較佳，以1 nm以上且250 nm以下為更佳。微粒子的數量平均粒徑愈小，可愈降低硬塗層之霧度，可愈提高微粒子與作為形成硬塗層之黏結劑之樹脂的密合性。The number average particle diameter of the fine particles is preferably from 1 nm to 1000 nm, more preferably from 1 nm to 500 nm, and more preferably from 1 nm to 250 nm. The smaller the number average particle size of the fine particles, the more the haze of the hard coat layer can be reduced, and the adhesion between the fine particles and the resin used as the binder for forming the hard coat layer can be improved.
在用以形成硬塗層的組成物中，微粒子之含量相對於活性能量線固化型樹脂100重量份，以10～80重量份為佳，以10～50重量份為較佳，以20～40重量份為更佳。若微粒子之含量為上述範圍，則霧度值、全光線穿透率等光學特性優異。In the composition used to form the hard coat layer, the content of the fine particles is preferably 10 to 80 parts by weight, preferably 10 to 50 parts by weight, and 20 to 40 parts by weight based on 100 parts by weight of the active energy ray curable resin. Parts by weight are better. If the content of fine particles is within the above range, optical properties such as haze value and total light transmittance will be excellent.
全光線穿透率（%），可使用例如市售之霧度計（日本電色公司製之「NDH 2000」）等，遵循JIS K-7361來量測。The total light transmittance (%) can be measured using, for example, a commercially available haze meter ("NDH 2000" manufactured by Nippon Denshoku Co., Ltd.) in compliance with JIS K-7361.
用以形成硬塗層之組成物，亦可包含用以使活性能量線固化型樹脂溶解或分散的溶劑。作為該溶劑，可列舉例如：甲醇、乙醇、異丙醇、正丁醇、異丁醇等醇類；乙二醇、乙二醇一丁基醚、乙酸乙二醇酯一乙基醚、二乙二醇、二乙二醇一丁基醚、二丙酮乙二醇等乙二醇類；甲苯、二甲苯等芳烴類；正己烷、正庚烷等脂族烴；乙酸乙酯、乙酸丁酯等酯類；甲基乙基酮、甲基異丁基酮等酮類；甲基乙基酮肟等肟類；以及由此等之2種以上而成之組合；等。The composition used to form the hard coat layer may also include a solvent used to dissolve or disperse the active energy ray-curable resin. Examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol acetate monoethyl ether, dibutyl alcohol, etc. Glycols such as ethylene glycol, diethylene glycol monobutyl ether, and diacetone glycol; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane and n-heptane; ethyl acetate, butyl acetate Esters; ketones such as methyl ethyl ketone and methyl isobutyl ketone; oximes such as methyl ethyl ketoxime; and combinations of two or more of these; etc.
在藉由紫外線使活性能量線固化型樹脂固化的情況下，用以形成硬塗層之組成物亦可更包含光聚合起始劑。作為光聚合起始劑，可列舉例如：以往眾所周知之光聚合起始劑，具體而言，可列舉例如：二苯甲酮、Ciba Specialty Chemicals Inc.製之「Darocur 1173」、「Irgacure 651」、「Irgacure 184」、「Irgacure 907」、「Irgacure 754」等。When the active energy ray-curable resin is cured by ultraviolet rays, the composition for forming the hard coat layer may further include a photopolymerization initiator. Examples of the photopolymerization initiator include conventionally well-known photopolymerization initiators. Specific examples include benzophenone, "Darocur 1173" and "Irgacure 651" manufactured by Ciba Specialty Chemicals Inc., "Irgacure 184", "Irgacure 907", "Irgacure 754", etc.
用以形成硬塗層之組成物，於上述微粒子及活性能量線固化型樹脂以外，亦可包含各種添加劑（例如：聚合抑制劑、抗氧化劑、紫外線吸收劑、抗靜電劑、光穩定劑、溶劑、消泡劑、均染劑）。The composition used to form the hard coat layer may also contain various additives (such as polymerization inhibitors, antioxidants, ultraviolet absorbers, antistatic agents, light stabilizers, solvents, etc.) in addition to the above-mentioned fine particles and active energy ray-curable resin. , defoaming agent, leveling agent).
藉由於上已述之本實施型態相關的製造方法，可製造包含液晶固化層的液晶固化薄膜。在此製造方法，通常可獲得包含基材、形成於此基材之支撐面上之液晶固化層，與形成於液晶固化層之上之硬塗層的液晶固化薄膜。By the manufacturing method related to this embodiment described above, a liquid crystal cured film including a liquid crystal cured layer can be manufactured. In this manufacturing method, a liquid crystal cured film including a substrate, a liquid crystal solidified layer formed on the supporting surface of the substrate, and a hard coating layer formed on the liquid crystal solidified layer can generally be obtained.
