TWI693998B - 積層薄膜之製造方法 - Google Patents

積層薄膜之製造方法 Download PDF

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TWI693998B
TWI693998B TW104104784A TW104104784A TWI693998B TW I693998 B TWI693998 B TW I693998B TW 104104784 A TW104104784 A TW 104104784A TW 104104784 A TW104104784 A TW 104104784A TW I693998 B TWI693998 B TW I693998B
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Taiwan
Prior art keywords
film
coating
laminated
manufacturing
temperature
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TW104104784A
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English (en)
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TW201542341A (zh
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內海京久
疋田伸治
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日商富士軟片股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/0046—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by constructional aspects of the apparatus
    • B32B37/0053—Constructional details of laminating machines comprising rollers; Constructional features of the rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/0277—Apparatus with continuous transport of the material to be cured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1403—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the type of electromagnetic or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/488—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives characterised by their shape, e.g. being fibres or being spherical being longitudinal, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/52—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
    • B29C65/524—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive by applying the adhesive from an outlet device in contact with, or almost in contact with, the surface of the part to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
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    • B29C65/524—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive by applying the adhesive from an outlet device in contact with, or almost in contact with, the surface of the part to be joined
    • B29C65/525—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive by applying the adhesive from an outlet device in contact with, or almost in contact with, the surface of the part to be joined by extrusion coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/78—Means for handling the parts to be joined, e.g. for making containers or hollow articles, e.g. means for handling sheets, plates, web-like materials, tubular articles, hollow articles or elements to be joined therewith; Means for discharging the joined articles from the joining apparatus
    • B29C65/7858—Means for handling the parts to be joined, e.g. for making containers or hollow articles, e.g. means for handling sheets, plates, web-like materials, tubular articles, hollow articles or elements to be joined therewith; Means for discharging the joined articles from the joining apparatus characterised by the feeding movement of the parts to be joined
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    • B29C65/7894—Means for handling of moving sheets or webs of continuously moving sheets or webs
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
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    • B29C66/723—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered
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    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
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Abstract

本發明提供一種積層薄膜之製造方法，其係可抑制硬化層的厚度不均、及積層薄膜全體出現皺紋。在塗布部(20)，將含有活性射線硬化型樹脂的塗布液塗布在被連續搬運的第一薄膜(10)的表面，在層合部(30)形成塗膜(22)，將被連續搬運的第二薄膜(50)層合在塗膜(22)上，以第一薄膜(10)與第二薄膜(50)夾住塗膜(22)，在硬化部(60)，在以第一薄膜(10)與第二薄膜(50)夾住塗膜(22)的狀態下，將第一薄膜(10)包繞住支承輥(62)，進行連續搬運，同時由紫外線照射裝置(64)照射紫外線，使塗膜(22)硬化，形成硬化層(28)，而製造出積層薄膜(70)。

Description

積層薄膜之製造方法
本發明關於一種積層薄膜之製造方法。
在光學元件、液晶顯示器或有機EL顯示器等的顯示裝置、半導體裝置、薄膜太陽能電池等的各種裝置中，利用了像是氣體障蔽薄膜、保護薄膜、濾光片或抗反射薄膜等，由多個薄膜所構成的積層薄膜。關於此積層薄膜之製造方法，已有文獻提出各種方法。
