TW201545883A - 聚酯膜及其製造方法 - Google Patents

聚酯膜及其製造方法 Download PDF

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Publication number
TW201545883A
TW201545883A TW104113619A TW104113619A TW201545883A TW 201545883 A TW201545883 A TW 201545883A TW 104113619 A TW104113619 A TW 104113619A TW 104113619 A TW104113619 A TW 104113619A TW 201545883 A TW201545883 A TW 201545883A
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Taiwan
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particles
polyester film
group
aqueous coating
weight
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TW104113619A
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English (en)
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TWI569971B (zh
Inventor
蓸恩惠
朴載奉
白尙鉉
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可隆股份有限公司
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
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    • B05D3/00—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
    • 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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    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—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
    • 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
    • B05D7/04—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 to surfaces of films or sheets
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Abstract

本發明提供一種用於轉移膜之聚酯膜。更具體而言，本發明是有關於一種用於轉移膜之聚酯膜及其製造方法，所述聚酯膜具有能夠附著於硬塗層表面之塗層，以使得在形成硬塗層時，在施用硬塗層溶液後在固化硬塗層溶液之過程中光滑地形成所述表面，以賦予室內產品表面光澤度，且所述聚酯膜具有極佳的脫模特性以易於在硬塗層完全固化後移除。

Description

聚酯膜及其製造方法
以下揭示內容是有關於一種用於轉移膜之聚酯膜及其製造方法。更具體而言， 以下揭示內容是有關於一種用於轉移膜之聚酯膜及其製造方法， 所述聚酯膜具有能夠附著於硬塗層表面之塗層， 以使得在形成硬塗層時， 在施用硬塗層溶液後在固化硬塗層溶液之過程中光滑地形成所述表面， 以賦予室內產品表面光澤度， 且所述聚酯膜具有極佳的脫模特性以易於在硬塗層完全固化後移除。
近來，在用於諸如家具、地板或類似物之室內產品的光學膜中，藉由施用紫外光（ ultraviolet，UV）可固化樹脂在印刷層上形成硬塗層以便賦予其光澤度。
硬塗層藉由以下方法形成：施用UV可固化樹脂，在上面層壓有轉移膜之狀態中經由UV固化製程完全固化所述硬塗層，及移除轉移膜，以使得室內產品具有均一且光滑的表面。
在此種情況下，所用轉移膜應相對於硬塗層具有極佳的脫模特性且易於層壓及移除。
本發明之一實施例是關於提供一種用於轉移膜之聚酯膜， 所述聚酯膜能夠在形成硬塗層時層壓於硬塗層上以便賦予室內產品表面光澤度， 從而使得硬塗層之表面光滑地形成； 且所述聚酯膜具有極佳的脫模特性，以便易於在硬塗層完全固化後移除。
本發明之另一實施例是關於提供一種聚酯膜，所述聚酯膜包含含有粒子之塗層，以使得硬塗層之表面光滑地形成且具有極佳的脫模特性，且塗層中之粒子具有極佳的分散特性。