液晶固化層之厚度，得以可使相位差等特性位於期望之範圍的方式來適當設定。具體而言，液晶固化層之厚度以0.5 μm以上為佳，以1.0 μm以上為較佳，且以10 μm以下為佳，以7 μm以下為較佳。The thickness of the liquid crystal solidified layer is appropriately set so that characteristics such as phase difference are within a desired range. Specifically, the thickness of the liquid crystal solidified layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, 10 μm or less, and preferably 7 μm or less.
硬塗層之厚度，以0.5 μm以上且20 μm以下為佳，以0.5 μm以上且10 μm以下為較佳，以0.5 μm以上且8 μm以下為更佳。The thickness of the hard coat layer is preferably from 0.5 μm to 20 μm, preferably from 0.5 μm to 10 μm, and more preferably from 0.5 μm to 8 μm.
［任意工序］[Any process]
於上已述之實施型態相關的液晶固化薄膜之製造方法亦可更包含任意工序組合至於上已述之工序3A及工序3B。The manufacturing method of the liquid crystal cured film related to the above-described embodiments may further include any combination of steps as to the above-described steps 3A and 3B.
液晶固化薄膜之製造方法，舉例而言，亦可包含：自支撐面剝離液晶固化層的工序、於液晶固化層之上或硬塗層之上進一步形成任意層體的工序。並且，液晶固化薄膜之製造方法亦可包含於工序3A之後將液晶固化層加熱的工序。The manufacturing method of the liquid crystal cured film may also include, for example, the process of peeling off the liquid crystal cured layer from the supporting surface, and the process of further forming any layer on the liquid crystal cured layer or on the hard coat layer. Moreover, the manufacturing method of a liquid crystal cured film may also include the process of heating a liquid crystal solidified layer after process 3A.
作為任意層體，可列舉：相位差薄膜；用以與其他部件接合的接合層；優化薄膜之滑順性的基墊層；抗反射層；防汙層；等。Examples of any layer include: retardation film; a bonding layer used to bond with other components; a base layer to optimize the smoothness of the film; an anti-reflective layer; an antifouling layer; etc.
再者，本實施型態之液晶固化薄膜之製造方法，舉例而言，亦可包含將形成於基材上之液晶固化層轉印至任意薄膜層的工序。據此，舉例而言，液晶固化薄膜之製造方法亦可包含在將形成於基材上之液晶固化層與任意薄膜層貼合後，視需求將基材剝離，以獲得包含液晶固化層及任意薄膜層之液晶固化薄膜的工序。此時，於貼合亦可使用適切的黏合劑或接合劑。Furthermore, the manufacturing method of the liquid crystal solidified film of this embodiment may also include, for example, the process of transferring the liquid crystal solidified layer formed on a base material to any thin film layer. Accordingly, for example, the manufacturing method of the liquid crystal cured film may also include laminating the liquid crystal cured layer formed on the substrate with any film layer, and then peeling off the substrate if necessary to obtain a liquid crystal cured film including the liquid crystal cured layer and any film layer. The process of liquid crystal curing thin film layer. At this time, appropriate adhesive or jointing agent can also be used for bonding.
並且，液晶固化薄膜之製造方法，亦可包含於工序3A之前使在工序2形成之液晶組成物之層體乾燥的工序。此種乾燥得藉由自然乾燥、加熱乾燥、減壓乾燥、減壓加熱乾燥等乾燥方法來達成。藉由此種乾燥，可自液晶組成物之層體將溶媒去除。Furthermore, the method of manufacturing a liquid crystal cured film may include a step of drying the layer of the liquid crystal composition formed in
［液晶固化薄膜的用途］[Applications of liquid crystal curable films]
藉由本實施型態之液晶固化薄膜之製造方法獲得之液晶固化薄膜，得使用於各類用途。舉例而言，得與偏光件組合而做成偏光板。在做成偏光板的情況下，藉由設置於有機電致發光顯示裝置（以下適時稱作「有機EL顯示裝置」。）之顯示面可抑制外部光線的反射，故為合適。The liquid crystal cured film obtained by the manufacturing method of the liquid crystal cured film of this embodiment can be used for various purposes. For example, it can be combined with a polarizer to make a polarizing plate. When used as a polarizing plate, it is suitable to suppress reflection of external light by being provided on the display surface of an organic electroluminescence display device (hereinafter referred to as "organic EL display device").