例如專利文獻1揭示將基材薄膜與第1鑄型薄膜供給至隔著間隙並行配置的一對輥，並將紫外線硬化型樹脂液朝向輥的間隙吐出，同時使兩輥往彼此咬合的方向旋轉，使紫外線硬化型樹脂液被夾在基材薄膜與第1鑄型薄膜之間，以這樣的方式，在夾住的狀態下進行紫外線照射，使樹脂液硬化，藉此製造出積層薄膜的方法。
先前技術文獻 專利文獻
專利文獻1 日本特開平9-024571號公報
然而，在專利文獻1的方法中，會有硬化層發生厚度不均、或者積層薄膜全體出現皺紋的問題。
本發明是鑑於這樣的情況而完成，目的為提供一種積層薄膜之製造方法，其係可抑制硬化層的厚度不均以及積層薄膜全體出現皺紋。
本實施形態之積層薄膜之製造方法至少包含：在被連續搬運的第一薄膜的表面塗布含有活性射線硬化型樹脂的塗布液，而形成塗膜的步驟；將包繞層合輥而被連續搬運的第二薄膜層合在塗膜上，並以第一薄膜與第二薄膜夾住塗膜的步驟；及在以第一薄膜與第二薄膜夾住塗膜的狀態下，將第一薄膜及第二薄膜之任一者包繞住支承輥，進行連續搬運，同時照射活性射線，使塗膜硬化，而形成硬化層的步驟。其中，使第一薄膜及第二薄膜相對於支承輥錯開地接觸，且在其表面形成塗膜的第一薄膜一開始接觸、包繞住支承輥的位置，至連續搬運的第二薄膜層合至該塗膜上的位置的距離為30mm以上。層合輥與支承輥的距離為第一薄膜、使塗膜硬化而成的硬化層、與第二薄膜的合計厚度值以上。
合適的情況為對塗膜照射活性射線之前的第一薄膜及第二薄膜的溫度與對塗膜照射活性射線之後的第一薄膜及第二薄膜的溫度的差為25℃以下。
合適的情況為在使第一薄膜及第二薄膜之任一者與支承輥接觸時，支承輥的溫度與第一薄膜的溫度差、及支承輥的溫度與第二薄膜的溫度的差為25℃以下。
合適的情況為第一薄膜及第二薄膜的溫度在玻璃轉移溫度以下。
合適的情況為第一薄膜及第二薄膜的至少一者為具備障蔽膜之障蔽薄膜，障蔽薄膜具備透氧率為1.00cm3/(m2．day．atm)以下的障蔽膜。此外，1.00cm3/(m2．day．atm)相當於9.87×10-6ml/(m2．day．Pa)。
合適的情況為第一薄膜及第二薄膜的至少一者具備硬塗層。
合適的情況為塗布液含有量子點及量子棒的至少一者。
合適的情況為障蔽膜含有選自氮化矽、氮氧化矽、氧化矽、氧化鋁中的至少一種化合物之無機膜。
合適的情況為第一薄膜及第二薄膜的至少一者具備光擴散層。
合適的情況為塗布液的黏度在40mPa．s~400mPa．s的範圍。
依據本發明之製造方法，可抑制硬化層的厚度不均及積層薄膜全體出現皺紋。
1‧‧‧製造設備
10‧‧‧第一薄膜
20‧‧‧塗布部
22‧‧‧塗膜
24‧‧‧模具塗布機
26‧‧‧支承輥
28‧‧‧硬化層
30‧‧‧層合部
32‧‧‧層合輥
34‧‧‧加熱室
36‧‧‧開口部
38‧‧‧開口部
50‧‧‧第二薄膜
60‧‧‧硬化部
62‧‧‧支承輥
64‧‧‧紫外線照射裝置
70‧‧‧積層薄膜
80‧‧‧剝離輥
P‧‧‧層合位置
第1圖為積層薄膜之製造設備的概略構成圖。
第2圖為積層薄膜之製造設備的部分放大圖。
以下依據附加圖式，對本發明之合適的實施形態作說明。本發明可藉由以下的合適的實施形態來作說明。在不脫離本發明的範圍之下可藉由許多手段進行變更，且可利用本實施形態以外的其他實施形態。所以，在本發明的範圍內的全部變更也都包括在申請專利範圍。
此處，圖中，相同的記號所表示的部分是具有同樣機能的同樣要素。另外，在本說明書中，使用「~」來表示數值範圍的情況，「~」所表示的上限、下限的數值也包括在數值範圍。
本發明人等針對積層薄膜的製造方法之中硬化層厚度不均及積層薄膜全體出現皺紋專心研究探討。以往的方法是將基材薄膜與第1鑄型薄膜供給至一對輥，並將紫外線硬化型樹脂液朝向旋轉的輥的間隙吐出，並且夾住。由於旋轉的輥會振動，因此所塗布的樹脂液層會產生厚度不均。因此會有對硬化層厚度的精密度不良的問題。另外，並沒有支撐住積層薄膜就進行紫外線的照射。因此會有因為紫外線照射的熱而在積層薄膜出現皺紋的問題。發明人等發現這些問題，而完成本發明。
本實施形態之積層薄膜之製造方法具有下述步驟作為主要構成：將含有活性射線硬化型樹脂的塗布液塗布在被連續搬運的第一薄膜的表面，而形成塗膜的步驟；將被連續搬運的第二薄膜層合在塗膜上，並以第一薄膜與第二薄膜夾住塗膜的步驟；在以第一薄膜與第二薄膜夾住塗膜的狀態下，將第一薄膜及第二薄膜之任一者包繞住支承輥，進行連續搬運，同時照射活性射線，使塗膜硬化，而形成硬化層的步驟。
本實施形態是在第一薄膜上形成既定厚度的塗膜之後，使第二薄膜層合於塗膜，因此可抑制塗膜的厚度不均。另外，照射活性射線時，在以第一薄膜與第 二薄膜夾住塗膜的狀態下，將第一薄膜及第二薄膜的任一者包繞住支承輥，並且連續搬運，因此可抑制第一薄膜與第二薄膜出現皺紋。
參考第1圖、第2圖來說明本實施形態之積層薄膜之製造方法。在本實施形態中，積層薄膜是指至少具有以兩個薄膜夾住藉由活性射線所硬化的樹脂的硬化層而成的結構的薄膜。