在一個通用態樣中，聚酯膜包含：由聚酯樹脂製成之基底層；及堆疊於基底層之一個表面或兩個表面上之塗層。
其中所述塗層使用含有由以下化學式1表示之矽烷偶合劑及粒子之水性塗佈組成物形成。
[化學式1]
在化學式1中，X為直鏈、分支鏈或環狀(C1-C12)烴基，具有一個或至少兩個選自以下之官能基：乙烯基、環氧基、胺基、甲基丙烯酸基、丙烯酸基以及氫硫基，且R1 至R3 各獨立地為(C1-C5)烷基。
在另一通用態樣中，聚酯膜之製造方法包含：
a)熔融擠壓（melt-extruding）聚酯樹脂以製造聚酯薄片；
b)在縱向（machine direction）拉伸聚酯薄片；
c)將含有由以下化學式1表示之矽烷偶合劑及粒子之水性塗佈組成物塗佈於在縱向拉伸之聚酯膜之一個表面或兩個表面上，且在橫向（transverse direction）拉伸經塗佈之聚酯膜；以及
d)熱定形經雙軸向拉伸之聚酯膜。
[化學式1]
在化學式1中，X為直鏈、分支鏈或環狀(C1-C12)烴基，具有一個或至少兩個選自以下之官能基：乙烯基、環氧基、胺基、甲基丙烯酸基、丙烯酸基以及氫硫基，且R1 至R3 各獨立地為(C1-C5)烷基。
根據本發明之聚酯膜可具有極佳的轉移特性及脫模特性，從而在用作轉移膜時易於層壓及移除，且形成均一且光滑的塗層。
在下文中， 將提供示例性實施例以更詳細地闡述本發明。然而， 本發明不限於所述示例性實施例。
在形成具有脫模特性之塗層時使用聚合物黏合劑樹脂及無機粒子的情況下，存在即使固體含量低但轉移仍不完全進行的問題，且黏合劑樹脂具有與硬塗層之高度黏著特性，使得脫模特性可能劣化。本發明者已進行研究以解決這些問題，且因此，本發明者發現可藉由使用矽烷偶合劑代替聚合物黏合劑樹脂對粒子進行黏合且與聚酯基底層形成有機-無機混合來形成具有極佳脫模特性之塗層，從而完成本發明。
此外，本發明者發現，在使用矽烷偶合劑藉由在線（in-line）塗佈方法形成塗層之情況下，與聚酯基底層之黏著特性及表面光滑度極佳，且會防止粒子聚結，使得所述塗層適合於製造用於轉移膜之所需聚酯膜，從而完成本發明。
此外，本發明者發現，在使用水性組成物製造膜以使所述組成物可在線塗佈時，可藉由調節所述組成物之pH以防止粒子聚結及藉由在pH經調節以防止粒子聚結的環境下添加粒子而提供具有極佳脫模特性之膜，從而完成本發明。
在本發明之一個態樣中，可使用（但不限於）任何矽烷偶合劑，只要可進行水解及縮合反應、且其具有官能基充當能夠連接至所用粒子（更具體而言，無機粒子）之錨即可。
更詳細而言，根據本發明之一態樣，聚酯膜包含由聚酯樹脂製成之基底層及堆疊於基底層之一個表面或兩個表面上之塗層， 其中所述塗層藉由塗佈及乾燥含有由以下化學式1表示之矽烷偶合劑及粒子之水性塗佈組成物形成。
[化學式1]
在化學式1中，X為直鏈、分支鏈或環狀(C1-C12)烴基，具有一個或至少兩個選自以下之官能基：乙烯基、環氧基、胺基、甲基丙烯酸基、丙烯酸基以及氫硫基，且R1 至R3 各獨立地為(C1-C5)烷基。
在本發明之一個態樣中，塗層可含有10重量%至90重量%之粒子。
在本發明之一個態樣中，粒子可具有10奈米至200奈米之平均粒徑，且為選自氧化矽、氧化鋁、氧化鋯以及氧化鈦粒子中之任一種或至少兩種無機粒子。
在本發明之一個態樣中，由化學式1表示之矽烷偶合劑可為選自由以下組成的族群之任一者或至少兩者：[3-(2-胺基乙基胺基)丙基]三甲氧基矽烷、N-(2-胺基乙基-3-胺基丙基)三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三丙氧基矽烷、3-胺基丙基三甲氧基矽烷以及3-胺基丙基三乙氧基矽烷，但未必僅限於此。
在本發明之一個態樣中，水性塗佈組成物可含有醇類溶劑或水以進行水解或縮合反應。
在本發明之一個態樣中，當粒子之pH為鹼性時，水性塗佈組成物可含有用於將整個組成物之pH調節至8或大於8之pH調節劑，且當粒子之pH為酸性時，水性塗佈組成物可含有用於將整個組成物之pH調節至5或小於5之pH調節劑。
在本發明之一個態樣中，塗層可藉由在線塗佈方法塗佈。
在本發明之一個態樣中，塗層可具有10奈米至500奈米之乾燥塗層厚度，但不限於此。
在本發明之一個態樣中，聚酯膜可具有12微米至250微米之整體厚度，但不限於此。
另外，根據本發明之另一態樣，聚酯膜之製造方法包含：
a)熔融擠壓聚酯樹脂以製造聚酯薄片；
b)在縱向拉伸聚酯薄片；
c)將含有由以下化學式1表示之矽烷偶合劑及粒子之水性塗佈組成物塗佈於在縱向拉伸之聚酯膜之一個表面或兩個表面上，且在橫向拉伸經塗佈之聚酯膜；以及
d)熱定形經雙軸向拉伸之聚酯膜。
[化學式1]
在化學式1中，X為直鏈、分支鏈或環狀(C1-C12)烴基，具有一個或至少兩個選自以下之官能基：乙烯基、環氧基、胺基、甲基丙烯酸基、丙烯酸基以及氫硫基，且R1 至R3 各獨立地為(C1-C5)烷基。
在下文中，將詳細闡述本發明之一態樣。
本發明之特徵在於：賦予聚酯膜之一個表面或兩個表面轉移特性及脫模特性之塗層是藉由在線塗佈方法形成。