［作用、效果］[Effect]
在本實施型態中，自工序2往工序3A之運送（2－3A），藉由以非接觸狀態支撐薄膜之液晶組成物層側之面的運送部件（2－3A），自已進行工序2後至進行工序3A為止的期間，維持與薄膜之液晶組成物層側之面的非接觸狀態來進行。並且，在本實施型態中，自工序3A往工序3B之運送（3A－3B），藉由以非接觸狀態支撐薄膜之液晶固化層側之面的運送部件（3A－3B），自已進行工序3A後至進行工序3B為止的期間，維持與薄膜之液晶固化層側之面的非接觸狀態來進行。In this embodiment, the transportation from
其結果，根據本實施型態之液晶固化薄膜之製造方法，可提供防止在已形成液晶組成物之層體的基材產生傷痕及其他缺失的液晶固化薄膜之製造方法。As a result, according to the method of manufacturing a liquid crystal cured film of this embodiment, it is possible to provide a method of manufacturing a liquid crystal cured film that prevents scratches and other defects from occurring on a base material on which a layer of a liquid crystal composition is formed.
［實施型態2］[Implementation type 2]
以下參照圖5，同時說明本發明之實施型態2相關的薄膜之製造方法及製造裝置。圖5係繪示於實施型態2相關的薄膜之製造方法使用之裝置200的側視示意圖。The following describes a thin film manufacturing method and a manufacturing apparatus according to
本實施型態之薄膜之製造方法，就不包含將保護薄膜貼合於在賦予定向限制力的工序A之後獲得之基材1A的保護薄膜貼合工序這點，與實施型態1有所差異。下面對於與實施型態1同樣的構造，附上相同符號，省略重複的說明。The film manufacturing method of this embodiment is different from the first embodiment in that it does not include a protective film laminating step of laminating the protective film to the
在本實施型態之薄膜之製造方法中，已進行工序A後之基材1A，可藉由運送部件221&222運送至塗布裝置210。於運送至塗布裝置210的基材1A之表面1A1塗布液晶組成物，藉此可獲得具備基材1與形成於基材之表面1A1之液晶組成物層5的薄膜10（參照圖2）。在本實施型態之薄膜之製造方法中，由於不包含保護薄膜貼合工序，故不包含將保護薄膜剝離的工序（工序B1）及將保護薄膜剝離後之基材的張力阻斷的工序（工序B2）。In the film manufacturing method of this embodiment, the
於本實施型態之薄膜之製造方法使用之裝置，具備：於基材1之表面S塗布液晶組成物以形成液晶組成物層5的塗布裝置210，與將基材1（基材1A）運送至塗布裝置210的運送部件221&222。在本實施型態中使用之運送部件221&222，係以非接觸狀態支撐基材1之表面1A1的運送部件，係至進行工序2為止的期間維持與基材之表面S的非接觸狀態來進行基材之運送的運送部件。運送部件221&222為與在實施型態1說明之運送部件121&122相同的形狀（圓筒形），係與運送方向平行之截面形狀為圓形的運送部件。The device used in the thin film manufacturing method of this embodiment includes: a
在圖5中，207及208係軋輥，但此等軋輥207&208與基材1A之上側面接觸而不與基材1A之表面1A1（在圖5中之下側面）接觸。因此，在本實施型態之薄膜之製造方法中，至進行工序2為止的期間，亦得維持與基材1（1A）之表面1A1的非接觸狀態來進行基材1（基材1A）的運送。In Figure 5, 207 and 208 are rollers, but these
其次，說明本實施型態之作用及效果。Next, the functions and effects of this embodiment will be described.
在本實施型態之薄膜之製造方法中，將自送出裝置201送出的基材1沿A1所示之方向運送，在賦予定向限制力之裝置202中，對基材1之表面1A1賦予定向限制力（工序A）。藉由進行工序A，可獲得經賦予定向限制力之基材1A。In the film manufacturing method of this embodiment, the
藉由在以非接觸狀態支撐基材1A之表面1A1的狀態下運送的運送部件221&222，將已進行工序A後之基材（基材1A）運送至塗布裝置210。藉此，至進行工序2為止的期間，可維持運送部件與基材1A之表面1A1的非接觸狀態來進行已進行工序A後之基材1A的運送。The base material (
其次，進行於已運送至塗布裝置210的基材1A之表面1A1塗布液晶組成物以形成液晶組成物層5的工序2。藉此，可獲得如圖2所示之具備基材1A與形成於基材1A之表面1A1上之液晶組成物層5的薄膜10。Next, the
在本實施型態之薄膜之製造方法中，至進行工序2為止的期間，亦藉由以非接觸狀態支撐基材1（基材1A）之表面1A1的運送部件221&222維持與基材1（1A）之表面1A1的非接觸狀態，來進行基材1（基材1A）的運送。In the film manufacturing method of this embodiment, until
其結果，根據本實施型態之薄膜之製造方法，可提供防止在塗布有液晶組成物之基材中產生傷痕的薄膜之製造方法及製造裝置。As a result, according to the thin film manufacturing method of this embodiment, it is possible to provide a thin film manufacturing method and a manufacturing apparatus that prevent scratches from occurring on a base material coated with a liquid crystal composition.
