TW202330284A - Laminate structure, hardcoat film including the same, window and display device using the same - Google Patents
Laminate structure, hardcoat film including the same, window and display device using the same Download PDFInfo
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- TW202330284A TW202330284A TW111135693A TW111135693A TW202330284A TW 202330284 A TW202330284 A TW 202330284A TW 111135693 A TW111135693 A TW 111135693A TW 111135693 A TW111135693 A TW 111135693A TW 202330284 A TW202330284 A TW 202330284A
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- layer
- easy
- mentioned
- laminate
- film
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Landscapes
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
Description
本發明涉及具備透明聚醯亞胺系基材層和易黏接層的層疊體、包含上述層疊體的硬塗膜以及應用其的視窗和圖像顯示裝置。The present invention relates to a laminate comprising a transparent polyimide base material layer and an easily bonding layer, a hard coat film comprising the laminate, and a window and an image display device using the same.
近年來，液晶顯示(liquid crystal display：LCD)裝置或有機發光顯示(organic light emitting display：OLED)裝置等之類的圖像顯示裝置的薄型化以及軟性化一直在持續。由此，上述圖像顯示裝置廣泛應用於以便攜為特徵的各種智慧設備(smart device)，從智慧手機(smart phone)、平板(tablet)PC到各種可穿戴設備(wearable device)。In recent years, image display devices such as liquid crystal display (LCD) devices and organic light emitting display (OLED) devices have been thinned and flexible. Therefore, the above-mentioned image display device is widely used in various smart devices characterized by portability, ranging from smart phones, tablet PCs to various wearable devices.
為此，一直對能夠代替傳統鋼化玻璃材質的視窗膜的光學用塑膠膜進行著研究。上述光學用塑膠膜例如可以包含聚對苯二甲酸乙二醇酯(PET)、聚醚碸(PES)、聚萘二甲酸乙二醇酯(PEN)、聚丙烯酸酯(PAR)、聚碳酸酯(PC)、聚醯亞胺(PI)等之類的樹脂物質。其中，聚醯亞胺由於具有優異的機械性質、耐化學性、耐試劑性、高耐熱性以及電絕緣性等優異的物性，因此被用作電氣/電子用耐熱膜、液晶取向膜、半導體用材料、成型部件用材料、黏接劑等。For this reason, studies have been conducted on plastic films for optics that can replace conventional window films made of tempered glass. The plastic film for optics mentioned above may include, for example, polyethylene terephthalate (PET), polyether ether (PES), polyethylene naphthalate (PEN), polyacrylate (PAR), polycarbonate Resin substances such as (PC), polyimide (PI) and the like. Among them, polyimide has excellent physical properties such as excellent mechanical properties, chemical resistance, chemical resistance, high heat resistance, and electrical insulation, so it is used as a heat-resistant film for electrical/electronics, a liquid crystal alignment film, and a semiconductor. Materials, materials for molded parts, adhesives, etc.
但是，對於這樣的聚醯亞胺系膜而言，存在由於形成分子內電荷轉移絡合物(Charge Transfer Complex)而吸收短波長區域的光從而呈現特有的黃色光的特性。這種高黃色度(YI；Yellow Index)不僅使透過度降低，還存在使顯示器固有的顏色失真的問題，因此難以用作顯示器用最外側膜。However, such a polyimide-based film has a characteristic of exhibiting characteristic yellow light by forming an intramolecular charge transfer complex (Charge Transfer Complex) to absorb light in a short-wavelength region. Such a high yellowness (YI; Yellow Index) not only reduces the transmittance, but also has the problem of distorting the inherent color of the display, so it is difficult to be used as the outermost film for a display.
因此，作為既透明又具有對於折疊的耐久性的高分子膜，需要開發抑制了以往的黃色聚醯亞胺系膜中的黃色的透明的聚醯亞胺系基材膜。為了製造這種抑制了黃色的透明的聚醯亞胺系基材膜，已知有將包含CF1、CF2或CF3等大體積的C-F鍵的取代基導入到基材的技術。但是，該情況下，雖然具有能夠抑制聚醯亞胺系膜的黃色而確保透明度的優點，但是存在C-F鍵的鍵能大而不易分解，且由於具有接觸角大的F元素而非常不適合與其他基材接合的問題。Therefore, as a transparent polymer film having durability against folding, it is necessary to develop a transparent polyimide-based base film that suppresses yellowness in conventional yellow polyimide-based films. In order to produce such a yellow-suppressed transparent polyimide-based substrate film, a technique of introducing a substituent including a bulky C-F bond such as CF1, CF2, or CF3 into the substrate is known. However, in this case, although there is an advantage of being able to suppress the yellowness of the polyimide-based film and ensure transparency, the C-F bond has a large bond energy and is not easily decomposed, and it is very unsuitable for other materials due to the F element having a large contact angle. Substrate bonding issues.
關於此，韓國專利公告公報第10-0601308號提供了一種實現了與金屬的優異的黏接特性的對於聚醯亞胺膜的表面進行常壓電漿處理的方法，韓國專利公開公報第10-2019-0081823號提供了一種聚醯亞胺基板和包含其的顯示基板模組，該聚醯亞胺基板透過熱固化處理而捲曲特性和耐衝擊性優異，從而有效用作軟性電子設備的外覆基板。In this regard, Korean Patent Publication No. 10-0601308 provides a method for performing atmospheric pressure plasma treatment on the surface of a polyimide film that achieves excellent adhesion properties to metals. Korean Patent Publication No. 10- No. 2019-0081823 provides a polyimide substrate and a display substrate module containing it. The polyimide substrate has excellent curling characteristics and impact resistance through heat curing treatment, so that it can be effectively used as an outer cover of flexible electronic devices substrate.
然而，以往的聚醯亞胺系基材膜的情況下，存在黃色未被充分抑制或者接觸角沒有充分降低而可能發生基材間的剝離現象的問題。However, in the case of the conventional polyimide-based base film, there is a problem that the peeling phenomenon between base materials may occur because yellowness is not sufficiently suppressed or the contact angle is not sufficiently lowered.
因此，實際情況是，作為抑制了黃色聚醯亞胺系膜中的黃色的透明的聚醯亞胺系基材，需要開發在與其他基材接合時即使實施電漿處理也確保足夠低的接觸角從而在與其他基材或面板黏接時介面密合力優異，且對於實現軟性特性具有適當的耐久性的硬塗膜。Therefore, the actual situation is that as a transparent polyimide-based substrate that suppresses the yellow color in the yellow polyimide-based film, it is necessary to develop a substrate that ensures a sufficiently low contact even if plasma treatment is performed when bonding with other substrates. Therefore, when bonding with other substrates or panels, it is a hard coating film with excellent interface adhesion and appropriate durability for realizing soft properties.
［現有技術文獻］[Prior art literature]
＜專利文獻＞ 專利文獻1：韓國專利公告公報第10-0601308號 專利文獻2：韓國專利公開公報第10-2019-0081823號 ＜Patent Document＞ Patent Document 1: Korean Patent Gazette Publication No. 10-0601308 Patent Document 2: Korean Patent Publication No. 10-2019-0081823
［所要解決的[to be solved 課題］subject]
為了解決上述問題，本發明的一目的在於，提供一種用於硬塗膜的層疊體，該層疊體具有優異的密合性、耐溶劑性和彎曲性，常壓電漿處理後，表面的接觸角為35°以下。In order to solve the above-mentioned problems, an object of the present invention is to provide a laminated body for a hard coat film, which has excellent adhesion, solvent resistance and flexibility, and after atmospheric pressure plasma treatment, the surface contact The angle is 35° or less.
此外，本發明的一目的在於，提供包含上述層疊體的硬塗膜以及應用了該硬塗膜的視窗和圖像顯示裝置。Another object of the present invention is to provide a hard coat film including the above laminate, and a window and an image display device to which the hard coat film is applied.
但是，本發明所要解決的課題不受以上提及的課題的限制，本領域的一般具有通常知識者應當可以由以下記載明確理解未提到的其他課題。However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and those with ordinary knowledge in the art should be able to clearly understand other problems not mentioned from the following description.