在塗層藉由離線（off-line）塗佈方法形成於聚酯膜上之情況下，會增加製程且塗層厚度變厚，使得成本可能與在線塗佈方法相比增加。因此，本發明者之一目標是藉由使用在線塗佈方法塗佈水性塗佈組成物以形成在拉伸過程中乾燥及固化之塗層，提供能夠實現除塗層厚度薄及塗層對聚酯膜之黏著力強之外對水及溶劑之耐受性亦極佳的聚酯膜。
在本發明中，基底層可為由聚酯樹脂製成之膜。更詳細而言，基底層可由聚對苯二甲酸乙二酯或聚萘二甲酸乙二酯製成。更佳地，當使用固有黏度為0.6至0.7之聚對苯二甲酸乙二酯時，其耐氣候性及耐水解性可更佳。此外，聚酯膜可具有12微米至250微米之厚度。在厚度為上述範圍的情況下，可實現極佳的生產率及各種堆疊結構。更佳地，在使用略微粗糙（更具體而言，表面粗糙度為10奈米或小於10奈米）之超透明聚酯膜的情況下，粗糙度不轉移至塗層。
此外，可藉由在與對應於上面形成有塗層之基底層的聚酯膜表面相對之表面上進行電暈處理（corona treatment）或使用不同黏著組成物而賦予黏著特性。
在本發明中，藉由塗佈及乾燥含有由以下化學式1表示之矽烷偶合劑及粒子之水性塗佈組成物而形成的塗層可藉由在線塗佈方法形成。
[化學式1]
在化學式1中，X為直鏈、分支鏈或環狀(C1-C12)烴基，具有一個或至少兩個選自以下之官能基：乙烯基、環氧基、胺基、甲基丙烯酸基、丙烯酸基以及氫硫基，且R1 至R3 各獨立地為(C1-C5)烷基。
在本發明之一個態樣中，粒子可為無機粒子。詳言之，粒子可為選自由以下組成的族群之任一者或至少兩者：氧化矽、氧化鋁、氧化鋯以及氧化鈦粒子，但未必僅限於此。粒子之平均粒徑不受特別限制，但可在10奈米至200奈米、更佳50奈米至200奈米範圍內，此之所以較佳是因為可形成適於用作轉移膜之塗層，且所述塗層可藉由在線塗佈方法形成。
粒子可以10重量%至90重量%、更佳20重量%至50重量%之含量含於塗層中，且其他成分可由矽烷偶合劑及添加劑構成。在粒子含量小於10重量%之情況下，表面粗糙度顯著低，使得可能發生捲繞缺陷（winding defect）及阻斷問題（blocking problem），且在含量大於90重量%之情況下，霧度（haze）可能迅速增加或可能產生粒子聚結。
在化學式1中，X為化學結合至諸如各種合成樹脂等有機材料的官能基，且由OR1至OR3表示之烷氧基部分為化學結合至諸如玻璃、金屬等無機材料的官能基。
將闡述由化學式1表示之矽烷偶合劑的反應機制。矽烷偶合劑之烷氧基矽烷基（Si-OR）藉由水或水分水解，從而轉化為矽烷醇基（Si-OH），且此矽烷醇基與無機材料之表面藉由縮合反應而形成Si-O-M鍵（M意指在有機材料中）。X為另一官能基，結合至有機材料或可與有機材料相容，從而使無機材料與有機材料彼此化學結合。
亦即，水性塗佈組成物可含有醇類溶劑或水以進行水解或縮合反應，且較佳地，使用水之情況有利於應用於在線塗佈製程。在使用醇類溶劑之情況下，可使用具有良好揮發性之快速乾燥溶劑，諸如異丙醇、正丙醇等。
烷基包含直鏈烷基及分支鏈烷基兩者，且更具體而言，在化學式1中，R1 至R3 可各獨立地為乙基或甲基。
更詳細而言，由化學式1表示之矽烷偶合劑可為選自由以下組成的族群之任一者或至少兩者：[3-(2-胺基乙基胺基)丙基]三甲氧基矽烷、N-(2-胺基乙基-3-胺基丙基)三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三丙氧基矽烷、3-胺基丙基三甲氧基矽烷以及3-胺基丙基三乙氧基矽烷，但未必僅限於此。
根據本發明，可使用矽烷偶合劑使無機粒子附著至由聚酯樹脂製成之基底層，及實現自將黏著有本發明聚酯膜之黏著表面的極佳脫模特性。亦即，在使用黏合劑樹脂將無機粒子塗佈於基底層上之情況下，黏合劑樹脂與將黏著有所述膜之黏著表面（更具體而言，硬塗層）之間的黏著特性強，使得脫模特性可能劣化，但在根據本發明之聚酯膜中，可藉由使用矽烷偶合劑進一步改良脫模特性。
另外，使用含有矽烷偶合劑、無機粒子以及水之水性塗佈組成物藉由在線塗佈方法形成塗層，使得對聚酯基底層之黏著特性可為極佳的，且可形成顯著薄的塗層。
在此種情況下，可藉由調節水性塗佈組成物之pH而進一步改良矽烷偶合劑與無機粒子之間的分散性，使得無機粒子可均一地分散於塗層中。分散性得以改良，此由於可進一步改良脫模特性而為較佳的。因此，在根據本發明之聚酯膜中，使用含有由化學式1表示之矽烷偶合劑及粒子之水性塗佈組成物形成堆疊於由聚酯樹脂製成之基底層的一個表面或兩個表面上的塗層，但粒子與水性塗佈組成物之間的pH差可小於3，更佳小於2。
一般而言，粒子是以含有粒子之分散溶液形式購得，但作為本發明者研究之結果，發現可藉由在製備水性塗佈組成物時添加pH調節劑而進一步改良粒子分散溶液之分散性。另外，發現在製備水性塗佈組成物時根據粒子分散溶液之pH而調節所添加組成物之pH後，在穩定形成酸性或鹼性環境時注入粒子的情況下，可進一步改良粒子之分散性。在此種情況下，可藉由與其他成分組合而實現極佳的脫模特性以及轉移特性，且表面可變得均一且光滑。