藉由本實施型態之薄膜之製造方法獲得之薄膜，可作為製造液晶固化薄膜的薄膜使用。使用藉由本實施型態之薄膜之製造方法獲得之薄膜的液晶固化薄膜，可藉由與在實施型態1說明之液晶固化薄膜之製造方法相同的方法來製造。The film obtained by the film production method of this embodiment can be used as a film for producing a liquid crystal cured film. The liquid crystal cured film using the film obtained by the film production method of this embodiment can be produced by the same method as the liquid crystal cured film production method described in
『實施例』"Example"
以下揭示實施例以具體說明本發明。惟本發明並非受限於以下所揭示之實施例者，在不脫離本發明之申請專利範圍及其均等之範圍的範圍內，得任意變更而實施。The following examples are disclosed to specifically illustrate the present invention. However, the present invention is not limited to the embodiments disclosed below, and may be arbitrarily modified and implemented within the scope of the patentable scope of the present invention and its equivalent scope.
在以下說明中，表示量的「%」及「份」，除非另有註記，否則係重量基準。並且，於以下說明的操作，除非另有註記，否則在常溫常壓大氣中進行。In the following description, "%" and "parts" of amounts expressed are based on weight unless otherwise noted. In addition, unless otherwise noted, the operations described below are performed in the atmosphere at normal temperature and pressure.
［評價方法］[Evaluation method]
（A.傷痕狀缺陷的檢查）(A. Inspection of scar-like defects)
（A-1）檢查對象的準備(A-1) Preparation of inspection objects
在各例中，將保護薄膜（藤森工業股份有限公司製之MASTACK TFB系列）貼合於經取樣之基材以製作附保護薄膜之試樣薄膜。In each case, a protective film (MASTACK TFB series manufactured by Fujimori Industrial Co., Ltd.) was bonded to the sampled base material to prepare a sample film with a protective film.
於表面狀態評價用角型材，將與附保護薄膜之試樣薄膜的保護薄膜貼合面為相反側之面配置於角型材側，並以強力磁石將附保護薄膜之試樣薄膜固定。將以不會在試樣薄膜產生折痕的方式自已固定於角型材之附保護薄膜之試樣薄膜剝下保護薄膜者（已固定於角型材之試樣薄膜），做成檢查對象。For the angle profile used for surface condition evaluation, place the surface opposite to the protective film-attached surface of the sample film with protective film on the corner profile side, and fix the sample film with protective film with a strong magnet. The sample film with the protective film attached to the corner profile that has been fixed to the corner profile in a manner that does not cause creases in the sample film is peeled off with the protective film (sample film that has been fixed to the corner profile) to be inspected.
（A-2）利用POLARION燈之傷痕狀缺陷的檢查(A-2) Inspection of scar-like defects using POLARION lamp
自檢查對象之試樣薄膜的邊緣部，在使POLARION燈（POLARION公司製之NP-1）自斜下方向照射的同時，使之依序沿TD方向移動，藉由目視來觀察傷痕狀缺陷的有無。將長度超過50 mm的傷痕判斷為傷痕狀缺陷，對檢測出的傷痕狀缺陷附加標記。From the edge of the sample film to be inspected, the POLARION lamp (NP-1 manufactured by POLARION Co., Ltd.) is irradiated from an oblique downward direction while sequentially moving in the TD direction, and the scar-like defects are visually observed. Yes or no. Wounds with a length exceeding 50 mm are judged as scar-like defects, and marks are attached to the detected scar-like defects.
對於檢測出的傷痕狀缺陷，沿MD方向量測長度，在長度未達1 m便中斷的情況下，沿MD方向觀察是否有其他傷痕狀缺陷，在沿MD方向間歇產生的情況下，判斷為1條。隨後量測傷痕狀缺陷之TD方向的位置。For the detected scar-like defects, measure the length along the MD direction. If the length is interrupted before reaching 1 m, observe whether there are other scar-like defects along the MD direction. If they occur intermittently along the MD direction, judge it to be 1 item. Then measure the position of the scar-like defect in the TD direction.
其次，進行檢測出的傷痕狀缺陷與傷痕狀缺陷之範本（日本瑞翁股份有限公司，內部管理品，光學薄膜用範本）的比較。在改變POLARION燈的照射角度、觀察的方向（角度）的同時，在範本與檢測出之傷痕狀缺陷之個別最可看見的條件下比較，量測長度及粗細較範本還大之傷痕狀缺陷的條數與其位置。在試樣薄膜之長度1 m×製品幅寬的範圍進行上述量測。Secondly, the detected scar-like defects were compared with a scar-like defect template (Japan Zeon Co., Ltd., internal control product, optical film template). While changing the illumination angle of the POLARION lamp and the direction (angle) of observation, compare the template and the detected scar-like defects under the most visible conditions, and measure the scar-like defects whose length and thickness are larger than those of the template. Number of bars and their positions. The above measurement is carried out in the range of the length of the sample film 1 m × the width of the product.