［解決課題的方法］[How to solve the problem]
為了實現上述技術課題，本發明涉及一種層疊體，其包含透明聚醯亞胺系基材層、以及在上述基材層的至少一面形成的由易黏接性組合物的固化物形成的易黏接層，上述易黏接層在表面不包含含有C-F鍵的取代基。In order to achieve the above-mentioned technical subject, the present invention relates to a laminate comprising a transparent polyimide-based base layer, and an easily-adhesive layer made of a cured product of an easily-adhesive composition formed on at least one side of the base layer. The bonding layer, the above-mentioned easy-adhesive layer does not contain a substituent containing a C-F bond on the surface.
本發明涉及一種層疊體，其特徵在於，常壓電漿處理後，上述易黏接層的接觸角為35°以下。The present invention relates to a laminate characterized in that, after atmospheric pressure plasma treatment, the contact angle of the above-mentioned easily bonding layer is 35° or less.
本發明涉及一種層疊體，上述易黏接層的厚度為40nm以上3㎛以下。The present invention relates to a laminate in which the thickness of the easily bonding layer is not less than 40 nm and not more than 3 ㎛.
本發明涉及一種層疊體，上述易黏接性組合物包含光聚合性化合物、溶劑和引發劑中的至少一種以上。The present invention relates to a laminate wherein the easily-adhesive composition includes at least one of a photopolymerizable compound, a solvent, and an initiator.
本發明涉及一種層疊體，其特徵在於，上述光聚合性化合物包含由不使上述透明聚醯亞胺系基材溶解的多官能丙烯酸酯單體和多官能丙烯酸酯低聚物所組成的組中的至少一種以上。The present invention relates to a laminate characterized in that the photopolymerizable compound includes a polyfunctional acrylate monomer and a polyfunctional acrylate oligomer that do not dissolve the transparent polyimide-based substrate. at least one of the above.
本發明涉及一種層疊體，上述易黏接性組合物還包含添加劑。The present invention relates to a laminate in which the above-mentioned easily-adhesive composition further includes an additive.
本發明涉及一種層疊體，上述C-F鍵為由C-FX表示的鍵，x為1至3。The present invention relates to a laminate wherein the C-F bond is a bond represented by C-FX, and x is 1 to 3.
本發明涉及一種層疊體，其用於硬塗膜。This invention relates to the laminated body used for a hard coat film.
此外，本發明涉及一種硬塗膜，其包含在上述基材層的與易黏接層不同的一面形成的硬塗層。Moreover, this invention relates to the hard coat film containing the hard coat layer formed on the surface different from the easily bonding layer of the said base material layer.
此外，本發明涉及一種硬塗膜，其用於軟性顯示器。Furthermore, the present invention relates to a hard coat film used for a flexible display.
此外，本發明涉及一種視窗，其包含上述硬塗膜。Moreover, this invention relates to the window containing the said hard coat film.
此外，本發明涉及一種圖像顯示裝置，其包含上述視窗。In addition, the present invention relates to an image display device including the above-mentioned window.
［發明效果］[Effect of the invention]
本發明的層疊體和包含其的硬塗膜表現出以下特性：密合性、耐溶劑性和彎曲性均優異，且常壓電漿處理後，易黏接層的接觸角為35°以下。The laminated body of the present invention and the hard coat film comprising the same exhibit the following properties: excellent adhesion, solvent resistance, and flexibility, and the contact angle of the easily-adhesive layer after atmospheric pressure plasma treatment is 35° or less.
因此，包含本發明的層疊體的圖像顯示裝置顯示出提高了的機械可靠性和軟性，對於軟性顯示器用硬塗膜而言具有優異的耐久性，能夠大幅提高製程速度。Therefore, an image display device including the laminate of the present invention exhibits improved mechanical reliability and flexibility, has excellent durability for a hard coating film for a flexible display, and can significantly increase a process speed.
為了對本發明之上述及其他方面有更佳的瞭解，下文特舉實施例，並配合所附圖式詳細說明如下：In order to have a better understanding of the above-mentioned and other aspects of the present invention, the following specific examples are given in detail with the accompanying drawings as follows:
本發明涉及包含透明聚醯亞胺系基材層以及在上述基材層的至少一面形成且在表面不含有C-F鍵的由易黏接性組合物的固化物形成的易黏接層的層疊體，適合用於軟性顯示器的硬塗膜、以及利用該硬塗膜的視窗和圖像顯示裝置。The present invention relates to a laminate comprising a transparent polyimide-based base layer and an easily-adhesive layer formed on at least one surface of the base layer and containing no C-F bond on the surface, which is formed of a cured product of an easily-adhesive composition , It is suitable for a hard coat film of a flexible display, and a window and an image display device using the hard coat film.
以下，將詳細說明本發明較佳的實施方式。Hereinafter, preferred embodiments of the present invention will be described in detail.
＜< 層疊Cascade 體body ＞>
本發明的層疊體在透明聚醯亞胺系基材層120的一面包含易黏接層110。第1圖繪示出了包含本發明的一實施例的層疊體的硬塗膜，如第1圖所繪示的那樣，本發明的層疊體可以是以基材層120為中心在層疊有硬塗層130的相反面形成有易黏接層110的結構。The laminate of the present invention includes an easily bonding layer 110 on one side of the transparent polyimide-based base material layer 120 . Figure 1 shows a hard coat film comprising a laminate according to an embodiment of the present invention. As shown in Figure 1, the laminate of the present invention may be centered on a substrate layer 120 laminated with hard coatings. The opposite surface of the coating layer 130 is formed with the structure of the easy-adhesive layer 110 .
本發明的層疊體的上述易黏接層的特徵在於，表面不包含C-F鍵。本發明中，所謂表面不包含C-F鍵，是指表面不包含含有C-F鍵的取代基，在測定表面元素含量時，其含義可以是測定到不包含F元素。上述“不包含”是包括實質上不包含的概念，其含義是以在上述易黏接層的表面所測定到的總元素含量100重量%為基準含量為0.5%以下。The above-mentioned easily-adhesive layer of the laminated body of this invention is characterized in that the surface does not contain a C-F bond. In the present invention, the so-called surface does not contain C-F bonds, which means that the surface does not contain substituents containing C-F bonds. When measuring the content of surface elements, it means that F elements are not included. The above-mentioned "not containing" is a concept including substantially not containing, and it means that the content is 0.5% or less based on 100% by weight of the total element content measured on the surface of the above-mentioned easily bonding layer.
本發明中，在易黏接層的表面所測定到的總元素是指利用測定表面的元素含量的公知的設備所能夠測定到的元素，作為一例，是指利用XPS設備等所能夠測定到的元素，但不限定於此。In the present invention, the total elements measured on the surface of the easily bonding layer refer to elements that can be measured using known equipment for measuring the element content on the surface, and as an example, refer to elements that can be measured using XPS equipment, etc. elements, but not limited to them.
上述C-F鍵是由C-F X表示的鍵，x可以為1至3。例如，由C-F X表示的鍵可以是CF 1、CF 2或CF 3，包含上述C-F鍵的取代基包括-CH 2F 1、-CHF 2、-CF 3等，但不限定於此。 The aforementioned CF bond is a bond represented by CF X , where x can be 1 to 3. For example, the bond represented by CF X may be CF 1 , CF 2 or CF 3 , and the substituents containing the aforementioned CF bond include -CH 2 F 1 , -CHF 2 , -CF 3 , etc., but are not limited thereto.
本發明的層疊體在常壓電漿處理後，上述易黏接層的接觸角可以為35°以下，該情況下，具有在與其他基材或面板附著來使用時，對於反復折疊等外部刺激的耐久性優異，不易發生剝離現象等優點。After the laminated body of the present invention is treated with atmospheric pressure plasma, the contact angle of the above-mentioned easy-adhesive layer may be 35° or less. In this case, when it is used by attaching to other substrates or panels, it may be vulnerable to external stimuli such as repeated folding. The durability is excellent, and the peeling phenomenon is not easy to occur.