詳言之，較佳的是當粒子之pH為鹼性時，水性塗佈組成物含有用於將整個組成物之pH調節至8或大於8之pH調節劑，且當粒子之pH為酸性時，水性塗佈組成物含有用於將整個組成物之pH調節至5或小於5之pH調節劑。由於由化學式1表示之矽烷偶合劑的pH為強鹼性，故僅當在組成物製備程序中即將注入粒子之前的pH被調節成酸性或鹼性環境時，方可製備出具有極佳的粒子分散性的組成物，且可減小塗層的粗糙度。
更具體而言，在用於水性塗佈組成物之粒子的pH為鹼性的情況下，可使用四烷基銨鹽用為pH調節劑，以將pH調節至8或大於8。舉例而言，可使用氫氧化四甲基銨、氫氧化四乙基銨或類似物，但pH調節劑不限於此。
另外，在粒子之pH為酸性的情況下，可使用甲酸、硫酸、硝酸、鹽酸、檸檬酸、馬來酸、蘋果酸、乳酸、草酸、鄰苯二甲酸、丁二酸或類似物作為pH調節劑以將整個組成物之pH調節至5或小於5，但pH調節劑不限於此。
此外，必要時，水性塗佈組成物可另外含有添加劑，諸如潤濕劑（wetting agent）、助滑劑（slip agent）、UV穩定劑、分散劑或類似物。
塗層可藉由在線塗佈方法塗佈，從而具有10奈米至500奈米之乾燥塗層厚度，但不限於此。在乾燥塗層厚度小於10奈米之情況下，可能無法實現滑動特性（slip property），且在乾燥塗層厚度大於500奈米之情況下，可能產生膜之間的阻斷。
更詳細而言，水性塗佈組成物可含有0.1重量%至0.5重量%的矽烷偶合劑、0.001重量%至0.1重量%的粒子、0.1重量%至2重量%的潤濕劑以及剩餘為水。此外，必要時，可進一步含有pH調節劑以製造與粒子相同的pH環境，使得粒子可均一地分散。
矽烷偶合劑較佳在整個水性塗佈組成物中以0.1重量%至0.5重量%之含量使用，且在含量小於0.1重量%之情況下，不可能固定所述粒子，且在含量大於0.5重量%之情況下，塗佈外觀可能不為極佳的。
粒子較佳在整個水性塗佈組成物中以0.001重量%至0.1重量%之含量使用，且在含量小於0.001重量%之情況下，滑動特性可能劣化且可能出現阻斷問題，且在含量大於0.1重量%之情況下，霧度可能迅速增加。
潤濕劑用於使乳液均一地塗佈於聚酯膜上，且使用選自聚乙二醇、聚乙烯酯、改質矽、氟混合物以及類似物中之一者，此由於會顯著改良塗佈特性而為較佳的。另外，就極佳的黏著特性而言，潤濕劑較佳在整個水性塗佈組成物中以0.1重量%至2重量%之含量使用。
用於改良粒子在水性塗佈組成物中之分散性的pH調節劑可以用於製造與粒子相同的pH環境的含量使用。
此外，本發明提供一種製造聚酯膜之方法，包括：
a)熔融擠壓聚酯樹脂以製造聚酯薄片；
b)在縱向拉伸聚酯薄片；
c)將含有由以下化學式1表示之矽烷偶合劑及粒子之水性塗佈組成物塗佈於在縱向拉伸之聚酯膜之一個表面或兩個表面上，且在橫向拉伸經塗佈之聚酯膜；以及
d)熱定形經雙軸向拉伸之聚酯膜。
[化學式1]
在化學式1中，X為直鏈、分支鏈或環狀(C1-C12)烴基，具有一個或至少兩個選自以下之官能基：乙烯基、環氧基、胺基、甲基丙烯酸基、丙烯酸基以及氫硫基，且R1 至R3 各獨立地為(C1-C5)烷基。
另外，聚酯膜之製造方法可在步驟d)後更包括在與上面形成有塗層之聚酯膜表面相對的表面上進行電暈處理。電暈處理是為了進一步改良印刷特性，且可使用任何電暈處理方法，只要其一般用於此項技術中即可。
步驟a)為經由T型模具（T-die）自圓筒熔融擠壓樹脂而製造薄片以製造聚酯膜的製程。
步驟b)為對聚酯薄片進行雙軸向拉伸以製造聚酯膜之製程，且縱向拉伸可較佳使用至少一個輥進行。
接著，在步驟c)中，藉由在線塗佈方法形成塗層。在此種情況下，可較佳使用水分散乳液以便用於在線塗佈。在此種情況下，用於形成塗層之水性塗佈組成物的組態可與上述相同，且較佳地，在塗佈時水性塗佈組成物可被塗佈成使得乾燥塗層厚度在拉伸後變成10奈米至500奈米。在藉由塗佈水性塗佈組成物形成塗層後，可橫向拉伸經塗佈之膜。在此情況下，橫向拉伸較佳使用拉幅機（tenter）進行。在此種情況下，拉伸率可為三至四倍。
接著，移除用於塗層之水，固化所述塗層且進行乾燥及熱定形製程以避免膜收縮。此時，熱定形溫度可為225℃至235℃。
在下文中，將提供實例以更詳細地闡述本發明。然而，本發明不限於以下實例。
如下量測本發明中之物理特性。
1)霧度
量測裝置：日本電色工業株式會社（Nippon Denshoku Kogyo Co. LTD.），NDH-5000，ASTM模式（ASTM D-1003）
量測方法：在量測塗層樣品之霧度三次後，計算平均值。
2)粗液穩定性（crude liquid stability）
藉由在粗液存放在室溫及潮濕下12小時或大於12小時時，當場測試粗液是否變化或是否產生粒子聚結來評估粗液穩定性。
○：粒子之塗佈外觀及分散性在粗液存放前後相似
×：粗液存放前後粒子之塗佈外觀及分散性存在變化
3)粒子之分散性
藉由使用掃描式電子顯微鏡（SEM）量測聚結粒子的數目（N數（N = 5））而評估塗層中粒子之分散性。在10,000倍放大倍率下由裸眼確認聚結粒子時，將粒徑為300奈米之聚結粒子的數目為5或大於5的情況評估為已產生聚結粒子，且將聚結粒子的數目小於5的情況評估為尚未產生聚結粒子。此處，在粒徑為300奈米之聚結粒子的數目為5或大於5的情況下，分散性不良。在此種情況下，脫模特性可能劣化。
