TWI722787B - Polyimide precursor composition and polyimide film, substrate for display device, and optical device prepared by using same - Google Patents
Polyimide precursor composition and polyimide film, substrate for display device, and optical device prepared by using same Download PDFInfo
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本申請案主張於2019年2月1日在韓國智慧財產局提出申請的韓國專利申請案第10-2019-0013486號、於2019年9月30日在韓國智慧財產局提出申請的韓國專利申請案第10-2019-0121176號、於2019年9月30日在韓國智慧財產局提出申請的韓國專利申請案第10-2019-0121177號、於2019年9月30日在韓國智慧財產局提出申請的韓國專利申請案第10-2019-0121178號、於2019年12月6日在韓國智慧財產局提出申請的韓國專利申請案第10-2019-0161494號、以及於2019年12月6日在韓國智慧財產局提出申請的韓國專利申請案第10-2019-0161495號的優先權的權利，所述韓國專利申請案的揭露內容全文併入本案供參考。 This application claims the Korean patent application No. 10-2019-0013486 filed with the Korean Intellectual Property Office on February 1, 2019, and the Korean patent application filed with the Korean Intellectual Property Office on September 30, 2019 No. 10-2019-0121176, Korean Patent Application No. 10-2019-0121177 filed with the Korean Intellectual Property Office on September 30, 2019, filed with the Korean Intellectual Property Office on September 30, 2019 Korean Patent Application No. 10-2019-0121178, Korean Patent Application No. 10-2019-0161494 filed at the Korean Intellectual Property Office on December 6, 2019, and Korean Intellectual Property Office on December 6, 2019 The Korean Patent Application No. 10-2019-0161495 filed by the Bureau of Property Management has the right to priority, and the disclosure content of the Korean patent application is incorporated into this case for reference in its entirety.
本揭露是有關於一種聚醯亞胺前驅物組成物及由其製備的聚醯亞胺膜、用於顯示器元件的基板及光學元件，並且更具體而言，是有關於一種具有改善的折射率的聚醯亞胺膜。 This disclosure relates to a polyimide precursor composition, a polyimide film prepared therefrom, a substrate for display elements, and optical elements, and more specifically, to a polyimide precursor composition with an improved refractive index Of polyimide film.
基於易於在大面積上製作並且厚度及重量可減小的平板顯示器(flat panel display，FPD)，顯示器元件市場正在快速變化。 此種平板顯示器包括液晶顯示器(liquid crystal display，LCD)、有機發光顯示器(organic light emitting display，OLED)或電泳元件。 Based on flat panel displays (FPD) that are easy to manufacture on a large area and can be reduced in thickness and weight, the display device market is rapidly changing. Such flat panel displays include liquid crystal displays (LCD), organic light emitting displays (OLED), or electrophoretic elements.
根據最近進一步擴展平板顯示器的應用及用途的努力，其中將柔性基板應用至平板顯示器的所謂的柔性顯示器元件受到了特別關注。基於例如智慧型電話等行動元件而具體評析了此種柔性顯示器元件的應用，並且逐漸擴展了其應用領域。 According to recent efforts to further expand the application and use of flat panel displays, so-called flexible display elements in which flexible substrates are applied to flat panel displays have received special attention. Based on mobile devices such as smart phones, the application of such flexible display devices has been specifically analyzed, and its application fields have been gradually expanded.
一般而言，在製造柔性顯示器元件及照明元件時，藉由在固化的聚醯亞胺上形成例如緩衝層、主動層及閘極絕緣體等多層無機膜來製造薄膜電晶體(thin film transistor，TFT)元件。 Generally speaking, when manufacturing flexible display elements and lighting elements, thin film transistors (TFTs) are manufactured by forming multilayer inorganic films such as buffer layers, active layers, and gate insulators on the cured polyimide. )element.
然而，當光發射至聚醯亞胺層(基板層)時，由於由無機膜製成的多層上層的折射率與聚醯亞胺層的折射率之間的差異，發射效率可能降低。 However, when light is emitted to the polyimide layer (substrate layer), the emission efficiency may decrease due to the difference between the refractive index of the multilayer upper layer made of an inorganic film and the refractive index of the polyimide layer.
本揭露的一個目的是提供一種用於生產具有改善的折射率的聚醯亞胺膜的聚醯亞胺前驅物組成物。 An object of the present disclosure is to provide a polyimide precursor composition for producing a polyimide film with an improved refractive index.
本揭露的另一目的是提供一種使用所述聚醯亞胺前驅物組成物製備的聚醯亞胺膜。 Another object of the present disclosure is to provide a polyimide film prepared by using the polyimide precursor composition.
本揭露的又一目的是提供一種用於顯示器元件的基板及包括聚醯亞胺膜的光學元件及其製備製程。 Another object of the present disclosure is to provide a substrate for a display device, an optical device including a polyimide film, and a preparation process thereof.
為達成本揭露的目的，提供了一種聚醯亞胺前驅物組成物，所述聚醯亞胺前驅物組成物包含以下作為聚合組分：一或多種二胺，包括以下化學式1的二胺；以及一或多種酸二酐，包括以下化學式2的四羧酸二酐。 For the purpose of cost disclosure, a polyimine precursor composition is provided. The polyimine precursor composition includes the following as polymerization components: one or more diamines, including the diamine of the following chemical formula 1; And one or more acid dianhydrides, including tetracarboxylic dianhydrides of the following chemical formula 2.
根據一個實施例，所述聚合組分可更包含以下化學式4的 二胺。 According to an embodiment, the polymerization component may further include the following chemical formula 4 Diamine.
在化學式4中，每個Z獨立地為選自-CONH-、-NHCO-、-C(=O)O-及-OC(=O)中的一者，R1、R2及R3各自獨立地選自：具有1至10個碳原子的經取代或未經取代的烷基、具有1至10個碳原子的鹵代烷基、具有1至10個碳原子的烯基及具有6至18個碳原子的芳基，n1、n2及n3各自獨立地為0至4的整數，且m為1至3的整數。 In Chemical Formula 4, each Z is independently one selected from -CONH-, -NHCO-, -C(=O)O-, and -OC(=O), and R 1 , R 2 and R 3 are each Independently selected from: substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, haloalkyl groups having 1 to 10 carbon atoms, alkenyl groups having 1 to 10 carbon atoms, and 6 to 18 carbon atoms For the aryl group of the carbon atom, n1, n2, and n3 are each independently an integer from 0 to 4, and m is an integer from 1 to 3.
根據一個實施例，相對於所述二胺的總含量，所述化學式1的二胺的含量可為70莫耳%或大於70莫耳%。 According to one embodiment, relative to the total content of the diamine, the content of the diamine of Chemical Formula 1 may be 70 mol% or more than 70 mol%.
根據一個實施例，相對於所述酸二酐的總含量，所述化學式2的四羧酸二酐的含量可為70莫耳%或大於70莫耳%。 According to an embodiment, relative to the total content of the acid dianhydride, the content of the tetracarboxylic dianhydride of Chemical Formula 2 may be 70 mol% or more than 70 mol%.