本發明的層疊體可以用於硬塗膜。The laminated body of this invention can be used for a hard coat film.
基材Substrate 層layer
上述基材層120用於代替以往的玻璃基板來支撐將要後述的易黏接層110以及其他基材或面板，可以為聚醯亞胺系基材層，較佳為透明聚醯亞胺系基材層。The above substrate layer 120 is used to replace the conventional glass substrate to support the easy-adhesive layer 110 and other substrates or panels to be described later, and may be a polyimide-based substrate layer, preferably a transparent polyimide-based substrate layer. material layer.
本發明中，上述“透明”的含義是可見光線的透過率為70%以上或80%以上。In the present invention, the above-mentioned "transparent" means that the transmittance of visible light is 70% or more or 80% or more.
具體而言，用作上述基材層的聚醯亞胺系膜是既透明又具有對於折疊的耐久性的高分子膜，可以使用在以往的黃色的聚醯亞胺系膜中抑制了黃色的透明的聚醯亞胺系基材膜。Specifically, the polyimide-based film used as the above-mentioned base material layer is a polymer film that is transparent and has durability against folding, and a yellow polyimide-based film that suppresses yellowness in the conventional yellow polyimide-based film can be used. Transparent polyimide base film.
在抑制了黃色的透明聚醯亞胺系膜的情況下，存在相當一部分的C-F鍵，因此具有在電漿處理後水接觸角降低不大的問題。在電漿處理時，具有284.8eV的鍵能的C-C鍵發生分離而與氧自由基等反應，形成C-O、C=O、COOH等鍵，由此表面轉變成親水性，使水接觸角降低。然而，鍵能高達290eV以上的C-F鍵由於電漿處理效率相對較低，即使在電漿處理後也維持高比率的C-F鍵，因此可能導致不易獲得充分低的接觸角的問題。In the case of a transparent polyimide-based film with suppressed yellow color, there is a problem in that a considerable portion of C-F bonds exists, and thus the water contact angle does not decrease significantly after plasma treatment. During plasma treatment, the C-C bond with a bond energy of 284.8eV is separated and reacts with oxygen free radicals to form bonds such as C-O, C=O, COOH, etc., so that the surface becomes hydrophilic and the water contact angle decreases. However, since the plasma treatment efficiency of C-F bonds with a bond energy as high as 290eV or more is relatively low, a high ratio of C-F bonds is maintained even after plasma treatment, which may cause a problem that it is difficult to obtain a sufficiently low contact angle.
如果接觸角無法充分降低，則在附著黏著劑或光學用黏著膜(OCA)等而與其他基材或面板附著來實施反復折疊等耐久性評價時，存在介面密合力不足而發生剝離現象等問題。If the contact angle cannot be sufficiently reduced, there will be problems such as insufficient interface adhesion and peeling when attaching adhesives or optical adhesive films (OCA) to other substrates or panels for durability evaluation such as repeated folding. .
為此，本發明透過在上述基材層的一面包含後述的易黏接層，從而改善了這樣的透明聚醯亞胺系基材層的問題。具體而言，本發明的透明聚醯亞胺系基材層在一面包含特定的易黏接層，表面不包含含有C-F鍵的取代基，因而具有優異的耐久性，能夠在常壓電漿處理後表現出充分低的接觸角。For this reason, the present invention improves the problem of such a transparent polyimide-based base material layer by including an easy-adhesive layer described later on one side of the base material layer. Specifically, the transparent polyimide-based substrate layer of the present invention includes a specific easy-adhesive layer on one side, and the surface does not include substituents containing C-F bonds, so it has excellent durability and can be treated with normal pressure plasma. exhibited a sufficiently low contact angle.
易黏接Easy to stick 層layer
上述易黏接層110可以透過在上述透明聚醯亞胺系基材層120的一面塗布易黏接性組合物後照射紫外線進行光固化來形成。上述易黏接性組合物包含易黏接性化合物、溶劑和引發劑中的至少一種以上，可以進一步包含添加劑。The easy-adhesive layer 110 may be formed by applying an easily-adhesive composition on one side of the transparent polyimide-based base material layer 120 and then irradiating ultraviolet rays to perform photocuring. The above-mentioned easily-adhesive composition contains at least one of an easily-adhesive compound, a solvent, and an initiator, and may further contain additives.
此時，塗布易黏接性組合物的方法只要是本技術所屬技術領域中能夠應用的方法就沒有特別限制，例如，可以利用棒塗方式、刮刀塗布(knife coating)方式、輥塗方式、刮板塗布(blade coating)方式、模塗方式、微凹版塗布方式、缺角輪塗布方式、狹縫式模塗方式、唇模塗布方式、溶液流延方式等。At this time, the method of coating the easily-adhesive composition is not particularly limited as long as it is a method applicable in the technical field of the present technology. Blade coating method, die coating method, micro gravure coating method, cut corner wheel coating method, slot die coating method, lip die coating method, solution casting method and the like.
上述易黏接層的厚度為40nm至3㎛，較佳為50nm至1㎛，這從密合力和耐久性方面考慮是較佳的。在小於40nm的情況下，無法充分防止基材的C-F鍵而可能不會明顯出現接觸角下降，在大於3㎛的情況下，存在軟性特性降低而在折疊時發生內部裂紋等擔憂。The thickness of the above-mentioned easy-adhesive layer is 40nm to 3㎛, preferably 50nm to 1㎛, which is preferable in terms of adhesion and durability. If it is less than 40nm, the C-F bond of the base material cannot be sufficiently prevented and the contact angle may not decrease significantly, and if it is more than 3㎛, there is a concern that the soft characteristics will decrease and internal cracks will occur during folding.
上述易黏接性化合物是能夠進行光聚合的化合物，只要不具有包含C-F鍵的取代基就沒有特別限制，可以包含多官能丙烯酸酯單體和多官能丙烯酸酯低聚物等。The above-mentioned easily-adhesive compound is a compound capable of photopolymerization, and is not particularly limited as long as it does not have a substituent including a C-F bond, and may include polyfunctional acrylate monomers, polyfunctional acrylate oligomers, and the like.
上述多官能丙烯酸酯單體較佳地不使透明聚醯亞胺系基材溶解，這是因為，在透明聚醯亞胺系基材發生溶解時，存在基材成分混入到易黏接層中而使易黏接層的表面的F濃度升高的擔憂。The above-mentioned polyfunctional acrylate monomer preferably does not dissolve the transparent polyimide-based substrate, because, when the transparent polyimide-based substrate is dissolved, there are components of the substrate mixed into the easily bonding layer. However, there is a concern that the F concentration on the surface of the easily bonding layer may increase.
上述多官能丙烯酸酯單體可以是光固化型多官能丙烯酸酯單體，具體而言，可舉出：具有甲基、乙基、丙基、丁基、戊基、己基、戊基、2-乙基己基、辛基、壬基、十二烷基、異癸基、月桂基、十六烷基、環己基、苄基、甲氧基乙基、乙氧基乙基、丁氧基乙基、苯氧基乙基、烯丙基、甲代烯丙基、縮水甘油基、2-羥基乙基、2-羥基丙基、3-氯-2-羥基丙基、二甲基氨基己基、二乙基氨基己基、異冰片基等之類的取代基的丙烯酸酯或甲基丙烯酸酯；乙二醇、二乙二醇、三乙二醇、丙二醇、三丙二醇、丁二醇、四亞甲基二醇、六亞甲基二醇、新戊二醇、丁二醇、己二醇、三羥甲基丙烷、季戊四醇、二季戊四醇等多官能性丙烯酸酯、甲基丙烯酸酯及其衍生物等。The above-mentioned multifunctional acrylate monomer can be a photocurable multifunctional acrylate monomer, specifically, can enumerate: have methyl, ethyl, propyl, butyl, pentyl, hexyl, pentyl, 2- Ethylhexyl, octyl, nonyl, dodecyl, isodecyl, lauryl, hexadecyl, cyclohexyl, benzyl, methoxyethyl, ethoxyethyl, butoxyethyl , phenoxyethyl, allyl, methallyl, glycidyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl, dimethylaminohexyl, di Acrylates or methacrylates with substituents such as ethylaminohexyl, isobornyl, etc.; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tripropylene glycol, butylene glycol, tetramethylene glycol Diol, hexamethylene glycol, neopentyl glycol, butylene glycol, hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol and other polyfunctional acrylates, methacrylates and their derivatives, etc.