4)脫模特性
在丙烯酸硬塗層組成物施用於聚氯乙烯膜上後，在實例及比較例中所製造之膜堆疊及壓緊於其上的狀態中，藉由固化硬塗層組成物形成硬塗層。接著，移除實例及比較例中製造之膜，從而如下評估脫模特性。
○：膜徹底分層而未與硬塗層組成物反應
×：膜與硬塗層組成物反應，從而黏著至其上而非層壓
5)塗佈特性
在螢光燈下由裸眼評估塗佈外觀水準。
○：不存在針孔且塗佈表面為乾淨的
×：存在針孔且塗佈表面完全不透明
6)墨水黏著特性
在使用印章筆（Name pen）在塗佈表面上寫字後，將3M膠帶附著於其上且使用橡膠輥（2公斤）在上面進行摩擦兩次。接著，在1分鐘後，移除3M膠帶且評估墨水黏著特性。
在此種情況下，將墨水轉移至3M膠帶之情況評估為良好，且將墨水未轉移之情況評估為較差。
[實例1]
水性塗佈組成物1之製備
添加0.1重量%的二氧化矽粒子（納爾科（Nalco），Nalco-2329，固體含量：40重量%，粒徑：80奈米，pH：8.2至8.6）且在藉由將0.23重量%的矽烷偶合劑（韓國道康寧有限公司（Dow Corning Korea Ltd.），Z-6020，固體含量：1重量%）、1重量%的潤濕劑（3M有限公司，FC-4432，固體含量：10重量%）、0.05重量%作為pH調節劑之氫氧化四乙基銨以及98.62重量%的水彼此混合且將pH調節至10而穩定形成鹼性環境的狀態中均一地分散。
聚酯膜之製造
在將水分被移除至含量為100 ppm或小於100 ppm之聚對苯二甲酸乙二酯碎片注入熔融擠壓機（melt-extruder）且熔融後，將所得物在擠壓穿過T型模具的同時迅速冷卻且藉由表面溫度為20℃之流延鼓（casting drum）凝固，從而製造厚度為2000微米之聚對苯二甲酸乙二酯薄片。
將所製造之聚對苯二甲酸乙二酯薄片在110℃下在縱向（machine direction，MD）拉伸3.5倍且在室溫下冷卻。接著，在藉由棒塗法（bar coating method）將水性塗佈組成物1塗佈於薄片之一個表面上後，預先加熱經拉伸之薄片，乾燥且隨後在140℃下在橫向（transverse direction，TD）拉伸3.5倍。接著，在235℃下在5階段拉幅機中進行熱處理後，使經熱處理之膜在縱向及橫向鬆弛達10%，在200℃下熱定形，從而製造包含在一個表面上形成之塗層且厚度為100微米之雙軸向拉伸膜。塗層在拉伸後之乾燥塗層厚度為75奈米。如上所述獲得之膜的物理特性示於下表1中。
[實例2]
水性塗佈組成物2之製備
添加0.1重量%的二氧化矽粒子（愛思奈米化學（AcenanoChem），AS-80K，固體含量：20重量%，粒徑：80奈米，pH：10至11.5）且在藉由將0.23重量%的矽烷偶合劑（韓國道康寧有限公司，Z-6020，固體含量：1重量%）、1重量%的潤濕劑（3M有限公司，FC-4432，固體含量：10重量%）、0.05重量%作為pH調節劑之氫氧化四乙基銨以及98.62重量%的水彼此混合且將pH調節至10而穩定形成鹼性環境的狀態中均一地分散。
聚酯膜之製造
在將水分被移除至含量為100 ppm或小於100 ppm之聚對苯二甲酸乙二酯碎片注入熔融擠壓機且熔融後，將所得物在擠壓穿過T型模具的同時迅速冷卻且藉由表面溫度為20℃之流延鼓凝固，從而製造厚度為2000微米之聚對苯二甲酸乙二酯薄片。
將所製造之聚對苯二甲酸乙二酯薄片在110℃下在縱向（MD）拉伸3.5倍且在室溫下冷卻。接著，在藉由棒塗佈法將水性塗佈組成物2塗佈於薄片之一個表面上後，預先加熱經拉伸之薄片，乾燥且隨後在140℃下在橫向（TD）拉伸3.5倍。接著，在235℃下在5階段拉幅機中進行熱處理後，使經熱處理之膜在縱向及橫向鬆弛達10%以在200℃下熱定形，從而製造包含在一個表面上形成之塗層且厚度為100微米之雙軸向拉伸膜。塗層在拉伸後之乾燥塗層厚度為75奈米。如上所述獲得之膜的物理特性示於下表1中。
[實例3]
水性塗佈組成物3之製備
添加0.1重量%的二氧化矽粒子（日產（Nissan），ST-YL，固體含量：38.2重量%，粒徑：50奈米至80奈米，pH：9.6）且在藉由將0.23重量%的矽烷偶合劑（韓國道康寧有限公司，Z-6020，固體含量：1重量%）、1重量%的潤濕劑（3M有限公司，FC-4432，固體含量：10重量%）、0.05重量%作為pH調節劑之氫氧化四乙基銨以及98.62重量%的水彼此混合且將pH調節至10而穩定形成鹼性環境的狀態中均一地分散。
聚酯膜之製造
在將水分被移除至含量為100 ppm或小於100 ppm之聚對苯二甲酸乙二酯碎片注入熔融擠壓機且熔融後，將所得物在擠壓穿過T型模具的同時時迅速冷卻且藉由表面溫度為20℃之流延鼓凝固，從而製造厚度為2000微米之聚對苯二甲酸乙二酯薄片。