（A-3）螢光燈反射檢查(A-3) Fluorescent lamp reflection inspection
將在（A-2）中超過範本之傷痕狀缺陷逐一切割成MD 20 cm×TD 15 cm的大小，夾於黑色塑膠瓦楞框。在暗室內的黑板之上以雙手握持試樣，將眼睛與試樣薄膜的距離、試樣薄膜與螢光燈的距離分別定為30 cm以下，改變試樣薄膜的角度，使螢光燈的光線反射，觀察是否可觀看到傷痕狀缺陷。傷痕狀缺陷的觀察，自試樣薄膜的兩面側進行，自MD方向及TD方向之兩方向照射螢光燈之光線來觀察。量測使螢光燈之光線反射而可觀看到的傷痕狀缺陷之數量與其位置。傷痕狀缺陷之數量揭示於表1。在傷痕狀缺陷之數量為150個以上的情況下，定為「多量」。Cut the scar-like defects that exceed the template in (A-2) one by one into sizes of
（B.漏光檢查）(B. Light leakage inspection)
於背光之上配置偏光板2片，於2個偏光板之間配置在各例製作之液晶固化薄膜。2片偏光板配置成平行尼寇稜鏡。液晶固化薄膜以液晶固化薄膜之慢軸與2片偏光板之穿透軸呈45°的方式配置。Two polarizing plates were placed on the backlight, and the liquid crystal cured film produced in each example was placed between the two polarizing plates. The two polarizing plates are arranged in parallel to each other. The liquid crystal cured film is arranged so that the slow axis of the liquid crystal cured film and the transmission axis of the two polarizing plates are 45°.
自配置於背光之上的偏光板／液晶固化薄膜／偏光板之堆疊體的正面側，藉由肉眼觀察漏光的有無，量測漏光之數量（亮點之數量）。對於檢測出之漏光，進行利用顯微鏡（倍率500倍，奧林巴斯股份有限公司製之偏光顯微鏡BX51-P）的觀察，判斷是否為由傷痕狀缺陷所導致者。排除由傷痕狀缺陷以外之原因所致的漏光，算出液晶固化薄膜每單位面積由傷痕狀缺陷所導致的亮點之數量。結果揭示於表1。The amount of light leakage (the number of bright spots) is measured by visually observing the presence or absence of light leakage from the front side of the stack of polarizing plate/liquid crystal cured film/polarizing plate placed on the backlight. The detected light leakage was observed using a microscope (500x magnification, polarizing microscope BX51-P manufactured by Olympus Co., Ltd.) to determine whether it was caused by a scar-like defect. Excluding light leakage caused by causes other than scar-like defects, calculate the number of bright spots caused by scar-like defects per unit area of the liquid crystal cured film. The results are revealed in Table 1.
［液晶化合物的說明］[Explanation of liquid crystal compounds]
在以下說明之實施例及比較例使用之液晶化合物1的結構，係如下述式（A-1）所示。The structure of the
『化3』（A-1）"Chemical 3" (A-1)
［液晶組成物的製備］[Preparation of liquid crystal composition]
將上述式（A-1）所示之「液晶化合物1」100重量份、光聚合起始劑（ADEKA ARKLS NCI730）4.0重量份、氟系界面活性劑（DIC公司製之「F562」）0.30重量份，以及作為溶媒之1,3-二氧𠷬243.4重量份混合，獲得液晶組成物（固體成分30%）。100 parts by weight of "
［實施例1］[Example 1]
使用在實施型態2作為薄膜之製造裝置說明的薄膜之製造裝置200（參照圖5），藉由以下程序製造實施例1之薄膜。The film of Example 1 was manufactured by the following procedure using the film manufacturing apparatus 200 (see FIG. 5 ) described as the film manufacturing apparatus in
（1-1.工序1）(1-1. Process 1)
（1-1-1.工序A）(1-1-1. Process A)
使用包含環烯烴聚合物之長條狀的樹脂薄膜（日本瑞翁股份有限公司製之ZeonorFilm；厚度115 μm）作為基材。將此基材自送出裝置201送出，運送至賦予定向限制力之裝置202，以延伸倍率1.5沿相對於基材之幅寬方向45°方向斜向延伸，賦予定向限制力。經賦予定向限制力之基材（以下亦稱作「基材X」），面內相位差Re為140 nm，厚度為77 μm。A long strip of resin film containing a cycloolefin polymer (ZeonorFilm manufactured by Zeon Co., Ltd.; thickness: 115 μm) was used as the base material. The base material is sent out from the
（1-1-2.利用運送部件的運送）(1-1-2. Transportation using transportation parts)
將2支由多孔質材料（材質：陶瓷，平均孔徑2 μm，Nano-TEM Co., Ltd.製）而成的圓筒狀之運送部件（漂浮運送部件）作為運送部件221&222使用，使在（1-1-1）製造之基材X以運送速度10 m/分鐘、運送張力300 N運送5分鐘後，使運送線停止，在較運送部件221&222還要下游側進行基材X的取樣，供於傷痕狀缺陷的檢查。所使用的運送部件，係具有將壓力為0.2 MPa之高壓空氣噴出之孔的部件。取樣藉由將基材X之全幅寬（約1330 mm）×約3000 mm（約4 m2
）程度之大小者切出來進行。在本例中使用之運送部件由於係以使基材漂浮之狀態（非接觸狀態）支撐同時運送的部件，故利用該運送部件之基材X的運送係維持運送部件與基材X之表面S的非接觸狀態來進行。Two cylindrical transport members (floating transport members) made of porous material (material: ceramic,