上述光固化型多官能丙烯酸酯單體只要是本技術領域中通常使用的就沒有特別限制，其中，較佳地為多官能(氨基甲酸酯)丙烯酸酯。上述多官能丙烯酸酯單體是3至10官能團的單體，這從形成交聯結構層方面考慮是較佳的。也可以與其一起混合使用1或2官能團的單體。The photocurable multifunctional acrylate monomer is not particularly limited as long as it is commonly used in this technical field, and among them, polyfunctional (urethane) acrylate is preferred. The above-mentioned multifunctional acrylate monomer is a monomer with 3 to 10 functional groups, which is preferable from the aspect of forming a cross-linked structure layer. Monomers with 1 or 2 functional groups can also be used in combination therewith.
上述多官能丙烯酸酯低聚物可以是光固化型多官能丙烯酸酯低聚物，通常使用環氧(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯、多面體低聚倍半矽氧烷(甲基)丙烯酸酯等，可以選擇使用一種以上。上述多官能丙烯酸酯低聚物是3至18官能團的單體，這從形成交聯結構層方面考慮是較佳的。也可以與其一起混合使用1或2官能團的低聚物。The above-mentioned multifunctional acrylate oligomers can be photocurable multifunctional acrylate oligomers, and epoxy (meth)acrylates, urethane (meth)acrylates, polyhedral oligomeric silsesquioxanes are usually used Alkane (meth)acrylate, etc., can select and use 1 or more types. The above-mentioned polyfunctional acrylate oligomer is a monomer with 3 to 18 functional groups, which is preferable from the viewpoint of forming a cross-linked structure layer. A monofunctional or bifunctional oligomer may also be used in combination therewith.
上述易黏接性化合物的含量沒有特別限制，相對於上述易黏接性組合物整體100重量份，較佳為1至20重量份。在含量小於1重量份的情況下，不易實現充分的硬度提高，在含量大於20重量份的情況下，可能發生難以塗布1㎛以下厚度的薄膜的問題。The content of the above-mentioned easily-adhesive compound is not particularly limited, and is preferably 1 to 20 parts by weight relative to 100 parts by weight of the above-mentioned easily-adhesive composition as a whole. When the content is less than 1 part by weight, it is difficult to achieve sufficient hardness improvement, and when the content exceeds 20 parts by weight, it may be difficult to apply a film with a thickness of 1㎛ or less.
上述溶劑起到將上述易黏接性化合物與引發劑、添加劑等易黏接性組合物混合的作用，只要能夠使組合物的黏度維持得低而能夠實現薄膜塗布就沒有特別限制。特別佳為透明聚醯亞胺系基材不易被溶解的貧溶劑，以便塗布在透明聚醯亞胺系基材上時，透明聚醯亞胺成分不會因溶劑而溶脹或溶解，從而向易黏接性化合物層的表面移動。The above-mentioned solvent plays a role of mixing the above-mentioned easily-adhesive compound with the easily-adhesive composition such as an initiator and an additive, and there is no particular limitation as long as the viscosity of the composition can be kept low to enable thin film coating. Particularly preferred is a poor solvent in which transparent polyimide-based substrates are not easily dissolved, so that when coated on transparent polyimide-based substrates, the transparent polyimide components will not be swollen or dissolved by the solvent, thereby facilitating The surface of the adhesive compound layer moves.
作為透明聚醯亞胺系基材不易被溶解的貧溶劑，代表性地，可以較佳地使用甲醇、乙醇、異丙醇、丁醇、甲基溶纖劑、乙基溶纖劑等醇系；二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、丙二醇單甲基醚等醚系；等，上述例示的溶劑可以各自單獨使用或將兩種以上組合使用。其中，特別佳為醇系溶劑，尤其最佳為異丙醇，這是因為，不僅能夠由於低表面張力而使易黏接層形成用組合物的塗布性變佳，還能夠由於是聚醯亞胺成分的溶解度最低的溶劑之一而使以上提及的基材成分向易黏接層的混入最少化。As a poor solvent in which transparent polyimide-based substrates are difficult to dissolve, alcohol-based solvents such as methanol, ethanol, isopropanol, butanol, methyl cellosolve, and ethyl cellosolve can be preferably used. ; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether and other ether systems; The solvents can be used alone or in combination of two or more. Among them, alcohol-based solvents are particularly preferable, and isopropanol is particularly preferable because not only the coating properties of the composition for forming an easily bonding layer can be improved due to low surface tension, but also because polyamide One of the solvents with the lowest solubility for the amine component minimizes the incorporation of the above-mentioned substrate components into the easy-bonding layer.
另外，為了確保易黏接性化合物與透明聚醯亞胺系基材的密合性，可以使用與貧溶劑一起混合有透明聚醯亞胺系基材易被溶解的良溶劑的混合溶劑。良溶劑與貧溶劑可以根據透明膜的材質而適當選擇。作為透明聚醯亞胺系基材易被溶解的良溶劑，有甲基乙基酮、甲基丁基酮、甲基異丁基酮、二乙基酮、二丙基酮、環己酮等酮系溶劑；乙酸乙酯、乙酸丙酯、乙酸正丁酯、乙酸叔丁酯、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、乙酸甲氧基丁酯、乙酸甲氧基戊酯等乙酸酯系溶劑；等。In addition, in order to secure the adhesion between the easily-adhesive compound and the transparent polyimide-based substrate, a mixed solvent may be used in which a good solvent in which the transparent polyimide-based substrate is easily dissolved is mixed with a poor solvent. A good solvent and a poor solvent can be appropriately selected according to the material of the transparent film. As a good solvent for transparent polyimide-based substrates, there are methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone, etc. Ketone solvents; ethyl acetate, propyl acetate, n-butyl acetate, tert-butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol Acetate-based solvents such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; etc.
最終，可以無限制地使用將溶劑混合而塗布後在易黏接層的表面不會檢測出C-F鍵的水準的配合比以及含量被優化後的組成。Ultimately, a composition in which solvents are mixed and coated at such a level that C-F bonds are not detected on the surface of the easily bonding layer and the content is optimized can be used without limitation.
這樣的溶劑的含量相對於上述易黏接性組合物整體100重量份較佳為10至98重量份，更佳為20至85重量份。如果上述溶劑的含量小於20重量份，則不僅黏度高而操作性降低，而且可能由此導致密合性降低。另一方面，在大於98重量份的情況下，存在乾燥過程中所需時間多，經濟性變差的問題，並且可能由於透明基材膜的溶脹嚴重而產生霧度(Haze)。為此，較佳地在上述範圍內適當使用溶劑。The content of such a solvent is preferably from 10 to 98 parts by weight, more preferably from 20 to 85 parts by weight, based on 100 parts by weight of the above-mentioned easily-adhesive composition as a whole. If the content of the above-mentioned solvent is less than 20 parts by weight, not only the viscosity is high to lower the workability, but also the adhesiveness may be lowered. On the other hand, when it is more than 98 parts by weight, there are problems in that the drying process takes a long time and the economic efficiency is poor, and haze may be generated due to severe swelling of the transparent base film. For this reason, it is preferable to use the solvent appropriately within the above-mentioned range.
上述引發劑只要是本技術領域中使用的就可以無限制地使用，較佳地使用自由基系引發劑、陽離子性引發劑等。The aforementioned initiators can be used without limitation as long as they are used in the technical field, but radical initiators, cationic initiators, and the like are preferably used.