將所製造之聚對苯二甲酸乙二酯薄片在110℃下在縱向（MD）拉伸3.5倍且在室溫下冷卻。接著，在藉由棒塗佈法將水性塗佈組成物3塗佈於薄片之一個表面上後，預先加熱經拉伸之薄片，乾燥且隨後在140℃下在橫向（TD）拉伸3.5倍。接著，在235℃下在5階段拉幅機中進行熱處理後，使經熱處理之膜在縱向及橫向鬆弛達10%以在200℃下熱定形，從而製造包含在一個表面上形成之塗層且厚度為100微米之雙軸向拉伸膜。塗層在拉伸後之乾燥塗層厚度為75奈米。如上所述獲得之膜的物理特性示於下表1中。
[實例4]
水性塗佈組成物4之製備
添加0.1重量%的二氧化矽粒子（日產，ST-ZL，固體含量：38.7重量%，粒徑：70奈米至100奈米，pH：9.3）且在藉由將0.23重量%的矽烷偶合劑（韓國道康寧有限公司，Z-6020，固體含量：1重量%）、1重量%的潤濕劑（3M有限公司，FC-4432，固體含量：10重量%）、0.05重量%作為pH調節劑之氫氧化四乙基銨以及98.62重量%的水彼此混合且將pH調節至10而穩定形成鹼性環境的狀態中均一地分散。
聚酯膜之製造
在將水分被移除至含量為100 ppm或小於100 ppm之聚對苯二甲酸乙二酯碎片注入熔融擠壓機且熔融後，將所得物在擠壓穿過T型模具的同時迅速冷卻且藉由表面溫度為20℃之流延鼓凝固，從而製造厚度為2000微米之聚對苯二甲酸乙二酯薄片。
將所製造之聚對苯二甲酸乙二酯薄片在110℃下在縱向（MD）拉伸3.5倍且在室溫下冷卻。接著，在藉由棒塗佈法將水性塗佈組成物4塗佈於薄片之一個表面上後，預先加熱經拉伸之薄片，乾燥且隨後在140℃下在橫向（TD）拉伸3.5倍。接著，在235℃下在5階段拉幅機中進行熱處理後，使經熱處理之膜在縱向及橫向鬆弛達10%以在200℃下熱定形，從而製造包含在一個表面上形成之塗層且厚度為100微米之雙軸向拉伸膜。塗層在拉伸後之乾燥塗層厚度為75奈米。如上所述獲得之膜的物理特性展示於下表1中。
[實例5]
水性塗佈組成物5之製備
添加0.1重量%的二氧化矽粒子（日產，ST-AK-YL，固體含量：30重量%至31重量%，粒徑：50奈米至80奈米，pH：3至5）且在藉由將0.23重量%的矽烷偶合劑（韓國道康寧有限公司，Z-6020，固體含量：1重量%）、1重量%的潤濕劑（3M有限公司，FC-4432，固體含量：10重量%）、0.05重量%作為pH調節劑之甲酸以及98.62重量%的水彼此混合且將pH調節至4而穩定形成酸性環境的狀態中均一地分散。
聚酯膜之製造
在將水分被移除至含量為100 ppm或小於100 ppm之聚對苯二甲酸乙二酯碎片注入熔融擠壓機且熔融後，將所得物在擠壓穿過T型模具的同時迅速冷卻且藉由表面溫度為20℃之流延鼓凝固，從而製造厚度為2000微米之聚對苯二甲酸乙二酯薄片。
將所製造之聚對苯二甲酸乙二酯薄片在110℃下在縱向（MD）拉伸3.5倍且在室溫下冷卻。接著，在藉由棒塗佈法將水性塗佈組成物5塗佈於薄片之一個表面上後，預先加熱經拉伸之薄片，乾燥且隨後在140℃下在橫向（TD）拉伸3.5倍。接著，在235℃下在5階段拉幅機中進行熱處理後，使經熱處理之膜在縱向及橫向鬆弛達10%以在200℃下熱定形，從而製造包含在一個表面上形成之塗層且厚度為100微米之雙軸向拉伸膜。塗層在拉伸後之乾燥塗層厚度為75奈米。如上所述獲得之膜的物理特性示於下表1中。
[比較例1]
水性塗佈組成物6之製備
添加0.1重量%的二氧化矽粒子（日產，ST-AK-YL，固體含量：30重量%至31重量%，粒徑：50奈米至80奈米，pH：3至5）且在藉由將0.23重量%的矽烷偶合劑（韓國道康寧有限公司，Z-6020，固體含量：1重量%）、1重量%的潤濕劑（3M有限公司，FC-4432，固體含量：10重量%）、0.05重量%作為pH調節劑之氫氧化四乙基銨以及98.62重量%的水彼此混合且將pH調節至10而穩定形成鹼性環境的狀態中均一地分散。
聚酯膜之製造
在將水分被移除至含量為100 ppm或小於100 ppm之聚對苯二甲酸乙二酯碎片注入熔融擠壓機且熔融後，將所得物在擠壓穿過T型模具的同時迅速冷卻且藉由表面溫度為20℃之流延鼓凝固，從而製造厚度為2000微米之聚對苯二甲酸乙二酯薄片。
將所製造之聚對苯二甲酸乙二酯薄片在110℃下在縱向（MD）拉伸3.5倍且在室溫下冷卻。接著，在藉由棒塗佈法將水性塗佈組成物6塗佈於薄片之一個表面上後，預先加熱經拉伸之薄片，乾燥且隨後在140℃下在橫向（TD）拉伸3.5倍。接著，在235℃下在5階段拉幅機中進行熱處理後，使經熱處理之膜在縱向及橫向鬆弛達10%以在200℃下熱定形，從而製造包含在一個表面上形成之塗層且厚度為100微米之雙軸向拉伸膜。塗層在拉伸後之乾燥塗層厚度為75奈米。如上所述獲得之膜的物理特性示於下表1中。
[比較例2]
水性塗佈組成物7之製備
在0.23重量%的矽烷偶合劑（韓國道康寧有限公司，Z-6020，固體含量：1重量%）、1重量%的潤濕劑（3M有限公司，FC-4432，固體含量：10重量%）以及98.67重量%的水彼此混合後，在pH為8時，添加0.1重量%的二氧化矽粒子（日產，ST-AK-YL，固體含量：30重量%至31重量%，粒徑：50奈米至80奈米，pH：3至5）且均一地分散。
聚酯膜之製造