第1圖表示積層薄膜的製造設備1的概略圖，第2圖為製造設備1的部分放大圖。首先，由未圖示的送出機，第一薄膜10會被連續搬運到塗布部20。第一薄膜10會由送出機以例如1~50m/分鐘的搬運速度送出。但是不受限於此搬運速度。送出時，可對第一薄膜10施加例如20~150N/m的張力。從防止皺紋與防止薄膜滑動造成的瑕疵的觀點看來，宜為30~100N/m。
第一薄膜10具有相對向的第一表面與第二表面，且具有長形的形狀。第一薄膜10之第一表面與第二表面的距離，亦即厚度，宜為10~100μm。從減低適用的製品厚度的需求與防止皺紋的觀點看來，第一薄膜10的厚度以15μm~60μm為更佳。另外，第一薄膜10具有例如300~1500mm的寬度。第一薄膜10的厚度及寬度可依照適用的製品適當地選擇。
第一薄膜10宜採用含有選自醯化纖維素、環狀烯烴、丙烯酸系樹脂、聚對苯二甲酸乙二酯樹脂、及聚碳酸酯樹脂中的至少1種作為主成分的薄膜。第一薄膜10可達成保護後述塗膜22、及硬化層28不接觸氧氣 的作用，因此透氧率宜為1.00×10-4~1.00cm3/(m2．day．atm)。從透氧率的觀點看來，第一薄膜10宜以聚對苯二甲酸乙二酯樹脂作為主成分。為了達成上述透氧率，宜使用障蔽薄膜。此障蔽薄膜包含第一薄膜10與形成於第一薄膜10的第一表面或第二表面的障蔽膜。在第一薄膜10中，除了上述主成分的樹脂之外，還可含有例如可塑劑、紫外線吸收劑等。
在塗布部20，含有活性射線硬化型樹脂的塗布液會被塗布在被連續搬運的第一薄膜10的表面，而形成塗膜22(參考第2圖)。在塗布部20設置了例如模具塗布機24以及與模具塗布機24相對向而配置的支承輥26。將第一薄膜10之與形成有塗膜22的表面為相反側的表面包繞住支承輥26，塗布液會由模具塗布機24的吐出口塗布在被連續搬運的第一薄膜10的表面，而形成塗膜22。
此處塗膜22是指厚度調整成大致均勻的第一薄膜10上之硬化前的塗布液。塗膜22的厚度可因應適用的製品等適當地設定。塗膜22具有例如10~80μm的厚度。塗膜22可在例如相對於所設定的厚度為±5%的範圍內形成。
在本實施形態中已揭示利用擠壓塗布法的模具塗布機24作為塗布裝置，然而並不受其限定。只要可形成既定厚度的塗膜22，則可使用利用簾幕式塗布法、擠壓塗布法、棒塗布法或輥塗布法等各種方法的塗布裝置。
塗布部20所使用的塗布液含有活性射線硬化型樹脂。活性射線硬化型樹脂是指藉由照射活性射線，經過交聯反應、聚合反應而硬化的樹脂。活性射線是指紫外線、電子束、放射線(α射線、β射線、γ射線等)等電磁波。作為活性射線硬化型樹脂，可採用例如具有光線(紫外線)、電子束、放射線硬化性的多官能單體或多官能寡聚物的官能基的樹脂，其中以光聚合性官能基為佳。光聚合性官能基可列舉(甲基)丙烯醯基、乙烯基、苯乙烯基、烯丙基等的不飽和的聚合性官能基等。
塗布液的溶劑可使用例如有機溶劑。有機溶劑包括醇類、酮類、酯類、脂肪族烴類、醯胺類、醚類、醚醇類。這些溶劑以併用2種以上為佳，併用3種以上為更佳。
塗布液具有例如20~600mPa．s的黏度。從氣泡防止與厚度均勻性的觀點看來，塗布液的黏度係以40~400mPa．s為佳。
在塗布液中，除了可加入活性射線硬化型樹脂之外，還可加入量子點。量子點是指具有由量子局限效應所產生的光學特性且粒徑為奈米尺度的結晶粒子。量子點已知有例如核-殼結構的量子點。就核-殼結構的量子點而言，若以核/殼來表示，可列舉CdSe/ZnS、CdSe/CdS、CdTe/CdS、InP/ZnS、GaP/ZnS、Si/ZnS、InN/GaN等。但是，量子點的結構不受核-殼結構所限定。量子點可藉由改變其大小來改變光學特性。量子點的粒徑愈小，量子點發光的能量愈大。另外還可使用量子棒 來代替量子點。量子棒是指具有與量子點同樣的特性且為細長形狀的粒子。亦可同時使用量子點與量子棒。含有量子點及/或量子棒的積層薄膜亦被稱為量子點薄膜。量子點可參考例如日本特開2012-169271號公報的第0060~0066段，但並不受限於此處所記載者。量子點可完全沒有限制地使用市售品。量子點的發光波長通常可藉由粒子的組成、大小來調整。
在製造量子點薄膜的情況，宜適用本實施形態的方法。例如以往的技術在硬化步驟之中，若照射活性射線，則塗膜的溫度會上昇。隨著溫度上昇，會有構成量子點的重金屬飛散的問題。另一方面，依據本實施形態，由於塗膜22被第一薄膜10與第二薄膜50夾住，因此可防止塗膜22中的重金屬飛散，同時使塗膜22硬化。
另外，塗膜22會被第一薄膜10與第二薄膜50夾住，因此可減少硬化時氧氣的影響。所以，依照硬化樹脂的種類，在硬化時不需以非活性氣體(例如氮氣)進行驅氣。
通過塗布部20而形成塗膜22的第一薄膜10，會被連續搬運至層合部30。在層合部30，被連續搬運的第二薄膜50會層合在塗膜22上，並藉由第一薄膜10與第二薄膜50將塗膜22夾住。