具體而言，有Irgacure 184、Irgacure 369、Irgacure 651、Irgacure 819、Irgacure 907、安息香烷基醚(Benzionalkylether)、二苯甲酮(Benzophenone)、苄基二甲基縮醛(Benzyl dimethyl katal)、羥基環己基苯基丙酮(Hydroxycyclohexyl phenylacetone)、氯代苯乙酮(Chloro acetophenone)、1,1-二氯苯乙酮(1,1-Dichloro acetophenone)、二乙氧基苯乙酮(Diethoxy acetophenone)、羥基苯乙酮(Hydroxy Acetophenone)、2-氯噻噸酮(2-Choro thioxanthone)、2-ETAQ(2-Ethyl Anthraquinone：2-乙基蒽醌)、1-羥基-環己基-苯基-酮(1-Hydroxy-cyclohexylphenyl-ketone)、2-羥基-2-甲基-1-苯基-1-丙酮(2-Hydroxy-2-methyl-1-phenyl-1-propanone)、2-羥基-1-[4-(2-羥基乙氧基)苯基]-2-甲基-1-丙酮(2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl- 1-propanone)、苯甲醯甲酸甲酯(methylbenzoylformate)、雙(2,4,6-三甲基苯甲醯)苯基氧化膦、2-羥基-2-甲基-1-苯基丙烷-1-酮等，它們可以單獨使用或將兩種以上混用。Specifically, there are Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, benzoin alkyl ether (Benzionalkylether), benzophenone (Benzophenone), benzyl dimethyl acetal (Benzyl dimethyl katal), hydroxyl Hydroxycyclohexyl phenylacetone, Chloro acetophenone, 1,1-Dichloro acetophenone, Diethoxy acetophenone, Hydroxy Acetophenone, 2-Chorothioxanthone, 2-ETAQ (2-Ethyl Anthraquinone: 2-Ethyl Anthraquinone), 1-Hydroxy-Cyclohexyl-Phenyl-Kone (1-Hydroxy-cyclohexylphenyl-ketone), 2-Hydroxy-2-methyl-1-phenyl-1-propanone (2-Hydroxy-2-methyl-1-phenyl-1-propanone), 2-Hydroxy-1 -[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone) , methylbenzoylformate, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropane-1-one, etc. , they can be used alone or in combination of two or more.
這樣的引發劑相對於上述易黏接性組合物整體100重量份可以按照0.1至10重量份、較佳地按照1至5重量份範圍來使用。本發明中，如果其含量小於0.1重量份，則組合物的固化速度慢，可能出現未固化而機械物性降低，另一方面，如果大於10重量份，則可能由於過固化而使塗膜產生裂紋。Such an initiator can be used in an amount of 0.1 to 10 parts by weight, preferably in a range of 1 to 5 parts by weight, based on 100 parts by weight of the above-mentioned easily-adhesive composition as a whole. In the present invention, if the content is less than 0.1 parts by weight, the curing speed of the composition is slow, and the mechanical properties may be reduced due to uncured. On the other hand, if it is more than 10 parts by weight, the coating film may be cracked due to overcuring. .
本發明的一實施方式中，上述組合物還可以進一步包含添加劑。作為上述添加劑，可以追加使用丙烯酸系或有機矽系流平劑等，能夠起到提高表面流平性的作用。在上述易黏接性組合物包含上述流平劑的情況下，在形成塗膜時防止組合物內產生凝集的現象而使其均勻地形成，具有能夠賦予平滑性和塗布性的優點。In one embodiment of the present invention, the above composition may further contain additives. As the above-mentioned additives, an acrylic or silicone-based leveling agent can be additionally used to improve surface leveling properties. When the above-mentioned easily-adhesive composition contains the above-mentioned leveling agent, when forming a coating film, it prevents aggregation phenomenon in the composition and forms it uniformly, which has the advantage of being able to impart smoothness and coatability.
上述流平劑可以應用本領域通常使用的流平劑。其中，更佳為有機矽系流平劑，例如，可以使用有機矽二丙烯酸酯系或有機矽聚丙烯酸酯系化合物等，且可以將它們單獨使用或將兩種以上混合使用，但並非一定限定於這些流平劑。As the above-mentioned leveling agent, a leveling agent commonly used in the art can be used. Among them, organosilicon-based leveling agents are more preferable, for example, organosilicon diacrylate or organosilicon polyacrylate compounds can be used, and they can be used alone or in combination of two or more, but not necessarily limited for these leveling agents.
上述添加劑可以在不阻礙本發明的效果的範圍內透過適當調節含量進行添加。The above-mentioned additives can be added by appropriately adjusting the content within the range that does not hinder the effect of the present invention.
＜< 硬塗膜Hard coating ＞>
本發明的硬塗膜只要包含上述層疊體就沒有特別限定。The hard coat film of the present invention will not be particularly limited as long as it includes the above-mentioned laminate.
本發明的實施例的硬塗膜100如第1圖所繪示的那樣可以包含上述層疊體以及在基材層120的易黏接層110相反一面所形成的硬塗層130。The hard coat film 100 of the embodiment of the present invention may include the above-mentioned laminated body and the hard coat layer 130 formed on the opposite side of the easy-adhesive layer 110 of the substrate layer 120 as shown in FIG. 1 .
硬塗層可以透過本技術領域已知的方法來製造。硬塗層的厚度沒有特別限定，例如，可以為5至100㎛。在厚度為上述範圍內的情況下，能夠表現出更加優異的硬度和軟性，防止捲曲現象。Hard coatings can be produced by methods known in the art. The thickness of the hard coat layer is not particularly limited, and may be, for example, 5 to 100㎛. When the thickness is within the above range, more excellent hardness and softness can be exhibited, and curling can be prevented.
將上述硬塗膜乾燥的步驟可以利用加熱板、熱風迴圈爐、紅外線爐等加熱機構來實施，可以以50至150℃或者50至100℃溫度來實施。The step of drying the above-mentioned hard coating film can be implemented by using a heating mechanism such as a heating plate, a hot air circulation furnace, an infrared furnace, etc., and can be implemented at a temperature of 50 to 150°C or 50 to 100°C.
使上述硬塗膜固化的步驟中，照射190nm至450nm、比如200nm至500nm的UV光線等活性射線。作為照射時所使用的光源，可以使用低壓水銀燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、氬氣雷射器等，根據情況不同也可以使用X射線、電子射線等。In the step of curing the hard coat film, active rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm, are irradiated. As a light source used for irradiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, argon lasers, etc. can be used, and X-rays, electron beams, etc. can also be used depending on the case.
對上述硬塗膜的易黏接層進行常壓電漿處理的步驟中，將易黏接層設置成電漿處理面後，在吹入氮氣和空氣的狀態下以0.5至3KW的輸出功率進行電漿處理，從而使表面得到親水處理。特別是，透過在1atm(760Torr)大氣壓而非真空下產生電漿來對表面進行處理的過程，從而能夠將表面能調節成符合所期望的製程條件。In the step of performing normal-pressure plasma treatment on the easy-adhesive layer of the above-mentioned hard coating film, after setting the easy-adhesive layer as the plasma-treated surface, the process is carried out at an output power of 0.5 to 3KW under the state of blowing nitrogen and air. Plasma treatment to make the surface hydrophilic. In particular, the surface energy can be adjusted to meet the desired process conditions by generating plasma at 1 atm (760 Torr) atmospheric pressure instead of vacuum to process the surface.
＜< 圖picture 像picture 顯show 示裝置display device ＞>
本發明的實施例提供包含上述硬塗膜的視窗和圖像顯示裝置。Embodiments of the present invention provide a window and an image display device including the above-mentioned hard coat film.
例如，可以作為包含上述硬塗膜的視窗或視窗層疊體來使用，此時，可以在硬塗膜所形成的視窗的一面層疊偏光層或觸控感測器層中的至少一種。這樣的視窗或視窗層疊體可以作為形成在圖像顯示裝置的最外表面的視窗膜來使用。另外，上述硬塗膜例如也可以***至圖像顯示裝置的內部。For example, it can be used as a window or a window laminate including the above-mentioned hard coat film. In this case, at least one of a polarizing layer and a touch sensor layer can be laminated on one side of the window formed by the hard coat film. Such a window or a window laminate can be used as a window film formed on the outermost surface of an image display device. Moreover, the said hard coat film can also be inserted in the inside of an image display apparatus, for example.