在將水分被移除至含量為100 ppm或小於100 ppm之聚對苯二甲酸乙二酯碎片注入熔融擠壓機且熔融後，將所得物在擠壓穿過T型模具的同時迅速冷卻且藉由表面溫度為20℃之流延鼓凝固，從而製造厚度為2000微米之聚對苯二甲酸乙二酯薄片。
將所製造之聚對苯二甲酸乙二酯薄片在110℃下在縱向（MD）拉伸3.5倍且在室溫下冷卻。接著，在藉由棒塗佈法將水性塗佈組成物7塗佈於薄片之一個表面上後，預先加熱經拉伸之薄片，乾燥且隨後在140℃下在橫向（TD）拉伸3.5倍。接著，在235℃下在5階段拉幅機中進行熱處理後，使經熱處理之膜在縱向及橫向鬆弛達10%以在200℃下熱定形，從而製造包含在一個表面上形成之塗層且厚度為100微米之雙軸向拉伸膜。塗層在拉伸後之乾燥塗層厚度為75奈米。如上所述獲得之膜的物理特性示於下表1中。
[比較例3]
水性塗佈組成物8之製備
添加0.1重量%的二氧化矽粒子（納爾科，Nalco-2329，固體含量：40重量%，粒徑：80奈米，pH：8.2至8.6）且在藉由將0.23重量%的矽烷偶合劑（韓國道康寧有限公司，Z-6020，固體含量：1重量%）、1重量%的潤濕劑（3M有限公司，FC-4432，固體含量：10重量%）、0.05重量%作為pH調節劑之甲酸以及98.62重量%的水彼此混合且將pH調節至4而穩定形成酸性環境的狀態中均一地分散。
聚酯膜之製造
在將水分被移除至含量為100 ppm或小於100 ppm之聚對苯二甲酸乙二酯碎片注入熔融擠壓機且熔融後，將所得物在擠壓穿過T型模具的同時迅速冷卻且藉由表面溫度為20℃之流延鼓凝固，從而製造厚度為2000微米之聚對苯二甲酸乙二酯薄片。
將所製造之聚對苯二甲酸乙二酯薄片在110℃下在縱向（MD）拉伸3.5倍且在室溫下冷卻。接著，在藉由棒塗佈法將水性塗佈組成物8塗佈於薄片之一個表面上後，預先加熱經拉伸之薄片，乾燥且隨後在140℃下在橫向（TD）拉伸3.5倍。接著，在235℃下在5階段拉幅機中進行熱處理後，使經熱處理之膜在縱向及橫向鬆弛達10%以在200℃下熱定形，從而製造包含在一個表面上形成之塗層且厚度為100微米之雙軸向拉伸膜。塗層在拉伸後之乾燥塗層厚度為75奈米。如上所述獲得之膜的物理特性示於下表1中。
[比較例4]
水性塗佈組成物9之製備
在4重量%的胺基甲酸酯黏合劑（DKS，H-3，固體含量：1重量%）、1重量%的潤濕劑（3M有限公司，FC-4432，固體含量：10重量%）以及94.9重量%的水彼此混合後，添加0.1重量%的二氧化矽粒子（日產，ST-AK-YL，固體含量：30重量%至31重量%，粒徑：50奈米至80奈米，pH：3至5）且均一地分散。
聚酯膜之製造
在將水分被移除至含量為100 ppm或小於100 ppm之聚對苯二甲酸乙二酯碎片注入熔融擠壓機且熔融後，將所得物在擠壓穿過T型模具的同時迅速冷卻且藉由表面溫度為20℃之流延鼓凝固，從而製造厚度為2000微米之聚對苯二甲酸乙二酯薄片。
將所製造之聚對苯二甲酸乙二酯薄片在110℃下在縱向（MD）拉伸3.5倍且在室溫下冷卻。接著，在藉由棒塗佈法將水性塗佈組成物9塗佈於薄片之一個表面上後，預先加熱經拉伸之薄片，乾燥且隨後在140℃下在橫向（TD）拉伸3.5倍。接著，在235℃下在5階段拉幅機中進行熱處理後，使經熱處理之膜在縱向及橫向鬆弛達10%以在200℃下熱定形，從而製造包含在一個表面上形成之塗層且厚度為100微米之雙軸向拉伸膜。塗層在拉伸後之乾燥塗層厚度為90奈米。
如上所述獲得之膜的物理特性示於下表1中。
[比較例5]
水性塗佈組成物10之製備
在2.27重量%的丙烯酸黏合劑（羅門哈斯公司（Rohm & Haas），P-3208，固體含量：1重量%）、1重量%的潤濕劑（3M有限公司，FC-4432，固體含量：10重量%）以及96.63重量%的水彼此混合後，添加0.1重量%的二氧化矽粒子（日產，ST-AK-YL，固體含量：30重量%至31重量%，粒徑：50奈米至80奈米，pH：3至5）且均一地分散。
聚酯膜之製造
在將水分被移除至含量為100 ppm或小於100 ppm之聚對苯二甲酸乙二酯碎片注入熔融擠壓機且熔融後，將所得物在擠壓穿過T型模具的同時迅速冷卻且藉由表面溫度為20℃之流延鼓凝固，從而製造厚度為2000微米之聚對苯二甲酸乙二酯薄片。
將所製造之聚對苯二甲酸乙二酯薄片在110℃下在縱向（MD）拉伸3.5倍且在室溫下冷卻。接著，在藉由棒塗佈法將水性塗佈組成物10塗佈於薄片之一個表面上後，預先加熱經拉伸之薄片，乾燥且隨後在140℃下在橫向（TD）拉伸3.5倍。接著，在235℃下在5階段拉幅機中進行熱處理後，使經熱處理之膜在縱向及橫向鬆弛達10%以在200℃下熱定形，從而製造包含在一個表面上形成之塗層且厚度為100微米之雙軸向拉伸膜。塗層在拉伸後之乾燥塗層厚度為90奈米。如上所述獲得之膜的物理特性示於下表1中。