根據一個實施例，所述聚醯亞胺前驅物組成物中含有的聚醯胺酸在整個重覆結構可包括70莫耳%或大於70莫耳%的化學式3的重覆結構。 According to one embodiment, the polyimide contained in the polyimide precursor composition may include 70 mol% or more than 70 mol% of the repeating structure of Chemical Formula 3 in the entire repeating structure.
根據一個實施例，相對於所述二胺的所述總含量，所述化學式4的二胺的含量可為0莫耳%至30莫耳%。 According to one embodiment, relative to the total content of the diamine, the content of the diamine of Chemical Formula 4 may be 0 mol% to 30 mol%.
根據一個實施例，所述聚醯亞胺前驅物組成物中含有的所述聚醯胺酸可包括以下化學式5的重覆結構：
在化學式5中，每個Z獨立地為選自-CONH-、-NHCO-、-C(=O)O-及-OC(=O)中的一者，R1、R2及R3各自獨立地選自：具有1至10個碳原子的經取代或未經取代的烷基、具有1至10個碳原子的鹵代烷基、具有1至10個碳原子的烯基及具有6至18個碳原子的芳基，n1、n2及n3各自獨立地為0至4的整數，且 m為1至3的整數。 In Chemical Formula 5, each Z is independently one selected from -CONH-, -NHCO-, -C(=O)O- and -OC(=O), and R 1 , R 2 and R 3 are each Independently selected from: substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, haloalkyl groups having 1 to 10 carbon atoms, alkenyl groups having 1 to 10 carbon atoms, and 6 to 18 carbon atoms For the aryl group of the carbon atom, n1, n2, and n3 are each independently an integer from 0 to 4, and m is an integer from 1 to 3.
為達成其他目的，提供了一種聚醯亞胺膜，所述聚醯亞胺膜包含聚醯亞胺前驅物組成物的固化產物。 In order to achieve other objectives, a polyimide film is provided. The polyimide film comprises a cured product of a polyimine precursor composition.
根據一個實施例，可藉由包括以下步驟的方法來製備聚醯亞胺膜：將聚醯亞胺前驅物組成物塗佈至載體基板上；以及加熱並固化所塗佈的所述聚醯亞胺前驅物組成物。 According to one embodiment, the polyimide film may be prepared by a method including the following steps: coating a polyimide precursor composition on a carrier substrate; and heating and curing the coated polyimide film Amine precursor composition.
根據一個實施例，所述聚醯亞胺膜在532奈米的波長下在面內方向上的折射率可為1.75或大於1.75。 According to an embodiment, the refractive index of the polyimide film in the in-plane direction at a wavelength of 532 nm may be 1.75 or greater than 1.75.
根據一個實施例，聚醯亞胺膜可具有540℃或大於540℃的Td_1%、以及-50ppm/℃至50ppm/℃的熱膨脹係數(coefficient of thermal expansion，CTE)。 According to one embodiment, the polyimide film may have a Td_1% of 540°C or greater, and a coefficient of thermal expansion (CTE) of -50 ppm/°C to 50 ppm/°C.
根據又一實施例，提供了一種用於顯示器元件的基板，所述基板包括聚醯亞胺膜。 According to yet another embodiment, there is provided a substrate for a display element, the substrate including a polyimide film.
根據再一實施例，提供了一種包括聚醯亞胺膜的光學元件。 According to yet another embodiment, an optical element including a polyimide film is provided.
根據本揭露，可自聚醯亞胺前驅物組成物提供一種具有改善的耐熱性及折射率的聚醯亞胺膜，所述聚醯亞胺前驅物組成物包含化學式1的二胺及化學式2的酸二酐作為聚合組分，藉此可減小與上層的折射率的差異，並且可改善底部發射效率。 According to the present disclosure, a polyimide film with improved heat resistance and refractive index can be provided from the polyimide precursor composition. The polyimide precursor composition includes the diamine of Chemical Formula 1 and Chemical Formula 2 The acid dianhydride is used as the polymerization component, thereby reducing the difference in refractive index from the upper layer and improving the bottom emission efficiency.
由於可對本揭露進行各種修改及改變，因此在圖式中示出了具體實施例，並且將在詳細說明中詳細描述。然而，應理解，本發明並不旨在僅限於特定實施例，而是包括落入本發明的精神及範圍內的所有修改、等效形式及替代形式。在本揭露的以下說明中，若確定對已知功能的詳細說明可能使本發明的標的物模糊不清，則將省略對所述已知功能的詳細說明。 Since various modifications and changes can be made to the present disclosure, specific embodiments are shown in the drawings and will be described in detail in the detailed description. However, it should be understood that the present invention is not intended to be limited to specific embodiments, but includes all modifications, equivalent forms, and alternative forms that fall within the spirit and scope of the present invention. In the following description of the present disclosure, if it is determined that the detailed description of the known function may obscure the subject matter of the present invention, the detailed description of the known function will be omitted.
在本揭露中，除非另有說明，否則所有化合物或有機基可經取代或未經取代。本文中，術語「經取代」意指化合物或有機基中含有的至少一個氫被選自由以下組成的群組中的取代基取代：鹵素原子、具有1至10個碳原子的烷基、鹵代烷基、具有3至30個碳原子的環烷基、具有6至30個碳原子的芳基、羥基、具有1至10個碳原子的烷氧基、羧基、醛基、環氧基、氰基、硝基、胺基、磺酸基或其衍生物。 In this disclosure, unless otherwise specified, all compounds or organic groups may be substituted or unsubstituted. Herein, the term "substituted" means that at least one hydrogen contained in a compound or an organic group is substituted with a substituent selected from the group consisting of halogen atoms, alkyl groups having 1 to 10 carbon atoms, halogenated alkyl groups , Cycloalkyl groups having 3 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms, carboxyl groups, aldehyde groups, epoxy groups, cyano groups, Nitro, amine, sulfonic acid or derivatives thereof.
在包括聚醯亞胺膜作為基板層的柔性顯示器中，在製造元件或發光元件時，藉由在固化的聚醯亞胺膜上形成由多層無機膜(例如，緩衝層、主動層及閘極絕緣體)製成的膜來製造TFT元件。 In a flexible display that includes a polyimide film as a substrate layer, when manufacturing devices or light-emitting elements, a multilayer inorganic film (for example, buffer layer, active layer, and gate electrode) is formed on the cured polyimide film. Insulator) to produce a TFT element.
一般而言，在高度透明的聚醯亞胺膜的情形中，折射率為 n=1.65或小於1.65，但當光發射至聚醯亞胺層時，由於包括無機膜的上層的折射率(n=1.8或大於1.8)與聚醯亞胺層的折射率之間的差異，發射效率可被降低。 Generally speaking, in the case of a highly transparent polyimide film, the refractive index is n=1.65 or less than 1.65, but when light is emitted to the polyimide layer, due to the difference between the refractive index of the upper layer including the inorganic film (n=1.8 or more than 1.8) and the refractive index of the polyimide layer, The emission efficiency can be reduced.
因此，為提高自柔性顯示器元件至基板層的底部發射效率，需要一種元件配置，所述元件配置藉由減小所配置的各個層之間的折射率的差異來減少內部耗散的光的量。 Therefore, in order to improve the emission efficiency from the flexible display element to the bottom of the substrate layer, a device configuration is required that reduces the amount of internally dissipated light by reducing the difference in refractive index between the various layers of the configuration. .