（1-2.工序2）(1-2. Process 2)
將傷痕狀缺陷之檢查之後的基材X切割成A3尺寸程度，獲得方形狀的基材X。於該方形狀的基材X之配置有運送部件221之側之面（在圖5中之下側面）塗布液晶組成物，獲得於表面S形成有液晶組成物層的基材X。The base material X after inspection of scar-like defects is cut into approximately A3 size, and a square-shaped base material X is obtained. The liquid crystal composition is applied to the side of the square-shaped substrate X where the
（1-3.工序3A）(1-3. Process 3A)
使形成有液晶組成物層之基材X的液晶組成物層在110℃乾燥4分鐘後，進行UV照射，使液晶組成物層固化，以製造液晶固化薄膜。對於所獲得之液晶固化薄膜進行漏光檢查，結果揭示於表1。UV照射的條件定為1000 mJ/cm2 。The liquid crystal composition layer of the base material X on which the liquid crystal composition layer was formed was dried at 110° C. for 4 minutes, and then UV irradiated to solidify the liquid crystal composition layer to produce a liquid crystal cured film. The obtained liquid crystal cured film was subjected to light leakage inspection, and the results are shown in Table 1. The UV irradiation conditions were set to 1000 mJ/cm 2 .
［比較例1～5］[Comparative Examples 1 to 5]
在實施例1之（1-1-2）中，除了使用以下運送部件代替漂浮運送部件以外，進行與實施例1相同的操作。在比較例1～5，利用運送部件的基材X之運送，係在運送部件與基材X之表面S接觸的狀態下進行。 比較例1之運送部件（微細溝輥）：於表面進行溝加工之圓筒狀的運送輥（Rz（最大高度）＝0.8 μm）（材質：於鋁材原管之表面鍍鉻，野村鍍金製之運送輥） 比較例2之運送部件（特殊基墊輥）：具備凹凸結構的特殊基墊輥（Rz＝5 μm）（材質：於鋁材原管之表面鍍鉻，野村鍍金製之運送輥） 比較例3之運送部件（鍍鉻輥）：鍍鉻輥（Rz＝0.8 μm）（材質：於鋁材原管之表面鍍鉻，OTEC股份有限公司製之運送輥） 比較例4之運送部件（鍍DLC輥）：經過類鑽碳（DLC）之表面處理的輥（韋克斯硬度約2000，Rz＝0.4 μm）（材質：於鋁材原管之表面施以鍍鉻，先表面研磨再鍍DLC，野村鍍金製之運送輥） 比較例5之運送部件（PTFE輥）：聚四氟乙烯（PTFE）輥（於運送輥（OTEC股份有限公司製之運送輥）纏繞有PTFE管（GUNZE股份有限公司製之氟PFA熱收縮管100PB）者）In Example 1 (1-1-2), the same operation as in Example 1 was performed except that the following conveyance member was used instead of the floating conveyance member. In Comparative Examples 1 to 5, the conveyance of the base material X by the conveyance member was performed in a state where the conveyance member was in contact with the surface S of the base material X. Transport member of Comparative Example 1 (fine groove roller): cylindrical transport roller with a grooved surface (Rz (maximum height) = 0.8 μm) (Material: chrome plated on the surface of the original aluminum pipe, made by Nomura gold plating) conveyor roller) The conveying part of Comparative Example 2 (special base roller): Special base roller with concave and convex structure (Rz=5 μm) (Material: chrome plating on the surface of the original aluminum pipe, Nomura gold-plated conveying roller) Conveying parts (chromium-plated roller) of Comparative Example 3: Chrome-plated roller (Rz=0.8 μm) (Material: chrome-plated surface of aluminum original pipe, conveying roller manufactured by OTEC Co., Ltd.) Transport component of Comparative Example 4 (DLC-plated roller): Roller surface-treated with diamond-like carbon (DLC) (Weckers hardness approximately 2000, Rz = 0.4 μm) (Material: Chromium plating on the surface of the original aluminum tube , first surface grinding and then DLC plating, Nomura gold-plated transport roller) Conveying member (PTFE roller) of Comparative Example 5: Polytetrafluoroethylene (PTFE) roller (conveying roller (conveying roller manufactured by OTEC Co., Ltd.) wrapped with a PTFE tube (fluorine PFA heat shrinkable tube 100PB manufactured by GUNZE Co., Ltd.) )By)