上述圖像顯示裝置包括液晶顯示裝置、電致發光顯示裝置、電漿顯示裝置、場發射顯示裝置等各種圖像顯示裝置，可以是保有軟性、彎曲特性的軟性顯示裝置。The above-mentioned image display device includes various image display devices such as liquid crystal display device, electroluminescent display device, plasma display device, field emission display device, etc., and may be a flexible display device that maintains flexibility and bending characteristics.
該情況下，本發明的實施例的硬塗層疊體可以更加有效地用作上述軟性顯示裝置的視窗或視窗層疊體。透過本發明的實施例的硬塗膜所包含的基材層和易黏接層的相互作用，能夠同時提高視窗的軟性和耐久性，還能夠同時實現抗靜電性能。由此，能夠在提高例如上述軟性顯示裝置的耐衝擊性、耐磨性的同時在彎曲、折彎(bending)時也防止裂紋、剝離等之類的損傷。In this case, the hard-coat laminated body of the Example of this invention can be used more effectively as a window or a window laminated body of the said flexible display device. Through the interaction between the substrate layer and the easy-adhesive layer contained in the hard coating film of the embodiment of the present invention, the softness and durability of the window can be improved at the same time, and the antistatic performance can also be realized at the same time. Thereby, for example, while improving the impact resistance and abrasion resistance of the above-mentioned flexible display device, it is possible to prevent damages such as cracks and peeling during bending and bending.
以下，為了幫助本發明的理解，提供包含具體實施例和比較例在內的實驗例，但這只是用於例示本發明，並非限制隨附的權利要求範圍，對於本領域具有通常知識者而言，顯而易見的是，在本發明的範疇和技術思想範圍內可以對實施例進行各種各樣的變更以及修改，當然這樣的變更以及修改也屬於隨附的權利要求範圍。另外，除非特別提及，則以下表示含量的“%”和“份”為重量基準。Below, in order to help the understanding of the present invention, provide the experimental example that comprises specific embodiment and comparative example, but this is only for illustrating the present invention, is not to limit the scope of the appended claims, for those skilled in the art , it is obvious that various changes and modifications can be made to the embodiments within the scope and technical idea of the present invention, and of course such changes and modifications also belong to the scope of the appended claims. In addition, "%" and "parts" representing contents below are based on weight unless specifically mentioned.
合成例：易黏接性Synthesis Example: Easy Adhesiveness 組Group 合物compound 製造manufacture
製造例Manufacturing example 11
利用攪拌機配合19重量份的氨基甲酸酯丙烯酸低聚物(美來納米科技(Mirae Nanotech)公司，RSP-1)、1重量份的1-羥基環己基苯基酮、80重量份的異丙醇來製造易黏接性組合物。Utilize the stirrer to coordinate the urethane acrylic oligomer (Mirae Nanotech (Mirae Nanotech) company, RSP-1) of 19 weight parts, the 1-hydroxycyclohexyl phenyl ketone of 1 weight part, the isopropanol of 80 weight parts Alcohol to make easy-adhesive composition.
製造例Manufacturing example 22
利用攪拌機配合18.9重量份的6官能氨基甲酸酯丙烯酸酯(共榮社(KYOEISHA)，UA-306I)、80重量份的異丙醇、1重量份的1-羥基環己基苯基酮、0.1重量份的有機矽系添加劑(BYK公司，BYK-310)來製造易黏接性組合物。Utilize the mixer to coordinate 18.9 parts by weight of 6-functional urethane acrylate (KYOEISHA, UA-306I), 80 parts by weight of isopropanol, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, 0.1 Organosilicon-based additives (BYK company, BYK-310) in parts by weight are used to make the adhesive composition.
製造例Manufacturing example 33
利用攪拌機配合18.9重量份的6官能氨基甲酸酯丙烯酸酯(共榮社，UA-306I)、80重量份的異丙醇、1重量份的1-羥基環己基苯基酮、0.1重量份的有機矽系添加劑(BYK公司，BYK-333)來製造易黏接性組合物。Utilize a mixer to mix 18.9 parts by weight of 6-functional urethane acrylate (Kyoei Corporation, UA-306I), 80 parts by weight of isopropanol, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, 0.1 parts by weight of Organosilicon-based additives (BYK company, BYK-333) were used to make the adhesive composition.
製造例Manufacturing example 44
利用攪拌機配合19重量份的氨基甲酸酯丙烯酸低聚物(美來納米科技公司，RSP-1)、1重量份的1-羥基環己基苯基酮、80重量份的甲基乙基酮來製造易黏接性組合物。Utilize stirrer to coordinate the urethane acrylic acid oligomer (Meilai Nanotechnology Company, RSP-1) of 19 weight parts, the 1-hydroxycyclohexyl phenyl ketone of 1 weight part, the methyl ethyl ketone of 80 weight parts to come Make an easily-adhesive composition.
製造例Manufacturing example 55
利用攪拌機配合18.9重量份的6官能氨基甲酸酯丙烯酸酯(共榮社，UA-306I)、80重量份的甲基乙基酮、1重量份的1-羥基環己基苯基酮、0.1重量份的有機矽系添加劑(BYK公司，BYK-333)來製造易黏接性組合物。Utilize a mixer to mix 18.9 parts by weight of 6-functional urethane acrylate (Kyoei Corporation, UA-306I), 80 parts by weight of methyl ethyl ketone, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, 0.1 parts by weight Parts of silicone-based additives (BYK company, BYK-333) to make an easy-adhesive composition.
製造例Manufacturing example 66
利用攪拌機配合30重量份的氟系丙烯酸酯(共榮社，LINC-3A)、1重量份的1-羥基環己基苯基酮、69重量份的甲基乙基酮來製造易黏接性組合物。Use a mixer to mix 30 parts by weight of fluorine-based acrylate (Kyoei Corporation, LINC-3A), 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, and 69 parts by weight of methyl ethyl ketone to create an easy-adhesive combination thing.
實Reality 施例、Example, 比Compare 較compare 例和Example and 參ginseng 考Test 例：example: 層疊Cascade 體的Body 製造manufacture
實Reality 施例Example 11
將上述製造例1的易黏接性組合物以厚度800nm塗布於聚醯亞胺系基材(住友化學公司，50um)並且進行80℃、2分鐘乾燥，以500mJ/cm 2的光量進行UV固化而製作具有易黏接層的透明聚醯亞胺系膜後進行常壓電漿處理，然後確認物性。 The above-mentioned easy-adhesive composition of Production Example 1 was coated on a polyimide-based substrate (Sumitomo Chemical Co., 50um) with a thickness of 800nm, dried at 80°C for 2 minutes, and UV-cured with a light intensity of 500mJ/ cm2 On the other hand, the transparent polyimide film with an easy-to-adhesive layer was produced, and then subjected to atmospheric pressure plasma treatment, and then the physical properties were confirmed.
實Reality 施例Example 22
將上述製造例1的易黏接性組合物以厚度450nm塗布於聚醯亞胺系基材並且進行80℃、2分鐘乾燥，以500mJ/cm 2的光量進行UV固化而製作具有易黏接層的透明聚醯亞胺系膜後進行常壓電漿處理，然後確認物性。 The above-mentioned easy-adhesive composition of Production Example 1 was coated on a polyimide-based substrate with a thickness of 450 nm, dried at 80°C for 2 minutes, and UV-cured with a light intensity of 500 mJ/ cm2 to produce an easy-adhesive layer The transparent polyimide film was treated with atmospheric pressure plasma, and then the physical properties were confirmed.
實Reality 施例Example 33
將上述製造例1的易黏接性組合物以厚度200nm塗布於聚醯亞胺系基材並且進行80℃、2分鐘乾燥，以500mJ/cm 2的光量進行UV固化而製作具有易黏接層的透明聚醯亞胺系膜後進行常壓電漿處理，然後確認物性。 The above-mentioned easy-adhesive composition of Production Example 1 was coated on a polyimide-based substrate with a thickness of 200nm and dried at 80°C for 2 minutes, and UV-cured with a light intensity of 500mJ/ cm2 to produce an easy-adhesive layer The transparent polyimide film was treated with atmospheric pressure plasma, and then the physical properties were confirmed.