為解決如上所述的先前技術的問題，本揭露的一個實施例提供一種聚醯亞胺前驅物組成物，所述聚醯亞胺前驅物組成物包含以下作為聚合組分：一或多種二胺，包括以下化學式1的二胺；以及一或多種酸二酐，包括以下化學式2的四羧酸二酐。 In order to solve the above-mentioned problems of the prior art, one embodiment of the present disclosure provides a polyimide precursor composition, the polyimine precursor composition includes the following as polymerization components: one or more diamines , Including the diamine of the following chemical formula 1; and one or more acid dianhydrides, including the tetracarboxylic dianhydride of the following chemical formula 2.
在化學式1中，含氟(F)的取代基可減少聚醯亞胺結構中或鏈之間的堆積(packing)，並且由於空間位阻(steric hindrance)及電性效應而減弱產色(chromogenic)及電***互作用，且因此在可見光區域中表現出高透明度。 In Chemical Formula 1, fluorine (F)-containing substituents can reduce the packing in the polyimide structure or between chains, and reduce chromogenicity due to steric hindrance and electrical effects. ) And electrical interaction, and therefore exhibit high transparency in the visible light region.
根據一個實施例，相對於聚合組分中所有二胺的總含量，化學式1的二胺的含量可為70莫耳%或大於70莫耳%、或80莫耳%或大於80莫耳%、或90莫耳%或大於90莫耳%。 According to one embodiment, relative to the total content of all diamines in the polymerization component, the content of the diamine of Chemical Formula 1 may be 70 mol% or more than 70 mol%, or 80 mol% or more than 80 mol%, Or 90 mol% or greater than 90 mol%.
根據一個實施例，相對於聚合組分中所有酸二酐的總含量，化學式2的酸二酐的含量可為70莫耳%或大於70莫耳%、或80莫耳%或大於80莫耳%、或90莫耳%或大於90莫耳%。 According to one embodiment, relative to the total content of all acid dianhydrides in the polymerization component, the content of the acid dianhydride of Chemical Formula 2 may be 70 mol% or more than 70 mol%, or 80 mol% or more than 80 mol% %, or 90 mol% or greater than 90 mol%.
作為另一選擇，聚醯亞胺前驅物可以相對於聚醯胺酸的整個重覆結構為70莫耳%或大於70莫耳%、或80莫耳%或大於80莫耳%的量包括化學式3的重覆結構，所述化學式3的重覆結構在聚醯胺酸的重覆結構中由化學式1的二胺及化學式2的酸酐形成。 Alternatively, the polyimide precursor may be 70 mol% or more than 70 mol%, or 80 mol% or more than 80 mol% relative to the entire repeating structure of the polyimide acid, including the chemical formula The repeating structure of Chemical Formula 3 is formed by the diamine of Chemical Formula 1 and the acid anhydride of Chemical Formula 2 in the repeating structure of polyamide acid.
此外，藉由使用化學式2的酸二酐與化學式1的二胺一起作為聚合組分，可獲得包括剛性重覆結構的聚醯亞胺結構。由此，藉由改善及誘發聚醯亞胺分子之間的取向及排序，可改善面內方向及厚度方向上的折射率。 In addition, by using the acid dianhydride of Chemical Formula 2 together with the diamine of Chemical Formula 1 as a polymerization component, a polyimide structure including a rigid repeating structure can be obtained. Thus, by improving and inducing the orientation and ordering between polyimide molecules, the refractive index in the in-plane direction and the thickness direction can be improved.
在由根據本揭露的聚醯亞胺前驅物組成物製備的聚醯亞胺中，相較於未添加包含單分子化合物的有機填料的聚醯亞胺，折射率可增加約0.01至0.1。作為另一選擇，折射率可提高0.01至0.05。 In the polyimide prepared from the polyimide precursor composition according to the present disclosure, the refractive index can be increased by about 0.01 to 0.1 compared to the polyimide without adding an organic filler containing a monomolecular compound. Alternatively, the refractive index can be increased by 0.01 to 0.05.
根據本揭露的聚醯亞胺前驅物可更包含具有化學式4的結構的二胺作為聚合組分。 The polyimide precursor according to the present disclosure may further include a diamine having the structure of Chemical Formula 4 as a polymerization component.
在化學式4中，每個Z獨立地為選自-CONH-、-NHCO-、-C(=O)O-及-OC(=O)中的一者，R1、R2及R3各自獨立地選自：具有1至10個碳原子的經取代或未經取代的烷基、具有1至10個碳原子的鹵代烷基、具有1至10個碳原子的烯基及具有6至18個碳原子的芳基， n1、n2及n3各自獨立地為0至4的整數，且m為1至3的整數。 In Chemical Formula 4, each Z is independently one selected from -CONH-, -NHCO-, -C(=O)O-, and -OC(=O), and R 1 , R 2 and R 3 are each Independently selected from: substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, haloalkyl groups having 1 to 10 carbon atoms, alkenyl groups having 1 to 10 carbon atoms, and 6 to 18 carbon atoms The aryl group of the carbon atom, n1, n2, and n3 are each independently an integer from 0 to 4, and m is an integer from 1 to 3.
根據一個實施例，相對於二胺的總含量，化學式4的二胺的含量可大於0且為30莫耳%或小於30莫耳%、20莫耳%或小於20莫耳%、或10莫耳%或小於10莫耳%。 According to one embodiment, relative to the total content of diamine, the content of the diamine of Chemical Formula 4 may be greater than 0 and 30 mol% or less than 30 mol%, 20 mol% or less than 20 mol%, or 10 mol%. Ear% or less than 10 mol%.
作為另一選擇，聚醯亞胺前驅物可以相對於聚醯胺酸的總重覆結構為大於0且為30莫耳%或小於30莫耳%、或20莫耳%或小於20莫耳%、或10莫耳%或小於10莫耳%的量在聚醯胺酸的重覆結構中包含化學式5的重覆結構。 As another option, the polyimide precursor may be greater than 0 and 30 mol% or less than 30 mol%, or 20 mol% or less than 20 mol% relative to the total repeating structure of the polyimide acid. , Or 10 mol% or an amount less than 10 mol% includes the repeating structure of Chemical Formula 5 in the repeating structure of polyamide acid.
其中，Z、R1、R2、R3、n1、n2及n3與化學式4中所定義的相同。 Among them, Z, R 1 , R 2 , R 3 , n1, n2 and n3 are the same as defined in Chemical Formula 4.
藉由使用具有化學式4以及化學式1的結構的二胺，本揭露可進一步改善聚醯亞胺膜的機械性質(模數及伸長率)、黏附性、折射率、特別是面內方向上的折射率。 By using the diamine with the structure of Chemical Formula 4 and Chemical Formula 1, the present disclosure can further improve the mechanical properties (modulus and elongation), adhesion, refractive index, especially refraction in the in-plane direction of the polyimide film rate.
除了化學式1的二胺及化學式2的酸二酐之外，根據本揭露的聚醯亞胺前驅物可更包含一或多種二胺及一或多種四羧酸二酐作為聚合組分。 In addition to the diamine of Chemical Formula 1 and the acid dianhydride of Chemical Formula 2, the polyimide precursor according to the present disclosure may further include one or more diamines and one or more tetracarboxylic dianhydrides as polymerization components.