用來層合塗膜22的第二薄膜50具有相對向的第一表面與第二表面，且具有長形的形狀。第二薄膜50之第一表面與第二表面的距離，亦即厚度係以 10μm~100μm為佳。從減低適用的製品厚度的需求與防止皺紋的觀點看來，第二薄膜50係以15μm~60μm為更佳。另外，第二薄膜50具有例如300~1500mm的寬度。第二薄膜50的厚度、及寬度可依照適用的製品適當地選擇。為了防止彎曲，使厚度與第一薄膜一致為較佳。為了防止彎曲，將第一薄膜10與第二薄膜50的厚度定為相同為較佳。
第二薄膜50宜採用含有選自醯化纖維素、環狀烯烴、丙烯酸系樹脂、聚對苯二甲酸乙二酯樹脂、及聚碳酸酯樹脂中的至少1種作為主成分的薄膜。第二薄膜50可達成保護塗膜22及硬化層28不接觸氧氣的作用，因此透氧率宜為1.00×10-4~1.00cm3/(m2．day．atm)。從透氧率的觀點看來，第二薄膜50宜以聚對苯二甲酸乙二酯樹脂為主成分。為了達成上述透氧率，宜使用障蔽薄膜。此障蔽薄膜包含第二薄膜50以及形成於第二薄膜50的第一表面或第二表面的障蔽膜。另外，在第二薄膜50中，除了上述主成分的樹脂之外，還可含有例如可塑劑、紫外線吸收劑等。
只要第一薄膜10及第二薄膜50的至少一者是障蔽薄膜即可，其透氧率只要在1.00cm3/(m2．day．atm)以下即可。此外，透氧率是在測定溫度23℃、相對濕度90%的條件下，使用透氧率測定裝置(MOCON公司製，OX-TRAN 2/20：商品名)所測得的值。
在第一薄膜10及第二薄膜50上的障蔽膜形成，亦即障蔽薄膜的形成，可在第一薄膜10與第二薄膜 50層合之前或之後的任一情況下進行。若考慮製程損失，則較希望在塗布高價的塗布液之前的層合之前進行障蔽膜的形成。為了減低層合時或層合後的皺紋或彎曲，第一薄膜10與第二薄膜50的楊氏模數、熱收縮率等的物理特性希望為相同特性。
障蔽膜只要至少含有無機膜即可，可為例如含有至少1層無機膜與至少1層有機層的障蔽積層體。
構成無機膜的無機材料並未受到特別限定，可使用例如金屬、或無機氧化物、氮化物、氮氧化物等的各種無機化合物。構成無機材料的元素宜為矽、鋁、鎂、鈦、錫、銦及鈰，可含有這些元素的一種或兩種以上。
在上述材料之中，障蔽膜係以含有選自氮化矽、氮氧化矽、氧化矽、氧化鋁中的至少一種化合物的無機膜為特佳。包含這些材料的無機膜，與有機膜的密著性良好，因此即使在無機膜有針孔的情況下，有機膜亦可有效地將針孔埋住，而能夠抑制破裂。另外，即使在進一步積層無機膜的情況下，也能夠形成極為良好的無機膜，可更進一步提高障蔽性。
另外，第一薄膜10及第二薄膜50的至少一者宜具備硬塗層。此處硬塗層意指具有耐刮傷性並且刮痕硬度(鉛筆法)(依據JIS K-5600(1999年)規格)(JIS：Japanese Industrial Standards)為H以上的塗層。刮痕硬度更佳為2H以上，最佳為3H以上。
硬塗層可藉由將含有具有不飽和雙鍵的化合物、聚合起始劑、因應必要含有透光性粒子、含氟或聚矽氧系化合物、有機溶劑的組成物(硬塗層形成材料物)直接或隔著其他層，塗布在第一薄膜10及第二薄膜50的至少一者，並使其乾燥、硬化而形成。硬塗層可參考例如日本特開2014-170130號公報的第0162~0189段，然而並不受此處所記載者所限定。
另外，第一薄膜10及第二薄膜50的至少一者宜具備光擴散層。光擴散層意指可使通過的光線發生散射的層。光擴散層可藉由將含有透光性粒子、基質形成成分(黏結劑用單體類等)及有機溶劑的塗布液直接或隔著其他層塗布在第一薄膜10及第二薄膜50的至少一者，使其乾燥．硬化而形成。光擴散層可參考例如日本特開2009-258716號公報的第0025~0099段，然而並不受限於此處所記載者。
在層合部30已設置層合輥32以及圍住層合輥32的加熱室34。在加熱室34已設置用以使第一薄膜10通過的開口部36及用以使第二薄膜50通過的開口部38。
在與層合輥32相對向的位置已配置支承輥62。形成有塗膜22的第一薄膜10，其與塗膜22的形成面相反側的表面會包繞住支承輥62，且被連續搬運到層合位置P。層合位置P意指第二薄膜50與塗膜22相接的位置。第一薄膜10在到達層合位置P之前，宜包繞住支承輥62。這是因為假如即便在第一薄膜10出現皺紋 的情況下，也可藉由支承輥62在到達層合位置P之前矯正皺紋而能夠除去。所以，第一薄膜10包繞住支承輥62的位置(接觸位置)至層合位置P的距離L1宜長，例如30mm以上為佳，其上限值可藉由支承輥62的直徑與通過線來決定。
在本實施形態中，藉由硬化部60所使用的支承輥62與層合輥32進行第二薄膜50的層合。亦即，將硬化部60所使用的支承輥62兼用作為層合部30所使用的輥。在層合部30，亦可另外設置與支承輥62不同的層合用輥，而不兼用支承輥62。