實Reality 施例Example 44
將上述製造例1的易黏接性組合物以厚度80nm塗布於聚醯亞胺系基材並且進行80℃、2分鐘乾燥，以500mJ/cm 2的光量進行UV固化而製作具有易黏接層的透明聚醯亞胺系膜後進行常壓電漿處理，然後確認物性。 The above-mentioned easy-adhesive composition of Production Example 1 was coated on a polyimide-based substrate with a thickness of 80nm and dried at 80°C for 2 minutes, and UV-cured with a light intensity of 500mJ/ cm2 to produce an easy-adhesive layer The transparent polyimide film was treated with atmospheric pressure plasma, and then the physical properties were confirmed.
實Reality 施例Example 55
將上述製造例2的易黏接性組合物以厚度450nm塗布於聚醯亞胺系基材並且進行80℃、2分鐘乾燥，以500mJ/cm 2的光量進行UV固化而製作具有易黏接層的透明聚醯亞胺系膜後進行常壓電漿處理，然後確認物性。 The above-mentioned easy-adhesive composition of Production Example 2 was coated on a polyimide-based substrate with a thickness of 450 nm, dried at 80°C for 2 minutes, and UV-cured with a light intensity of 500 mJ/ cm2 to produce an easy-adhesive layer The transparent polyimide film was treated with atmospheric pressure plasma, and then the physical properties were confirmed.
實Reality 施例Example 66
將上述製造例3的易黏接性組合物以厚度450nm塗布於聚醯亞胺系基材並且進行80℃、2分鐘乾燥，以500mJ/cm 2的光量進行UV固化而製作具有易黏接層的透明聚醯亞胺系膜後進行常壓電漿處理，然後確認物性。 The above-mentioned easy-adhesive composition of Production Example 3 was coated on a polyimide-based substrate with a thickness of 450 nm, dried at 80°C for 2 minutes, and UV-cured with a light intensity of 500 mJ/ cm2 to produce an easy-adhesive layer The transparent polyimide film was treated with atmospheric pressure plasma, and then the physical properties were confirmed.
比Compare 較compare 例example 11
將上述製造例4的易黏接性組合物以厚度450nm塗布於聚醯亞胺系基材並且進行80℃、2分鐘乾燥，以500mJ/cm 2的光量進行UV固化而製作具有易黏接層的透明聚醯亞胺系膜後進行常壓電漿處理，然後確認物性。 The above-mentioned easy-adhesive composition of Production Example 4 was coated on a polyimide-based substrate with a thickness of 450 nm, dried at 80°C for 2 minutes, and UV-cured with a light intensity of 500 mJ/ cm2 to produce an easy-adhesive layer The transparent polyimide film was treated with atmospheric pressure plasma, and then the physical properties were confirmed.
比Compare 較compare 例example 22
將上述製造例5的易黏接性組合物以厚度450nm塗布於聚醯亞胺系基材並且進行80℃、2分鐘乾燥，以500mJ/cm 2的光量進行UV固化而製作具有易黏接層的透明聚醯亞胺系膜後進行常壓電漿處理，然後確認物性。 The above-mentioned easy-adhesive composition of Production Example 5 was coated on a polyimide-based substrate with a thickness of 450 nm, dried at 80°C for 2 minutes, and UV-cured with a light intensity of 500 mJ/ cm2 to produce an easy-adhesive layer The transparent polyimide film was treated with atmospheric pressure plasma, and then the physical properties were confirmed.
比Compare 較compare 例example 33
將上述製造例6的易黏接性組合物以厚度800nm塗布於聚醯亞胺系基材並且進行80℃、2分鐘乾燥，以500mJ/cm 2的光量進行UV固化而製作具有易黏接層的透明聚醯亞胺系膜後進行常壓電漿處理，然後確認物性。 The above-mentioned easy-adhesive composition of Production Example 6 was coated on a polyimide-based substrate with a thickness of 800 nm, dried at 80°C for 2 minutes, and UV-cured with a light intensity of 500 mJ/ cm2 to produce an easy-adhesive layer The transparent polyimide film was treated with atmospheric pressure plasma, and then the physical properties were confirmed.
參ginseng 照例as usual 11
將上述製造例2的易黏接性組合物以厚度30nm塗布於聚醯亞胺系基材並且進行80℃、2分鐘乾燥，以500mJ/cm 2的光量進行UV固化而製作具有易黏接層的透明聚醯亞胺系膜後進行常壓電漿處理，然後確認物性。 The above-mentioned easy-adhesive composition of Production Example 2 was coated on a polyimide-based substrate with a thickness of 30 nm, dried at 80°C for 2 minutes, and UV-cured with a light intensity of 500mJ/ cm2 to produce an easy-adhesive layer The transparent polyimide film was treated with atmospheric pressure plasma, and then the physical properties were confirmed.
參ginseng 照例as usual 22
將上述製造例2的易黏接性組合物以厚度5㎛塗布於聚醯亞胺系基材並且進行80℃、2分鐘乾燥，以500mJ/cm 2的光量進行UV固化而製作具有易黏接層的透明聚醯亞胺系膜後進行常壓電漿處理，然後確認物性。 The above-mentioned easy-adhesive composition of Production Example 2 was coated on a polyimide-based substrate with a thickness of 5㎛, dried at 80°C for 2 minutes, and UV-cured with a light intensity of 500mJ/ cm2 to produce an easy-adhesive composition. The layered transparent polyimide film was subjected to atmospheric pressure plasma treatment, and then the physical properties were confirmed.
實驗experiment 例example
(1)層疊體的易黏接層表面的元素含量(1) Element content on the surface of the easy-adhesive layer of the laminate
將上述實施例1至6和比較例1至3中製造的層疊體剪切成2cm × 2cm大小而準備樣品後，利用Quantera Ⅱ (Ulvac-PHI) XPS設備200測定上述層疊體樣品表面的元素含量。具體而言，參照第2圖，將上述層疊體樣品210放入XPS設備200的Intro中，以真空度1×10 -4Pa維持1小時以上後，移動至主腔室(main chamber)，然後以真空度1×10 -7Pa維持1小時以上。之後，將X射線(X-ray)221以橫向200μm × 縱向200μm的面積、25W以及15kV條件照射於表面，測定樣品最外側面的任意位置3次，以平均值來計算表面的構成元素含量，將結果示於表1中。此時，由於上述所照射的X射線而從樣品的表面放出的光電子向檢測器(detector)222入射的平均自由程被設定為與樣品表面形成5°角。 After the laminates produced in the above-mentioned Examples 1 to 6 and Comparative Examples 1 to 3 were cut into a size of 2 cm × 2 cm to prepare samples, Quantera II (Ulvac-PHI) XPS equipment 200 was used to measure the element content on the surface of the above-mentioned laminate samples . Specifically, referring to FIG. 2, the above-mentioned laminate sample 210 was placed in the Intro of the XPS apparatus 200, maintained at a vacuum degree of 1×10 -4 Pa for more than 1 hour, then moved to the main chamber, and then Maintain at a vacuum degree of 1×10 -7 Pa for more than 1 hour. Afterwards, X-ray (X-ray) 221 is irradiated on the surface with an area of 200 μm in width × 200 μm in length, 25W and 15kV, and the arbitrary position of the outermost surface of the sample is measured 3 times, and the content of constituent elements on the surface is calculated by the average value. The results are shown in Table 1. At this time, the mean free path of photoelectrons emitted from the surface of the sample due to the above-mentioned irradiated X-rays incident on the detector (detector) 222 is set to form an angle of 5° with the surface of the sample.
[表1]
另外，透過如下方法來測定上述實施例1至6、比較例1至3以及參照例1至2中製造的層疊體的物性，將結果示於表2中。In addition, the physical properties of the laminates produced in Examples 1 to 6, Comparative Examples 1 to 3, and Reference Examples 1 to 2 were measured by the following methods, and the results are shown in Table 2.