四羧酸二酐是分子內芳族、脂環族或脂族四價有機基、或 其組合，其可為包括四價有機基的四羧酸二酐，其中脂族、脂環族或芳族四價有機基經由交聯結構彼此連接。作為另一選擇，可使用具有如下結構的酸二酐：單環或多環芳族結構、單環或多環脂環族結構、或其中前述結構中的二或更多者藉由單鍵或官能基連接的結構。作為另一選擇，其可選自具有剛性結構(例如，單獨的芳族、脂環族環結構、稠合的雜環結構或藉由單鍵連接的結構)的四價有機基。 Tetracarboxylic dianhydride is an intramolecular aromatic, alicyclic or aliphatic tetravalent organic group, or In combination, it may be a tetracarboxylic dianhydride including a tetravalent organic group, in which aliphatic, alicyclic or aromatic tetravalent organic groups are connected to each other via a crosslinking structure. Alternatively, an acid dianhydride having the following structure can be used: a monocyclic or polycyclic aromatic structure, a monocyclic or polycyclic alicyclic structure, or two or more of the foregoing structures by a single bond or The structure of the functional group connection. Alternatively, it may be selected from a tetravalent organic group having a rigid structure (for example, a separate aromatic, alicyclic ring structure, a fused heterocyclic structure, or a structure connected by a single bond).
舉例而言，四羧酸二酐可包括具有化學式6a至化學式6e的結構的四價有機基：
[化學式6c] [Chemical formula 6c]
在化學式6a至化學式6h中，R11至R24可各自獨立地選自： 選自-F、-Cl、-Br及-I的鹵素原子、羥基(-OH)、硫醇基(-SH)、硝基(-NO2)、氰基、具有1至10個碳原子的烷基、具有1至4個碳原子的鹵代烷氧基、具有1至10個碳原子的鹵代烷基及具有6至20個碳原子的芳基，a1為0至2的整數，a2為0至4的整數，a3為0至8的整數，a4及a5各自獨立地為0至3的整數，a6及a9各自獨立地為0至3的整數，並且a7及a8可各自獨立地為0至7的整數，a10及a12各自獨立地為0至3的整數，a11為0至4的整數，a15及a16各自獨立地為0至4的整數，a17及a18各自獨立地為0至4的整數，a6、a9、a13、a14、a19及a20各自獨立地為0至3的整數，且n為1至3的整數，A11及A16可各自獨立地選自由單鍵、-O-、-CR'R"-、-C(=O)-、-C(=O)NH-、-S-、-SO2-、伸苯基及其組合組成的群組，其中R'及R"可各自獨立地選自由氫原子、具有1至10個碳原子的烷基及具有1至10個碳原子的氟烷基組成的群組。 In Chemical Formula 6a to Chemical Formula 6h, R 11 to R 24 may each be independently selected from: halogen atoms selected from -F, -Cl, -Br, and -I, hydroxyl group (-OH), thiol group (-SH) , Nitro (-NO 2 ), cyano, alkyl having 1 to 10 carbon atoms, haloalkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 10 carbon atoms, and having 6 to 20 A carbon atom aryl group, a1 is an integer from 0 to 2, a2 is an integer from 0 to 4, a3 is an integer from 0 to 8, a4 and a5 are each independently an integer from 0 to 3, and a6 and a9 are each independently Is an integer from 0 to 3, and a7 and a8 may each independently be an integer from 0 to 7, a10 and a12 are each independently an integer from 0 to 3, a11 is an integer from 0 to 4, and a15 and a16 are each independently An integer from 0 to 4, a17 and a18 are each independently an integer from 0 to 4, a6, a9, a13, a14, a19, and a20 are each independently an integer from 0 to 3, and n is an integer from 1 to 3, A 11 and A 16 can be independently selected from single bond, -O-, -CR'R"-, -C(=O)-, -C(=O)NH-, -S-, -SO 2 -, A group consisting of phenylene and a combination thereof, wherein R'and R" can be independently selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and fluoroalkyl groups having 1 to 10 carbon atoms. Group.
作為另一選擇，四羧酸二酐可包括選自由以下化學式7a至化學式7n組成的群組中的四價有機基。 Alternatively, the tetracarboxylic dianhydride may include a tetravalent organic group selected from the group consisting of the following Chemical Formula 7a to Chemical Formula 7n.
化學式7a至化學式7n的四價有機基中的至少一個氫原子可被選自以下的取代基取代：選自-F、-Cl、-Br及-I的鹵素原子、羥基(-OH)、硫醇基(-SH)、硝基(-NO2)、氰基、具有1至10個碳原子的烷基、具有1至4個碳原子的鹵代烷氧基、具有1至10個碳原子的鹵代烷基或具有6至20個碳原子的芳基。舉例而言，鹵素原子可為氟(-F)，鹵代烷基為含有氟原子的具有1至10個碳原子的氟烷基，並且可選自氟甲基、全氟乙基、三氟甲基等，烷基可選自甲基、乙基、丙基、異丙基、第三丁基、戊基、或己基，且芳基可選自苯基及萘基，或可為包括氟原子的取代基，例如氟原子及氟烷基。 At least one hydrogen atom in the tetravalent organic group of Chemical Formula 7a to Chemical Formula 7n may be substituted with a substituent selected from the group consisting of halogen atoms selected from -F, -Cl, -Br and -I, hydroxyl (-OH), sulfur Alcohol group (-SH), nitro group (-NO 2 ), cyano group, alkyl group having 1 to 10 carbon atoms, halogenated alkoxy group having 1 to 4 carbon atoms, halogenated alkyl group having 1 to 10 carbon atoms Group or aryl group having 6 to 20 carbon atoms. For example, the halogen atom may be fluorine (-F), and the haloalkyl group is a fluoroalkyl group having 1 to 10 carbon atoms containing a fluorine atom, and may be selected from fluoromethyl, perfluoroethyl, and trifluoromethyl Etc., the alkyl group may be selected from methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, or hexyl, and the aryl group may be selected from phenyl and naphthyl, or may include fluorine atoms Substituents include fluorine atom and fluoroalkyl group.
二胺可選自由以下組成的群組：具有6至24個碳原子的單環或多環芳族二價有機基、具有6至18個碳原子的單環或多環脂環族二價有機基、或含有其中前述兩種有機基中的二或更多者藉由單鍵或官能基連接的結構的二價有機基，或者例如芳族或脂環族化合物等環狀化合物可為選自具有剛性結構(例如，單個或稠合的雜環環結構、或藉由單鍵連接的結構)的二價有機基中的一者。 The diamine can be selected from the group consisting of: a monocyclic or polycyclic aromatic divalent organic group with 6 to 24 carbon atoms, a monocyclic or polycyclic alicyclic divalent organic group with 6 to 18 carbon atoms Group, or a divalent organic group containing a structure in which two or more of the foregoing two organic groups are connected by a single bond or a functional group, or a cyclic compound such as an aromatic or alicyclic compound may be selected from One of the divalent organic groups having a rigid structure (for example, a single or fused heterocyclic ring structure, or a structure connected by a single bond).