在比較例1～5中，亦如同實施例1，對於在工序1之後取樣之基材X進行傷痕狀缺陷的檢查。並且，在比較例1～5中，亦使用將各例之傷痕狀缺陷之檢查之後的基材X切割成A3尺寸之方形狀的基材X，進行與實施例1之（1-2）及（1-3）相同的操作，製造液晶固化薄膜，對於各液晶固化薄膜進行漏光試驗。結果揭示於表1。In Comparative Examples 1 to 5, similarly to Example 1, the base material X sampled after the
『表1』
根據以上結果，可知在基材之運送係維持運送部件與基材之表面S的非接觸狀態來進行的實施例1，與比較例1～5相比，起因於傷痕狀缺陷之亮點的數量少。就上述結果而言，根據使用本發明所規定之運送部件的實施例1，得實現防止在塗布有液晶組成物之基材產生傷痕的薄膜之製造方法。From the above results, it can be seen that in Example 1, in which the substrate is transported while maintaining the non-contact state between the transport member and the surface S of the substrate, the number of bright spots caused by scar-like defects is smaller than in Comparative Examples 1 to 5. . From the above results, according to Example 1 using the transport member specified by the present invention, it is possible to realize a method of manufacturing a film that prevents scratches on a base material coated with a liquid crystal composition.
［其他實施型態］[Other implementation types]
（1）在上述實施型態，雖揭示作為運送部件整體係圓筒形且與運送方向平行之方向的截面呈圓形者，但運送部件不受限於此。運送部件只要於其至少一部分具有截面弧狀部即可，亦可為例如：在與運送方向平行之方向的截面形狀為扇形的運送部件、在與運送方向平行之方向的截面形狀為橢圓形的運送部件、如圖6所示與運送方向平行之方向的截面為拱形者。(1) In the above embodiment, it is disclosed that the conveying member is cylindrical as a whole and has a circular cross-section in a direction parallel to the conveying direction, but the conveying member is not limited to this. The conveying member only needs to have a cross-sectional arc at at least a part of the conveying member. For example, the conveying member may have a fan-shaped cross-sectional shape in a direction parallel to the conveying direction, or may have an elliptical cross-sectional shape in a direction parallel to the conveying direction. The conveying member has an arched cross section parallel to the conveying direction as shown in FIG. 6 .
在圖6所示之運送部件300中，300A至300B的部分300R係截面弧狀部。In the
（2）在上述實施型態中，雖揭示包含工序A的薄膜之製造方法，但本發明不受限於此。薄膜之製造方法亦可為不包含工序A者。此情況下，亦可在工序1中運送未賦予定向限制力之基材，在工序2中於前述基材形成液晶組成物之層體。(2) In the above-described embodiment, the method for manufacturing the thin film including step A is disclosed, but the present invention is not limited thereto. The film manufacturing method may not include step A. In this case, it is also possible to transport a base material to which no orientation restricting force is provided in
（3）在上述實施型態中，雖揭示將2個運送部件一併配置於基材之表面S側的態樣，但運送部件之數量及配置位置不受限於此。運送部件之數量可為1個，亦可為3個以上。並且，亦可將運送部件交互配置於基材之表面S側及與表面S為相反側之面。(3) In the above-mentioned embodiment, it is disclosed that two conveying members are arranged together on the surface S side of the base material, but the number and arrangement position of the conveying members are not limited thereto. The number of shipping parts can be 1 or 3 or more. Furthermore, the conveying members may be alternately arranged on the surface S side of the base material and on the surface opposite to the surface S.
（4）在上述實施型態中，雖揭示於液晶固化層之上進一步形成硬塗層的液晶固化薄膜之製造方法，但液晶固化薄膜之製造方法亦可為不包含形成硬塗層的工序（工序3B）者。(4) In the above embodiment, a method of manufacturing a liquid crystal cured film in which a hard coat layer is further formed on the liquid crystal solidified layer is disclosed. However, the method of manufacturing a liquid crystal cured film may not include the step of forming the hard coat layer ( Step 3B).