如表1中所示，在比較例1至比較例3中，水性塗佈組成物之pH不同於粒子之pH，使得產生粒子聚結。相反地，證實在實例1至實例5中，藉由將水性塗佈組成物之pH與粒子之pH調節至彼此相等而未產生粒子聚結，且脫模特性亦為極佳的。同時，證實在對應於施用胺基甲酸酯黏合劑或丙烯酸黏合劑代替矽烷偶合劑之情況的比較例4及比較例5中，粒子之分散度良好，但塗層厚度與使用矽烷偶合劑之情況相比增加20%，使得霧度高、脫模特性減小以及在一定程度上產生黏著力。
在上文中，雖然藉由示例性實施例來闡述本發明，但其僅供用於幫助完整地理解本發明。因此，本發明不限於所述示例性實施例。本發明所屬領域之技術人員可根據本說明而作出各種潤飾及變化。
因此，本發明之精神不應侷限於上述示例性實施例，且以下申請專利範圍以及對申請專利範圍之所有同等或等效潤飾均意欲包含於本發明之範疇及精神內。
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Claims (16)

  1. 一種聚酯膜，包括： 由聚酯樹脂製成之基底層；以及 堆疊於所述基底層之一個表面或兩個表面上的塗層， 其中所述塗層藉由塗佈及乾燥含有由以下化學式1表示之矽烷偶合劑及粒子之水性塗佈組成物而形成，以及 所述水性塗佈組成物與所述粒子之間的pH差小於3； [化學式1]在化學式1中，X為直鏈、分支鏈或環狀(C1-C12)烴基，具有一個或至少兩個選自以下之官能基：乙烯基、環氧基、胺基、甲基丙烯酸基、丙烯酸基以及氫硫基，且R1 至R3 各獨立地為(C1-C5)烷基。
  2. 如申請專利範圍第1項所述之聚酯膜，其中所述塗層含有10重量%至90重量%之所述粒子。
  3. 如申請專利範圍第1項所述之聚酯膜，其中所述粒子具有10奈米至200奈米之平均粒徑，且為選自由氧化矽粒子、氧化鋁粒子、氧化鋯粒子以及氧化鈦粒子組成之族群中之任一種或至少兩種無機粒子。
  4. 如申請專利範圍第1項所述之聚酯膜，其中由化學式1表示之所述矽烷偶合劑為選自由以下組成之族群中之任一者或至少兩者：[3-(2-胺基乙基胺基)丙基]三甲氧基矽烷、N-(2-胺基乙基-3-胺基丙基)三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三丙氧基矽烷、3-胺基丙基三甲氧基矽烷以及3-胺基丙基三乙氧基矽烷。
  5. 如申請專利範圍第1項所述之聚酯膜，其中所述水性塗佈組成物更含有醇類溶劑或水。
  6. 如申請專利範圍第1項所述之聚酯膜，其中當所述粒子之pH為鹼性時，所述水性塗佈組成物含有用於將整個所述組成物之pH調節至8或大於8之pH調節劑，且當所述粒子之pH為酸性時，所述水性塗佈組成物含有用於將整個所述組成物之pH調節至5或小於5之pH調節劑。
  7. 如申請專利範圍第1項所述之聚酯膜，其中所述塗層藉由在線塗佈方法形成。
  8. 如申請專利範圍第8項之聚酯膜，其中所述塗層具有10奈米至500奈米之乾燥塗層厚度。
  9. 如申請專利範圍第1項所述之聚酯膜，其中所述聚酯膜具有12微米至250微米之整體厚度。
  10. 如申請專利範圍第1項所述之聚酯膜，其中所述聚酯膜中粒徑為300奈米或大於300奈米之聚結粒子的數目小於5。
  11. 一種製造聚酯膜之方法，包括： a)熔融擠壓聚酯樹脂以製造聚酯薄片； b)在縱向拉伸所述聚酯薄片； c)將含有由以下化學式1表示之矽烷偶合劑及粒子之水性塗佈組成物塗佈於在經縱向拉伸之所述聚酯膜之一個表面或兩個表面上，且在橫向拉伸經塗佈之所述聚酯膜；以及 d)熱定形經雙軸向拉伸之所述聚酯膜； [化學式1]在化學式1中，X為直鏈、分支鏈或環狀(C1-C12)烴基，具有一個或至少兩個選自以下之官能基：乙烯基、環氧基、胺基、甲基丙烯酸基、丙烯酸基以及氫硫基，且R1 至R3 各獨立地為(C1-C5)烷基。
  12. 如申請專利範圍第11項所述之製造聚酯膜之方法，其中所述粒子具有10奈米至200奈米之平均粒徑，且為選自由氧化矽粒子、氧化鋁粒子、氧化鋯粒子以及氧化鈦粒子組成之族群之任一種或至少兩種無機粒子。
  13. 如申請專利範圍第11項所述之製造聚酯膜之方法，其中由化學式1表示之所述矽烷偶合劑為選自由以下組成之族群之任一者或至少兩者：[3-(2-胺基乙基胺基)丙基]三甲氧基矽烷、N-(2-胺基乙基-3-胺基丙基)三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三丙氧基矽烷、3-胺基丙基三甲氧基矽烷以及3-胺基丙基三乙氧基矽烷。
  14. 如申請專利範圍第11項所述之製造聚酯膜之方法，其中所述水性塗佈組成物更含有醇類溶劑或水。
  15. 如申請專利範圍第11項所述之製造聚酯膜之方法，其中當所述粒子之pH為鹼性時，所述水性塗佈組成物含有用於將整個所述組成物之pH調節至8或大於8之pH調節劑，且當所述粒子之pH為酸性時，所述水性塗佈組成物含有用於將整個所述組成物之pH調節至5或小於5之pH調節劑，但所述水性塗佈溶液與所述粒子之間的pH差小於3。
  16. 如申請專利範圍第11項所述之製造聚酯膜之方法，其中所述聚酯膜中粒徑為300奈米或大於300奈米之聚結粒子的數目小於5。
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