舉例而言，其可包括選自以下化學式8a至化學式8e的二價有機基。 For example, it may include a divalent organic group selected from the following Chemical Formula 8a to Chemical Formula 8e.
[化學式8c]
在化學式8a至化學式8e中，R31至R37可各自獨立地選自由以下組成的群組：選自-F、-Cl、-Br及-I的鹵素原子、羥基(-OH)、硫醇基(-SH)、硝基(-NO2)、 氰基、具有1至10個碳原子的烷基、具有1至4個碳原子的鹵代烷氧基、具有1至10個碳原子的鹵代烷基或具有6至20個碳原子的芳基， A21及A22可各自獨立地選自：單鍵、-O-、-CR'R"-(其中R'及R"可各自獨立地選自氫原子、具有1至10個碳原子的烷基(例如，甲基、乙基、丙基、異丙基、正丁基、第三丁基、戊基等)及具有1至10個碳原子的鹵代烷基(例如，選自三氟甲基等))、-C(=O)-、-C(=O)O-、-C(=O)NH-、-S-、-SO-、-SO2-、-O[CH2CH2O]y-(其中y為1至44的整數)、NH(C=O)NH-、-NH(C=O)O-、具有6至18個碳原子的單環或多環伸環烷基(例如，伸環己基等)、具有6至18個碳原子的單環或多環伸芳基(例如，伸苯基、萘基、伸芴基等)及其組合， b1為0至4的整數，b2為0至6的整數，b3為0至3的整數，b4及b5各自獨立地為0至4的整數，b7及b8各自獨立地為0至9的整數，並且b6及b9各自獨立地為0至3的整數。 In Chemical Formula 8a to Chemical Formula 8e, R 31 to R 37 may each independently be selected from the group consisting of halogen atoms selected from -F, -Cl, -Br and -I, hydroxyl (-OH), thiol Group (-SH), nitro group (-NO 2 ), cyano group, alkyl group having 1 to 10 carbon atoms, haloalkoxy group having 1 to 4 carbon atoms, haloalkyl group having 1 to 10 carbon atoms Or an aryl group having 6 to 20 carbon atoms, A 21 and A 22 can each be independently selected from: single bond, -O-, -CR'R"- (wherein R'and R" can be independently selected from Hydrogen atom, alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, n-butyl, tertiary butyl, pentyl, etc.) and having 1 to 10 carbon atoms The halogenated alkyl group (for example, selected from trifluoromethyl, etc.)), -C(=O)-, -C(=O)O-, -C(=O)NH-, -S-, -SO-, -SO 2 -, -O[CH 2 CH 2 O] y- (where y is an integer from 1 to 44), NH(C=O)NH-, -NH(C=O)O-, with 6 to 18 A monocyclic or polycyclic cycloalkylene group having 6 to 18 carbon atoms (e.g., cyclohexylene, etc.), a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms (e.g., phenylene, naphthyl, fluorene Base, etc.) and combinations thereof, b1 is an integer from 0 to 4, b2 is an integer from 0 to 6, b3 is an integer from 0 to 3, b4 and b5 are each independently an integer from 0 to 4, and b7 and b8 are each independently It is an integer from 0 to 9, and b6 and b9 are each independently an integer from 0 to 3.
作為另一選擇，二胺可包括選自由以下式9a至式9p組成的群組中的二價有機基。 Alternatively, the diamine may include a divalent organic group selected from the group consisting of the following formulas 9a to 9p.
化學式9a至化學式9p的二價有機基中的一或多個氫原子可被選自以下的取代基取代：選自-F、-Cl、-Br及-I的鹵素原子、羥基(-OH)、硫醇基(-SH)、硝基(-NO2)、氰基、具有1至10個碳原子的烷基、具有1至4個碳原子的鹵代烷氧基、具有1至10個碳原子的鹵代烷基及具有6至20個碳原子的芳基。舉例而言，鹵素原子可為氟(-F)，鹵代烷基為含有氟原子的具有1至10個碳原子的氟烷基，並且可選自氟甲基、全氟乙基、三氟甲基，烷基可選自甲基、乙基、丙基、異丙基、第三丁基、戊基、己基，且芳基可選自苯基及萘基，或可為包括氟原子的取代基，例如氟原子及氟烷基。 One or more hydrogen atoms in the divalent organic groups of Chemical Formula 9a to Chemical Formula 9p may be substituted by a substituent selected from the group consisting of halogen atoms selected from -F, -Cl, -Br and -I, and hydroxyl (-OH) , Thiol group (-SH), nitro group (-NO 2 ), cyano group, alkyl group having 1 to 10 carbon atoms, halogenated alkoxy group having 1 to 4 carbon atoms, having 1 to 10 carbon atoms The halogenated alkyl group and the aryl group having 6 to 20 carbon atoms. For example, the halogen atom may be fluorine (-F), and the haloalkyl group is a fluoroalkyl group having 1 to 10 carbon atoms containing a fluorine atom, and may be selected from fluoromethyl, perfluoroethyl, and trifluoromethyl , The alkyl group may be selected from methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, and the aryl group may be selected from phenyl and naphthyl, or may be a substituent including a fluorine atom , Such as fluorine atom and fluoroalkyl group.
根據本揭露的一個實施例，四羧酸二酐的總含量及二胺的含量可以1：1.1至1.1：1的莫耳比反應，或者為改善反應性及可 加工性，較佳的是四羧酸二酐的總含量相對於二胺過量反應，或二胺的含量相對於四羧酸二酐的總含量過量反應。 According to an embodiment of the present disclosure, the total content of tetracarboxylic dianhydride and the content of diamine can be reacted at a molar ratio of 1:1.1 to 1.1:1, or to improve reactivity and performance. For processability, it is preferable that the total content of tetracarboxylic dianhydride is reacted in excess relative to the diamine, or the content of diamine is reacted excessively relative to the total content of tetracarboxylic dianhydride.
根據本揭露的一個實施例，較佳的是四羧酸二酐的總含量與二胺的含量之間的莫耳比可為1：0.98至0.98：1或1：0.99至0.99：1。 According to an embodiment of the present disclosure, preferably, the molar ratio between the total content of tetracarboxylic dianhydride and the content of diamine may be 1:0.98 to 0.98:1 or 1:0.99 to 0.99:1.