1:基材
1A:經賦予定向限制力之基材
1A1:基材之塗布有液晶組成物之面（亦即表面S）
2:保護薄膜
5:液晶組成物層
10:薄膜
20:附保護薄膜之基材
100:薄膜之製造裝置
101、103:送出裝置
102:賦予定向限制力之裝置
104:收捲裝置
105A、105B、106A、106B:軋輥
107、108:吸輥
110:塗布裝置
121、122:運送部件
121R:截面弧狀部
200:薄膜之製造裝置
201:送出裝置
202:賦予定向限制力之裝置
207、208:軋輥
210:塗布裝置
221、222:運送部件
300:運送部件
300A:截面弧狀部之起點
300B:截面弧狀部之終點
300R:截面弧狀部1:
〈圖1〉圖1係繪示於實施型態1相關的薄膜之製造方法使用之裝置的側視示意圖。
〈圖2〉圖2係繪示在實施型態1相關的薄膜之製造方法中所獲得之薄膜的剖面示意圖。
〈圖3〉圖3係繪示附保護薄膜之基材的剖面示意圖。
〈圖4〉圖4係繪示運送部件的剖面示意圖。
〈圖5〉圖5係繪示於實施型態2相關的薄膜之製造方法使用之裝置的側視示意圖。
〈圖6〉圖6係繪示在其他實施型態說明之運送部件的剖面示意圖。<Fig. 1> Fig. 1 is a schematic side view of an apparatus used in the thin film manufacturing method according to
1:基材 1:Substrate
1A:經賦予定向限制力之基材 1A: Base material endowed with directional restraint force
1A1:基材之塗布有液晶組成物之面(亦即表面S) 1A1: The surface of the substrate coated with the liquid crystal composition (i.e. surface S)
2:保護薄膜 2: Protective film
10:薄膜 10:Film
20:附保護薄膜之基材 20: Base material with protective film
100:薄膜之製造裝置 100: Film manufacturing equipment
101、103:送出裝置 101, 103: sending device
102:賦予定向限制力之裝置 102: Device that imparts directional restriction force
104:收捲裝置 104: Rewinding device
105A、105B、106A、106B:軋輥 105A, 105B, 106A, 106B: Roller
107、108:吸輥 107, 108: Suction roller
110:塗布裝置 110: Coating device
121、122:運送部件 121, 122: Shipping parts
A1:方向 A1: Direction
Claims (13)
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| JP2018246100 | 2018-12-27 | ||
| JP2018-246100 | 2018-12-27 |
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| JP (1) | JP7409323B2 (en) |
| KR (1) | KR20210107677A (en) |
| CN (1) | CN113195111A (en) |
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| WO (1) | WO2020138212A1 (en) |
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| JP7507039B2 (en) | 2020-08-21 | 2024-06-27 | 日東電工株式会社 | Method for manufacturing optical film |
| JP2023013267A (en) * | 2021-07-15 | 2023-01-26 | 日東電工株式会社 | Manufacturing method of functional layer and manufacturing apparatus of the same |
| JP7379420B2 (en) * | 2021-07-15 | 2023-11-14 | 日東電工株式会社 | Functional layer manufacturing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006072298A (en) * | 2004-08-02 | 2006-03-16 | Nitto Denko Corp | Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, optical film and image display device |
| JP2011028039A (en) * | 2009-07-27 | 2011-02-10 | Nitto Denko Corp | Method for manufacturing laminated optical film |
| JP2016012031A (en) * | 2014-06-27 | 2016-01-21 | 日本ゼオン株式会社 | Method for manufacturing multilayer film, retardation film, circularly polarizing plate, and organic electroluminescence display device |
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| CN100392488C (en) * | 2004-08-02 | 2008-06-04 | 日东电工株式会社 | Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, optical film and image viewing display |
| JP2006099855A (en) | 2004-09-29 | 2006-04-13 | Fuji Photo Film Co Ltd | Transparent layer manufacturing method and transparent layer manufacture equipment |
| JP2008083244A (en) | 2006-09-26 | 2008-04-10 | Fujifilm Corp | Method and equipment for processing long-size material to be conveyed |
| JP2015143786A (en) | 2014-01-31 | 2015-08-06 | 住友化学株式会社 | liquid crystal cured film |
| CN107533179A (en) * | 2015-04-24 | 2018-01-02 | 日本瑞翁株式会社 | The manufacture method and multilayer film of multilayer film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006072298A (en) * | 2004-08-02 | 2006-03-16 | Nitto Denko Corp | Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, optical film and image display device |
| JP2011028039A (en) * | 2009-07-27 | 2011-02-10 | Nitto Denko Corp | Method for manufacturing laminated optical film |
| JP2016012031A (en) * | 2014-06-27 | 2016-01-21 | 日本ゼオン株式会社 | Method for manufacturing multilayer film, retardation film, circularly polarizing plate, and organic electroluminescence display device |
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| TW202032173A (en) | 2020-09-01 |
| KR20210107677A (en) | 2021-09-01 |
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| CN113195111A (en) | 2021-07-30 |
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| WO2020138212A1 (en) | 2020-07-02 |
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