將硬化部60所使用的支承輥62使用在層合部30，可減少輥的數目。另外還可將支承輥62使用作為對第一薄膜10加熱的加熱輥。
由未圖示的送出機送出的第二薄膜50會包繞層合輥32，並在層合輥32與支承輥62之間連續搬運。第二薄膜50會在層合位置P層合在形成於第一薄膜10的塗膜22上。藉此，以第一薄膜10與第二薄膜50夾住塗膜22。層合是指將第二薄膜50重疊、積層在塗膜22上。
層合輥32與支承輥62的距離L2，宜為第一薄膜10、使塗膜22硬化而成的硬化層28、與第二薄膜50的合計厚度值以上。另外，L2宜為第一薄膜10、塗膜22與第二薄膜50的合計厚度加上5mm的長度以下。藉由將距離L2定為合計厚度加上5mm的長度以下，可防止氣泡侵入第二薄膜50與塗膜22之間。層合輥32與 支承輥62的距離L2是指層合輥32的外周面與支承輥62之外周面的最短距離。
層合輥32與支承輥62的旋轉精密度，以徑向偏轉量來表示，為0.05mm以下，宜為0.01mm以下。徑向偏轉量愈小，愈能夠縮小塗膜22的厚度分布。
在使第二薄膜50層合於塗膜22上時，對第一薄膜10施加的張力與對第二薄膜50施加的張力的差宜小，以相同為較佳。張力的差愈小，愈能夠抑制皺紋的發生。
另外，為了抑制以第一薄膜10與第二薄膜50夾住塗膜22之後的熱變形，硬化部60的支承輥62的溫度與第一薄膜10的溫度之差、及支承輥62的溫度與第二薄膜50的溫度之差為30℃以下，宜為25℃以下，更佳為15℃以下，再更佳為相同溫度。
支承輥62的溫度與第一薄膜10的溫度之差、及支承輥62的溫度與第二薄膜50的溫度之差，意指第一薄膜10及第二薄膜50之任一者與支承輥62接觸時的溫度差，溫度差意指絕對值。
支承輥62的溫度一般而言具備溫度調節器，因此可將溫度調節器的溫度定為支承輥62的溫度。另外，第一薄膜10及前述第二薄膜50的溫度，可藉由非接觸的溫度偵測器，例如放射溫度計，直接測定溫度。
在為了縮小與支承輥62的溫度差而設置加熱室34的情況，宜在加熱室34內加熱第一薄膜10及第二薄膜50。例如在加熱室34中，可藉由未圖示的熱風產生裝置供給熱風來加熱第一薄膜10及第二薄膜50。
在第一薄膜10包繞住溫度調整後的支承輥62的情況，宜藉由支承輥62來加熱第一薄膜10。因此能夠更加容易使第一薄膜10與支承輥62成為相同的溫度。
另一方面，第二薄膜50與支承輥62保持著距離。於是，宜藉由將層合輥32設定為加熱輥，並以層合輥32直接加熱第二薄膜50。可使第二薄膜50的溫度接近支承輥62的溫度。但是，加熱室34及加熱輥並非必須，因應必要設置即可。
接下來，在以第一薄膜10與第二薄膜50夾住塗膜22的狀態下，被連續搬運至硬化部60。在硬化部60已設置支承輥62、以及位於與支承輥62相對向的位置而且作為活性射線照射裝置的紫外線照射裝置64。夾住塗膜22的第一薄膜10與第二薄膜50會在支承輥62與紫外線照射裝置64之間被連續搬運。
在硬化部60，在以第一薄膜10與第二薄膜50夾住塗膜22的狀態下將第一薄膜10包繞住支承輥62並連續搬運的同時由紫外線照射裝置64照射作為活性射線的紫外線，使塗膜22硬化，而形成硬化層28。
硬化層28是指含有能夠藉由活性射線硬化的化合物(活性射線硬化型樹脂)，化合物可藉由活性射線硬化的樹脂層。
在本實施形態中是將第一薄膜10側包繞住支承輥62並且連續搬運，然而亦可將第二薄膜50包繞住支承輥62並且連續搬運。
包繞住支承輥62是指第一薄膜10及第二薄膜50的任一者以某個包角與支承輥62的表面接觸的狀態。所以，在被連續搬運時，第一薄膜10及第二薄膜50會與支承輥62的旋轉同步移動。往支承輥62的包繞只要至少在照射紫外線時即可。
支承輥62具備圓柱狀的形狀本體與配置於本體兩端部的旋轉軸。支承輥62的本體具有例如
Figure 104104784-A0202-12-0015-5
200~1000mm的直徑。支承輥62的直徑
Figure 104104784-A0202-12-0015-6
並無限制，然而若考慮積層薄膜的彎曲變形、設備成本、旋轉精密度，則以
Figure 104104784-A0202-12-0015-7
300~500mm為佳。在支承輥62的本體已安裝溫度調節器，因此可調整支承輥62的溫度。
支承輥62溫度的選定，需考慮紫外線照射時的發熱、塗膜22的硬化效率高低以及第一薄膜10與第二薄膜50在支承輥62上皺紋變形的出現。支承輥62的溫度宜設定在例如10~95℃的範圍，15~85℃為較佳。藉由定在95℃以下，可抑制丙烯酸酯等的單體由塗膜揮發。另外，從設備的限制看來，宜為10℃以上。
此外，在本實施形態中，在硬化部60，對塗膜22照射活性射線的紫外線之前的第一薄膜10及第二薄膜50的溫度與對塗膜22照射紫外線之後的第一薄膜10及第二薄膜50的溫度之差宜為25℃以下。藉由將溫度差定在25℃以下，可抑制皺紋的發生。