可用於聚醯胺酸的聚合反應的有機溶劑包括：酮，例如γ-丁內酯、1,3-二甲基-2-咪唑啶酮、甲基乙基酮、環己酮、環戊酮或4-羥基-4-甲基-2-戊酮；芳族烴，例如甲苯、二甲苯或四甲基苯；二醇醚(溶纖劑)，例如乙二醇單***、乙二醇單甲醚、乙二醇單丁醚、二乙二醇單***、二乙二醇單甲醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、二丙二醇二***或三乙二醇單***；乙酸乙酯、乙酸丁酯、乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單***乙酸酯、二丙二醇單甲醚乙酸酯、乙醇、丙醇、乙二醇、丙二醇、卡必醇、二甲基丙醯胺(dimethylpropionamide，DMPA)、二乙基丙醯胺(diethylpropionamide，DEPA)、二甲基乙醯胺(dimethylacetamide，DMAc)、N,N-二乙基乙醯胺、二甲基甲醯胺(dimethylformamide，DMF)、二乙基甲醯胺(diethylformamide，DEF)、N-甲基吡咯啶酮(N-methylpyrrolidone，NMP)、N-乙基吡咯啶酮(N-ethylpyrrolidone，NEP)、N,N-二甲基甲氧基乙醯胺、二甲亞碸、吡啶、二甲基碸、六甲基磷醯胺、四甲基脲、N-甲基己內醯胺、四氫呋喃、間二噁烷(m-dioxane)、對二噁烷(p-dioxane)、1,2-二甲氧基乙烷、雙(2-甲氧基乙基)醚、1,2-雙(2-甲氧基乙氧基) 乙烷、雙[2-(2-甲氧基乙氧基)]醚、依庫艾馬德(Equamide)M100、Equamide B100等，且在該些溶劑中，可單獨使用一種類型或使用二或更多種類型的混合物。 Organic solvents that can be used for the polymerization of polyamide include: ketones, such as γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, and cyclopentanone Or 4-hydroxy-4-methyl-2-pentanone; aromatic hydrocarbons, such as toluene, xylene or tetramethylbenzene; glycol ethers (cellosolves), such as ethylene glycol monoethyl ether, ethylene glycol mono Methyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether or triethylene two Alcohol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, Ethanol, propanol, ethylene glycol, propylene glycol, carbitol, dimethylpropionamide (DMPA), diethylpropionamide (DEPA), dimethylacetamide (DMAc) , N,N-Diethylacetamide, dimethylformamide (DMF), diethylformamide (DEF), N-methylpyrrolidone (N-methylpyrrolidone, NMP) , N-ethylpyrrolidone (N-ethylpyrrolidone, NEP), N,N-dimethylmethoxyacetamide, dimethyl sulfide, pyridine, dimethyl sulfide, hexamethylphosphamide, four Methylurea, N-methylcaprolactam, tetrahydrofuran, m-dioxane, p-dioxane, 1,2-dimethoxyethane, bis(2- Methoxyethyl) ether, 1,2-bis(2-methoxyethoxy) Ethane, bis[2-(2-methoxyethoxy)]ether, Equamide M100, Equamide B100, etc., and among these solvents, one type can be used alone or two or More types of mixtures.
舉例而言，可用於二胺及酸二酐的聚合反應的有機溶劑可包括在25℃下具有正分佈係數(LogP值)的溶劑，並且有機溶劑可具有300℃或小於300℃的沸點。更具體而言，分佈係數LogP值可為0.01至3、或0.01至2、或0.1至2。 For example, the organic solvent that can be used for the polymerization reaction of diamine and acid dianhydride may include a solvent having a positive distribution coefficient (LogP value) at 25°C, and the organic solvent may have a boiling point of 300°C or less. More specifically, the distribution coefficient LogP value may be 0.01 to 3, or 0.01 to 2, or 0.1 to 2.
可使用來自ACD/實驗室(Labs)的ACD/坡塞塔(Percepta)平台的ACD/LogP模組來計算分佈係數。ACD/LogP模組使用基於使用2D分子結構的定量結構-性質關係(Quantitative Structure-Property Relationship，QSPR)方法學的演算法。 The ACD/LogP module from the ACD/Percepta platform of ACD/Labs can be used to calculate the distribution coefficient. The ACD/LogP module uses an algorithm based on the Quantitative Structure-Property Relationship (QSPR) methodology using 2D molecular structures.
具有正分佈係數(LogP)的溶劑可為醯胺系溶劑。醯胺系溶劑可為選自由二甲基丙醯胺(DMPA)、二乙基丙醯胺(DEPA)、N,N-二乙基乙醯胺(N,N-diethylacetamide，DEAc)、N,N-二乙基甲醯胺(DEF)及N-乙基吡咯啶酮(NEP)組成的群組中的至少一者。 The solvent having a positive distribution coefficient (LogP) may be an amide-based solvent. The amide-based solvent can be selected from dimethyl propylene amine (DMPA), diethyl propylene amine (DEPA), N, N-diethyl acetamide (N, N-diethylacetamide, DEAc), N, At least one of the group consisting of N-diethylformamide (DEF) and N-ethylpyrrolidone (NEP).
可根據用於製備聚醯亞胺前驅物的傳統方法(例如，溶液聚合)來執行用於使四羧酸二酐與二胺反應的方法。具體而言，所述前驅物可藉由將二胺溶解於有機溶劑中、且然後將四羧酸二酐添加至所得混合溶液中以引起聚合反應來製備。 The method for reacting tetracarboxylic dianhydride and diamine can be performed according to a conventional method (for example, solution polymerization) for preparing a polyimide precursor. Specifically, the precursor may be prepared by dissolving diamine in an organic solvent, and then adding tetracarboxylic dianhydride to the resulting mixed solution to cause a polymerization reaction.
聚合反應可在惰性氣體或氮氣流下執行，並且可在無水條件下進行。 The polymerization reaction can be performed under an inert gas or nitrogen flow, and can be performed under anhydrous conditions.
此外，在聚合反應時的反應溫度可為-20℃至80℃、或 0℃至80℃。若反應溫度太高，則反應性可能增加，分子量可能增加，並且前驅物組成物的黏度增加，此在製程方面可能是不利的。 In addition, the reaction temperature during the polymerization reaction may be -20°C to 80°C, or 0°C to 80°C. If the reaction temperature is too high, the reactivity may increase, the molecular weight may increase, and the viscosity of the precursor composition increases, which may be disadvantageous in terms of manufacturing process.
較佳的是，根據上述製備方法製備的聚醯胺酸溶液以考慮到在成膜製程期間的可加工性(例如，塗佈性質)使組成物具有適當黏度的量包含固體。 Preferably, the polyamide acid solution prepared according to the above-mentioned preparation method contains solids in an amount that allows the composition to have an appropriate viscosity in consideration of processability (for example, coating properties) during the film-forming process.
含有聚醯胺酸的聚醯亞胺前驅物組成物可呈溶解在有機溶劑中的溶液的形式。在具有此種形式的情形中，舉例而言，當在有機溶劑中合成聚醯亞胺前驅物時，溶液可為由此獲得的反應溶液本身或藉由用另一種溶劑稀釋反應溶液而獲得的溶液。此外，當聚醯亞胺前驅物作為粉末被獲得時，溶液可為藉由將粉末溶解在有機溶劑中獲得的溶液。舉例而言，在聚合反應中，可使用具有正LogP的有機溶劑，並且可使用具有負LogP的有機溶劑作為稍後將被混合的有機溶劑。 The polyimide precursor composition containing polyamide acid may be in the form of a solution dissolved in an organic solvent. In the case of such a form, for example, when the polyimide precursor is synthesized in an organic solvent, the solution may be the reaction solution thus obtained by itself or by diluting the reaction solution with another solvent. Solution. In addition, when the polyimide precursor is obtained as a powder, the solution may be a solution obtained by dissolving the powder in an organic solvent. For example, in the polymerization reaction, an organic solvent having a positive LogP may be used, and an organic solvent having a negative LogP may be used as an organic solvent to be mixed later.