(2)密合性(2) Adhesion
以易黏接層面成為上部的方式將基材膜利用透明黏著劑與玻璃接合後，用切割刀按照1mm間隔以橫向、縱向100個正方形的形態在層疊體面上形成切割痕，然後利用米其邦膠帶實施3次密合性測試。結果由“密合性測試後合格的四邊形的個數/100”來表示。After the substrate film is bonded to the glass with a transparent adhesive in such a way that the easy-to-adhesive layer becomes the upper part, cut marks are formed on the surface of the laminate with a cutting knife in the form of 100 squares in the horizontal and vertical directions at intervals of 1 mm, and then the surface of the laminate is cut using Migibon Adhesiveness tests were performed on the adhesive tape 3 times. The result is represented by "the number of qualified quadrilaterals after the adhesion test/100".
(3)耐溶劑性(3) Solvent resistance
在常溫下將1滴異佛爾酮滴於易黏接層面上，靜置30分鐘後，確認易黏接層面的變化，由此實施測試。如果易黏接層面沒有變化，則標記為合格，如果有變化，則標記為不合格。1 drop of isophorone was dropped on the easily-adhesive layer at room temperature, and after standing for 30 minutes, the change of the easily-adhesive layer was confirmed, and the test was carried out. If there is no change in the easy-to-bond level, it is marked as pass, and if there is a change, it is marked as fail.
(4)初始接觸角測定(4) Determination of initial contact angle
在常溫(25℃)下在易黏接性面上滴加水滴2ml後，1分鐘後利用接觸角測定儀(KRUSS公司的DSA100)測定相對於水滴的接觸角。接觸角是用相同的試樣對水滴的左右接觸角測定5次，並使用平均值。After dripping 2 ml of water droplets on the easily-adhesive surface at normal temperature (25° C.), 1 minute later, the contact angle with respect to the water droplets was measured with a contact angle meter (DSA100 from KRUSS). For the contact angle, the left and right contact angles of water droplets were measured five times using the same sample, and the average value was used.
(5)電漿處理後接觸角測定(5) Measurement of contact angle after plasma treatment
使用電漿處理器(MAK公司的Bar(MPPH 02))，對易黏接層面以輸出1.5KW、氮氣流量310Lpm、空氣(Air)流量3Lpm、速度55mm/sec、處理間隙(Gap)2.5mm進行電漿處理。在經電漿處理的易黏接層樣品上滴加水滴2ml後，利用接觸角測定儀(KRUSS公司的DSA100)測定相對於水滴的接觸角。接觸角是用相同的試樣對水滴的左右接觸角測定5次，並使用平均值。Use a plasma processor (Bar (MPPH 02) from MAK Company) to process the easily bonded surface with an output of 1.5KW, a nitrogen flow rate of 310Lpm, an air (Air) flow rate of 3Lpm, a speed of 55mm/sec, and a processing gap (Gap) of 2.5mm. Plasma treatment. After 2 ml of water droplets were dropped on the plasma-treated easy-adhesion layer sample, the contact angle with respect to the water droplets was measured with a contact angle meter (DSA100 of KRUSS Corporation). For the contact angle, the left and right contact angles of water droplets were measured five times using the same sample, and the average value was used.
(6)彎曲性(6) Flexibility
在易黏接層伸長的方向上將膜以半徑1mm間隔反復折疊和展開20萬次，由此實施彎曲試驗。The bending test was implemented by repeatedly folding and unfolding the film 200,000 times at intervals of 1 mm in radius in the direction in which the easily bonding layer was stretched.
＜評價基準＞ O：未發生斷裂或裂紋 X：發生斷裂或裂紋 ＜Evaluation criteria＞ O: No fracture or crack occurred X: Breakage or crack occurs
[表2]
參照表2，本發明的實施例的層疊體在密合性、耐溶劑性以及彎曲性試驗中均顯示出優異的結果。另外，本發明的實施例的層疊體顯示出常壓電漿處理後接觸角均為35°以下。另一方面，使用酮系溶劑即甲基乙基酮作為易黏接性組合物的溶劑的比較例的層疊體的常壓電漿處理後接觸角為39.7°以上，沒有表現出適合於軟性膜用途的程度的物理特性。Referring to Table 2, the laminates of Examples of the present invention showed excellent results in all of the adhesiveness, solvent resistance, and flexibility tests. In addition, the laminated bodies of the Examples of the present invention showed contact angles of 35° or less after atmospheric pressure plasma treatment. On the other hand, the contact angle of the laminate of the comparative example using methyl ethyl ketone, a ketone-based solvent, as the solvent of the easily-adhesive composition after atmospheric pressure plasma treatment was 39.7° or more, and it did not show that it is suitable for flexible films. Physical properties of degree of use.
作為參考，雖然實施例5與易黏接性組合物的構成相同，但易黏接性組合物的塗布厚度為30nm或5㎛(5,000nm)的參照例1以及2的層疊體的常壓電漿處理後接觸角為35°以上。For reference, although Example 5 has the same composition as the easily-adhesive composition, the atmospheric piezoelectricity of the laminates of Reference Examples 1 and 2 in which the coating thickness of the easily-adhesive composition was 30 nm or 5㎛ (5,000 nm) The contact angle after slurry treatment is above 35°.
因此，就本發明的層疊體而言，可知易黏接性組合物的塗布厚度為40nm以上3㎛以下、更佳以50nm至1㎛的範圍塗布而成的層疊體與脫離上述構成以及範圍的比較例和參考例的層疊體相比，物理特性優異，常壓電漿處理後接觸角低至35°以下。Therefore, in the laminated body of the present invention, it can be seen that the layered body in which the coating thickness of the easily-adhesive composition is not less than 40 nm and not more than 3 ㎛, more preferably in the range of 50 nm to 1 ㎛ is different from the above-mentioned configuration and range. Compared with the laminated body of the reference example, the physical properties were excellent, and the contact angle after atmospheric pressure plasma treatment was as low as 35° or less.
綜上所述，雖然本發明已以實施例揭露如上，然其並非用以限定本發明。本發明所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾。因此，本發明之保護範圍當視後附之申請專利範圍所界定者為準。To sum up, although the present invention has been disclosed by the above embodiments, it is not intended to limit the present invention. Those skilled in the art of the present invention can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be defined by the scope of the appended patent application.
100:硬塗膜 110:易黏接層 120:基材層 130:硬塗層 200:XPS設備 210:層疊體樣品 221:X射線 222:檢測器 100: hard coating film 110: Easy bonding layer 120: substrate layer 130: hard coating 200:XPS equipment 210: Laminate sample 221:X-ray 222: detector
第1圖概略性繪示了用於說明本發明的一實施方式的包含層疊體的硬塗膜的截面圖。 第2圖概略性繪示了本發明實施例的XPS設備的結構。 Fig. 1 schematically shows a cross-sectional view of a hard coat film including a laminate according to one embodiment of the present invention. FIG. 2 schematically illustrates the structure of an XPS device according to an embodiment of the present invention.
100:硬塗膜 100: hard coating film
110:易黏接層 110: Easy bonding layer
120:基材層 120: substrate layer
130:硬塗層 130: hard coating
Claims (12)
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| Application Number | Priority Date | Filing Date | Title |
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| KR10-2021-0144647 | 2021-10-27 | ||
| KR20210144647 | 2021-10-27 | ||
| KR10-2022-0005350 | 2022-01-13 | ||
| KR1020220005350A KR20230060423A (en) | 2021-10-27 | 2022-01-13 | A laminate structure, hardcoat film including the same, window and display device using the same |
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| Publication Number | Publication Date |
|---|---|
| TW202330284A true TW202330284A (en) | 2023-08-01 |
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| TW111135693A TW202330284A (en) | 2021-10-27 | 2022-09-21 | Laminate structure, hardcoat film including the same, window and display device using the same |
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| JP (1) | JP2023065333A (en) |
| CN (1) | CN116023867A (en) |
| TW (1) | TW202330284A (en) |
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- 2022-09-21 TW TW111135693A patent/TW202330284A/en unknown
- 2022-10-13 CN CN202211254338.0A patent/CN116023867A/en active Pending
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| JP2023065333A (en) | 2023-05-12 |
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