另外，第一薄膜10及第二薄膜50的溫度宜在玻璃轉移溫度(Tg)以下。藉由將第一薄膜10及第二薄膜50的溫度定在各薄膜(第一薄膜10及第二薄膜50)的 玻璃轉移溫度以下，可抑制第一薄膜10及第二薄膜50的剛性降低。藉由維持第一薄膜10及第二薄膜50的剛性，可抑制皺紋的發生。
尤其在本實施形態中，在塗膜22的形成後並不具備乾燥步驟。在不具備乾燥步驟的情況，照射至塗膜22的紫外線的照射量會增加。因此，與紫外線照射前相比，紫外線照射後的薄膜的溫度會有變高的傾向。所以，為了防止出現皺紋，在紫外線照射前後，抑制第一薄膜10及第二薄膜50的溫度上昇是重要的。
此處，對塗膜22照射活性射線之前，意指從最初照射活性射線的位置算起往上游側0.5m為止之間。照射活性射線之後，意指從最後照射活性射線的位置算起往下游側0.5m為止之間。此處，「上游」、「下游」是對於第一薄膜10及第二薄膜50的移動(搬運)方向來使用。相對於某個基準，位於移動(搬運)方向的一側的情況意指「下游」，位於與移動搬運方向相反側的情況意指「上游」。
第一薄膜10及第二薄膜50的溫度可藉由非接觸的溫度偵測器，例如放射溫度計，直接進行溫度測定。此外，第一薄膜10及第二薄膜50的玻璃轉移溫度可依據JIS K7121(1987年)作測定。
紫外線照射裝置64具有產生紫外線的光源。產生紫外線的光源可採用例如低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、碳弧燈、金屬鹵素燈、氙燈等。
由紫外線照射裝置64對塗膜22照射例如100~10000mJ/cm2的照射量的紫外線。紫外線的照射量可適當地設定。
層合位置P與紫外線照射裝置64的距離L3宜為30mm以上。在第二薄膜50剛層合於塗膜22時，容易因為層合輥32及支承輥62的旋轉精密度以及第一薄膜10及第二薄膜50的張力變動而導致塗膜22厚度不均。此狀態下，若由紫外線照射裝置64照射紫外線，則硬化層28會有厚度不均的情形。層合輥32與紫外線照射裝置64的距離L3宜增加。藉由增加距離L3，可矯正塗膜22到達紫外線照射裝置64之前的厚度不均。
藉由照射紫外線，塗膜22會成為硬化層28，可製造出含有第一薄膜10、硬化層28與第二薄膜50的積層薄膜70。積層薄膜70可藉由剝離輥80由支承輥62剝離。積層薄膜70被連續搬運至未圖示的纏繞機，然後藉由纏繞機將積層薄膜70纏繞成輥狀。
[實施例]
接下來，列舉實施例對本發明作進一步具體說明，然而本發明並不受其限定。
(實施例1)
準備具有厚度50μm與寬度1500mm的PET(聚對苯二甲酸乙二酯)薄膜(東洋紡績股份有限公司製，商品名：A4300：Tg70℃)作為第一薄膜，並且準備具有厚度50μm與寬度1500mm的PET(聚對苯二甲酸乙二酯)薄膜(東洋紡績股份有限公司製，商品名：A4300：Tg70℃)作為第二薄膜。
依據以下配方調整含有活性射線硬化型樹脂的塗布液。調製下述量子點分散液，以孔徑0.2μm的聚丙烯製濾膜過濾之後，減壓乾燥30分鐘，作為塗布液來使用。
(量子點分散液)
量子點1的甲苯分散液(發光極大波長：520nm) 10質量份
量子點2的甲苯分散液(發光極大波長：630nm) 1質量份
甲基丙烯酸月桂酯 2.4質量份
三羥甲基丙烷三丙烯酸酯 0.54質量份
光聚合起始劑 0.009質量份
(Irgacure 819(註冊商標)(Ciba Specialty Chemicals股份有限公司製))
黏度調整劑 0.09質量份
(發煙二氧化矽Aerosil(註冊商標)R812(日本Aerosil股份有限公司製))
量子點1、2採用具有下述核-殼結構(InP/ZnS)的奈米結晶。
量子點1：INP530-10(NN-labs公司製)
量子點2：INP620-10(NN-labs公司製)
塗布液的黏度為50mPa．s。
以1m/分鐘的速度、60N/m的張力連續搬運第一薄膜，同時由模具塗布機將塗布液塗布在第一薄膜 的表面，形成厚度為50μm的塗膜。接下來，將形成有塗膜的第一薄膜包繞住支承輥，並將第二薄膜層合在塗膜上。在以第一薄膜與第二薄膜夾住塗膜的狀態下包繞住支承輥，進行連續搬運，同時照射紫外線。
支承輥的直徑為
Figure 104104784-A0202-12-0019-9
300mm，支承輥的溫度為50℃。紫外線照射量為2000mJ。另外，L1為50mm、L2為1mm、L3為50mm。
藉由紫外線照射使塗膜硬化，形成硬化層，而製造出積層薄膜。積層薄膜的硬化層厚度為50±2μm。硬化層的厚度精密度良好，而為±4%。另外，藉由目視觀察，並未觀察到積層薄膜出現皺紋。
(實施例2)