根據一個實施例，可調節組成物的含量，使得聚醯亞胺前驅物的總含量為8重量%至25重量%，或者所述含量可被調節至10重量%至25重量%、或10重量%至25重量%或小於25重量%。 According to an embodiment, the content of the composition can be adjusted so that the total content of the polyimide precursor is 8% to 25% by weight, or the content can be adjusted to 10% to 25% by weight, or 10% by weight % To 25% by weight or less than 25% by weight.
作為另一選擇，聚醯亞胺前驅物組成物可被調節至具有3,000厘泊(cP)或大於3,000厘泊、或4,000厘泊或大於4,000厘泊的黏度。聚醯亞胺前驅物組成物的黏度為10,000厘泊或小於10,000厘泊、或9,000厘泊或小於9,000厘泊、或8,000厘泊或小於8,000厘泊。當聚醯亞胺前驅物組成物的黏度超過10,000厘泊 時，在處理聚醯亞胺膜期間的消泡效率降低。此不僅導致製程效率的降低，而且還由於氣泡產生而導致所生產的膜的表面粗糙度劣化。此可能導致電性性質、光學性質及機械性質的劣化。 Alternatively, the polyimide precursor composition can be adjusted to have a viscosity of 3,000 centipoise (cP) or greater than 3,000 centipoise, or 4,000 centipoise or greater than 4,000 centipoise. The viscosity of the polyimide precursor composition is 10,000 centipoise or less than 10,000 centipoise, or 9,000 centipoise or less than 9,000 centipoise, or 8,000 centipoise or less than 8,000 centipoise. When the viscosity of the polyimide precursor composition exceeds 10,000 centipoise When the polyimide film is processed, the defoaming efficiency is reduced. This not only leads to a reduction in process efficiency, but also deteriorates the surface roughness of the produced film due to the generation of bubbles. This may cause deterioration of electrical, optical, and mechanical properties.
此外，根據本揭露的聚醯亞胺可具有10,000克/莫耳至200,000克/莫耳、或20,000克/莫耳至100,000克/莫耳、或30,000克/莫耳至100,000克/莫耳的重量平均分子量。 In addition, the polyimide according to the present disclosure may have an amount of 10,000 g/mole to 200,000 g/mole, or 20,000 g/mole to 100,000 g/mole, or 30,000 g/mole to 100,000 g/mole. Weight average molecular weight.
此外，根據本揭露的聚醯亞胺的分子量分佈(Mw/Mn)較佳為1.1至2.5。當聚醯亞胺的重量平均分子量或分子量分佈超出上述範圍時，可能難以形成膜，或者聚醯亞胺膜的性質(例如，透射率、耐熱性及機械性質)可能劣化。 In addition, the molecular weight distribution (Mw/Mn) of the polyimide according to the present disclosure is preferably 1.1 to 2.5. When the weight average molecular weight or molecular weight distribution of the polyimide exceeds the above range, it may be difficult to form a film, or the properties of the polyimide film (for example, transmittance, heat resistance, and mechanical properties) may be deteriorated.
接下來，可將由於聚合反應而獲得的聚醯亞胺前驅物醯亞胺化以製備透明聚醯亞胺膜。 Next, the polyimide precursor obtained as a result of the polymerization reaction may be imidized to prepare a transparent polyimide film.
根據一個實施例，可藉由包括以下步驟的方法製備如上獲得的聚醯亞胺膜組成物：將聚醯亞胺膜組成物塗佈至基板上；以及加熱並固化所塗佈的聚醯亞胺膜組成物。 According to one embodiment, the polyimide film composition obtained as above may be prepared by a method including the following steps: coating the polyimide film composition on a substrate; and heating and curing the coated polyimide film composition Amine membrane composition.
此時，可使用玻璃、金屬基板或塑膠基板作為基板，對此並無特別限制。在所述基板中，在聚醯亞胺前驅物的醯亞胺化及固化製程期間具有優異的熱穩定性及化學穩定性、並且即使在無單獨的離型劑處理的情況下亦可容易地分離而不損害固化後形成的聚醯亞胺膜的玻璃基板可為較佳的。 At this time, glass, metal substrate or plastic substrate can be used as the substrate, and there is no particular limitation on this. In the substrate, it has excellent thermal and chemical stability during the imidization and curing process of the polyimide precursor, and it can be easily processed even without a separate release agent. It may be preferable to separate the glass substrate without damaging the polyimide film formed after curing.
此外，可根據傳統的塗佈方法執行塗佈步驟。旋塗方法的 具體實例可包括棒塗法(bar coating method)、輥塗法(roll coating method)、氣刀法(air-knife method)、凹版印刷法(gravure method)、反輥法(reverse roll method)、濕輥法(kiss roll method)、刮刀法(doctor blade method)、噴塗法(spray method)、浸漬法(dipping method)、刷塗法(brushing method)等。在該些方法中，更可取的是藉由澆鑄法(casting method)進行所述製程，所述澆鑄法不僅能夠實現連續的製程，而且能夠增加聚醯亞胺的醯亞胺化速率。 In addition, the coating step can be performed according to a conventional coating method. Spin coating method Specific examples may include bar coating method, roll coating method, air-knife method, gravure method, reverse roll method, wet Kiss roll method, doctor blade method, spray method, dipping method, brushing method, etc. Among these methods, it is more preferable to perform the process by a casting method, which can not only realize a continuous process, but also increase the imidization rate of the polyimide.
此外，聚醯亞胺前驅物組成物可以使得最終生產的聚醯亞胺膜具有適於顯示器基板的厚度的厚度範圍塗佈至基板上。 In addition, the polyimide precursor composition can make the final produced polyimide film having a thickness range suitable for the thickness of the display substrate to be coated on the substrate.
具體而言，可以使得具有10微米至30微米的厚度的量塗佈所述組成物。在塗佈聚醯亞胺前驅物組成物之後，必要時可在固化步驟之前進一步執行用於移除聚醯亞胺前驅物組成物中存在的溶劑的乾燥步驟。 Specifically, the composition may be coated in an amount having a thickness of 10 μm to 30 μm. After coating the polyimide precursor composition, if necessary, a drying step for removing the solvent present in the polyimine precursor composition may be further performed before the curing step.
可根據傳統方法執行所述乾燥步驟，且具體而言，可在140℃或小於140℃、或80℃至140℃的溫度下執行所述乾燥步驟。當乾燥步驟的溫度低於80℃時，乾燥步驟將變得更長，而當所述溫度超過140℃時，醯亞胺化快速進行，並且難以形成具有均勻厚度的聚醯亞胺膜。 The drying step may be performed according to a conventional method, and specifically, the drying step may be performed at a temperature of 140°C or less, or 80°C to 140°C. When the temperature of the drying step is lower than 80°C, the drying step becomes longer, and when the temperature exceeds 140°C, the imidization proceeds rapidly, and it is difficult to form a polyimide film having a uniform thickness.
接著，將聚醯亞胺前驅物組成物塗佈至基板上，並在紅外線(infrared radiation，IR)烘箱、熱空氣烘箱或熱板上進行熱處理。此時，熱處理溫度可在280℃至500℃、或300℃至450℃的溫度範圍中，並且可在上述溫度範圍內分多個階段執行熱處理。熱 處理步驟可執行20分鐘至70分鐘，或者可執行約20分鐘至60分鐘。 Then, the polyimide precursor composition is coated on the substrate and heat-treated in an infrared radiation (IR) oven, a hot air oven or a hot plate. At this time, the heat treatment temperature may be in a temperature range of 280°C to 500°C, or 300°C to 450°C, and the heat treatment may be performed in multiple stages within the above temperature range. heat The processing step may be performed for 20 minutes to 70 minutes, or may be performed for about 20 minutes to 60 minutes.