與實施例1同樣地調製出塗布液，並準備第一薄膜與第二薄膜。在實施例2中，使用作為黏度調整劑的發煙二氧化矽Aerosil(註冊商標)R812(日本Aerosil股份有限公司製)0.3質量份。塗布液的黏度為200mPa．s。以3m/分鐘的速度、60N/m的張力連續搬運第一薄膜，同時由模具塗布機將塗布液塗布在第一薄膜的表面，形成厚度為70μm的塗膜。接下來，將形成有塗膜的第一薄膜包繞住支承輥，並將第二薄膜層合在塗膜上。在以第一薄膜與第二薄膜夾住塗膜的狀態下包繞住支承輥，進行連續搬運，同時照射紫外線。
在使第一薄膜與支承輥接觸時，改變支承輥的溫度與第一薄膜的溫度之差，確認皺紋出現的狀況。以目視觀察皺紋的出現，將沒有觀察到皺紋情況評為 A，相對於A而言有觀察到皺紋的情況評為B。表1已揭示溫度條件與評估結果。此外，溫度差是以絕對值來表示。支承輥的直徑為
Figure 104104784-A0202-12-0020-11
300mm。
Figure 104104784-A0202-12-0020-1
如表1所示般，在溫度差大於25℃的測試2-1、2-4、2-5、2-8之中，觀察到皺紋出現，在溫度差為25℃以下的測試2-2、2-3、2-6、2-7之中，並未觀察到皺紋出現。此外，觀察到出現皺紋的測試2-1、2-4、2-5、2-8，與並未觀察到皺紋出現的測試2-2、2-3、2-6、2-7作比較，表示有觀察到皺紋，皺紋是在作為製品沒有問題的程度。
改變對塗膜照射紫外線之前的第一薄膜、及前述第二薄膜的溫度與對塗膜照射紫外線之後的第一薄膜及第二薄膜的溫度之差，確認皺紋出現的狀況。以目視觀察皺紋的出現，將沒有觀察到皺紋情況評為A，相對於A而言有觀察到皺紋的情況評為B。表2已揭示溫度條件與評估結果。此外，溫度差是以絕對值來表示。
Figure 104104784-A0202-12-0021-2
如表2所示般，在上昇溫度大於25℃的測試2-14觀察到出現皺紋，上昇溫度為25℃以下的測試2-9、2-10、2-11、2-12、2-13並未觀察到皺紋出現。此外，觀察到皺紋出現的測試2-14，與並未觀察到皺紋出現的測試2-9、2-10、2-11、2-12、2-13作比較，表示有觀察到皺紋，而皺紋是在作為製品沒有問題的程度。
1‧‧‧製造設備
10‧‧‧第一薄膜
20‧‧‧塗布部
24‧‧‧模具塗布機
26‧‧‧支承輥
30‧‧‧層合部
32‧‧‧層合輥
34‧‧‧加熱室
36‧‧‧開口部
38‧‧‧開口部
50‧‧‧第二薄膜
60‧‧‧硬化部
62‧‧‧支承輥
64‧‧‧紫外線照射裝置
70‧‧‧積層薄膜
80‧‧‧剝離輥
P‧‧‧層合位置

Claims (10)

  1. 一種積層薄膜之製造方法，其至少包含：將含有活性射線硬化型樹脂的塗布液塗布在被連續搬運的第一薄膜的表面，而形成塗膜的步驟；將包繞層合輥而被連續搬運的第二薄膜層合在該塗膜上，以該第一薄膜與該第二薄膜夾住該塗膜的步驟；及在以該第一薄膜與該第二薄膜夾住該塗膜的狀態下，將該第一薄膜及該第二薄膜之任一者包繞住支承輥，進行連續搬運，同時照射活性射線，使該塗膜硬化，而形成硬化層的步驟，其中，使第一薄膜及第二薄膜相對於支承輥錯開地接觸，且在其表面形成塗膜的第一薄膜一開始接觸、包繞住支承輥的位置，至連續搬運的第二薄膜層合至該塗膜上的位置的距離為30mm以上，該層合輥與該支承輥的距離為該第一薄膜、使該塗膜硬化而成的硬化層、與該第二薄膜的合計厚度值以上。
  2. 如請求項1之積層薄膜之製造方法，其中對該塗膜照射活性射線之前的該第一薄膜及該第二薄膜的溫度與對該塗膜照射活性射線之後的該第一薄膜及該第二薄膜的溫度的差為25℃以下。
  3. 如請求項1或2之積層薄膜之製造方法，其中在使該第一薄膜及該第二薄膜之任一者與該支承輥接觸時，該支承輥的溫度與該第一薄膜的溫度的差、及該支承輥的溫度與該第二薄膜的溫度的差為25℃以下。
  4. 如請求項1或2之積層薄膜之製造方法，其中該第一薄膜及該第二薄膜的溫度為玻璃轉移溫度以下。
  5. 如請求項1或2之積層薄膜之製造方法，其中該第一薄膜及該第二薄膜的至少一者為具備障蔽膜之障蔽薄膜，該障蔽薄膜具備透氧率為1.00cm3/(m2．day．atm)以下的障蔽膜。
  6. 如請求項1或2之積層薄膜之製造方法，其中該第一薄膜及該第二薄膜的至少一者具備硬塗層。
  7. 如請求項1或2之積層薄膜之製造方法，其中該塗布液含有量子點及量子棒的至少一者。
  8. 如請求項5之積層薄膜之製造方法，其中該障蔽膜為含有選自氮化矽、氮氧化矽、氧化矽、氧化鋁中的至少一種化合物的無機膜。
  9. 如請求項1或2之積層薄膜之製造方法，其中該第一薄膜及該第二薄膜的至少一者具備光擴散層。
  10. 如請求項1或2之積層薄膜之製造方法，其中該塗布液的黏度在40mPa．s~400mPa．s的範圍。
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