此後，可藉由根據傳統方法將形成於基板上的聚醯亞胺膜自基板剝離來生產聚醯亞胺膜。 Thereafter, the polyimide film can be produced by peeling the polyimide film formed on the substrate from the substrate according to a conventional method.
亦即，聚醯亞胺膜可包括聚醯亞胺前驅物組成物的固化產物。固化產物意指藉由聚醯亞胺前驅物組成物的固化步驟獲得的材料，並且固化步驟可在200℃或大於200℃、或200℃或大於200℃及350℃或小於350℃的溫度下執行。因此，聚醯亞胺膜可包括在200℃或大於200℃、或200℃或大於200℃及350℃或小於350℃的溫度下固化的聚醯亞胺前驅物組成物的固化產物。 That is, the polyimide film may include a cured product of the polyimide precursor composition. The cured product means the material obtained by the curing step of the polyimide precursor composition, and the curing step may be at a temperature of 200°C or more, or 200°C or more than 200°C and 350°C or less than 350°C carried out. Therefore, the polyimide film may include a cured product of the polyimide precursor composition cured at a temperature of 200°C or more, or 200°C or more than 200°C, and 350°C or less.
根據一個實施例，聚醯亞胺膜在532奈米的波長下在面內方向(TE)上的折射率可為1.75或大於1.75、或1.75或大於1.75及1.8或小於1.8。此外，聚醯亞胺膜在532奈米的波長下在厚度方向(TM)上的折射率可為1.5或大於1.5、或1.53或大於1.53、或1.5或大於1.5及1.6或小於1.6、或1.53或大於1.53及1.6或小於1.6。 According to one embodiment, the refractive index of the polyimide film in the in-plane direction (TE) at a wavelength of 532 nm may be 1.75 or greater than 1.75, or 1.75 or greater than 1.75 and 1.8 or less than 1.8. In addition, the refractive index of the polyimide film in the thickness direction (TM) at a wavelength of 532 nm can be 1.5 or more than 1.5, or 1.53 or more than 1.53, or 1.5 or more than 1.5 and 1.6 or less than 1.6, or 1.53 Or greater than 1.53 and 1.6 or less than 1.6.
量測折射率的方法的實例不受特別限制，但舉例而言，可使用稜鏡耦合器在532奈米的波長下量測折射率。 The example of the method of measuring the refractive index is not particularly limited, but for example, the refractive index can be measured at a wavelength of 532 nm using a stern coupler.
可自厚度為10±2微米的聚醯亞胺膜樣品量測折射率。當聚醯亞胺膜的厚度增大或減小一具體值時，在所述聚醯亞胺膜中量測的物理性質亦可改變某一值。 The refractive index can be measured from a polyimide film sample with a thickness of 10±2 microns. When the thickness of the polyimide film increases or decreases by a specific value, the physical properties measured in the polyimide film can also change a certain value.
因此，根據本揭露的聚醯亞胺膜可增加折射率，可用作柔 性顯示器元件中的基板層，並且可減少與構成元件的每個層的折射率的差異，藉此內部耗散的光的量減少並且底部發射的效率可被有效增加。 Therefore, the polyimide film according to the present disclosure can increase the refractive index and can be used as a flexible The substrate layer in the display element can reduce the difference in refractive index with each layer constituting the element, whereby the amount of internally dissipated light is reduced and the efficiency of bottom emission can be effectively increased.
根據本揭露的聚醯亞胺膜的熱膨脹係數(CTE)可在100℃或大於100℃及350℃或小於350℃下量測，並且在上述範圍中量測的CTE可為-5ppm/℃或大於-5ppm/℃及+15ppm/℃或小於+15ppm/℃、或-5ppm/℃或大於-5ppm/℃及+5ppm/℃或小於+5ppm/℃。 The coefficient of thermal expansion (CTE) of the polyimide film according to the present disclosure can be measured at 100°C or greater and 350°C or less than 350°C, and the CTE measured in the above range can be -5ppm/°C or Greater than -5ppm/°C and +15ppm/°C or less than +15ppm/°C, or -5ppm/°C or greater than -5ppm/°C and +5ppm/°C or less than +5ppm/°C.
藉由以下方式獲得熱膨脹係數：在將拉動聚醯亞胺膜樣品的力設定為0.01牛(N)或大於0.01牛及0.1牛或小於0.1牛、或0.01牛或大於0.01牛及0.05牛或小於0.05牛時，使用TMA(Q400，TA儀器公司(TA Instruments))量測熱膨脹變化的態樣，在100℃或大於100℃及350℃或小於350℃的溫度範圍中以1℃/分鐘或大於1℃/分鐘及10℃/分鐘或小於10℃/分鐘、或4℃/分鐘或大於4℃/分鐘及6℃/分鐘或小於6℃/分鐘的加熱速率執行初級加熱步驟，且然後在350℃至100℃的溫度範圍中以1℃/分鐘或大於1℃/分鐘及10℃/分鐘或小於10℃/分鐘、或3℃/分鐘或大於3℃/分鐘及5℃/分鐘或小於5℃/分鐘的冷卻速率進行冷卻。 The coefficient of thermal expansion is obtained by the following method: When the force pulling the polyimide film sample is set to 0.01 N (N) or greater than 0.01 N and 0.1 N or less than 0.1 N, or 0.01 N or greater than 0.01 N and 0.05 N or less When 0.05 N, use TMA (Q400, TA Instruments) to measure the state of thermal expansion change, at 100 ℃ or more than 100 ℃ and 350 ℃ or less than 350 ℃ in the temperature range of 1 ℃ / min or more Perform the primary heating step at a heating rate of 1°C/min and 10°C/min or less than 10°C/min, or 4°C/min or greater than 4°C/min and 6°C/min or less than 6°C/min, and then at 350 In the temperature range of ℃ to 100℃, 1℃/min or more than 1℃/min and 10℃/min or less than 10℃/min, or 3℃/min or more than 3℃/min and 5℃/min or less than 5 Cooling is performed at a cooling rate of °C/min.
由於聚醯亞胺膜在100℃或大於100℃及350℃或小於350℃的範圍內的熱膨脹係數滿足上述範圍，因此即使在聚醯亞胺膜中其亦可確保足夠的耐熱性，並且在將此用作塑膠基板時，其可防止塑膠基板在對形成於塑膠基板上的金屬層進行熱處理時因熱 受損，並且亦可抑制形成於塑膠基板上的金屬薄膜發生翹曲。 Since the thermal expansion coefficient of the polyimide film in the range of 100°C or more and 350°C or less than 350°C satisfies the above range, it can ensure sufficient heat resistance even in the polyimide film, and When this is used as a plastic substrate, it can prevent the plastic substrate from being heated due to heat treatment of the metal layer formed on the plastic substrate. It is damaged, and can also suppress the warpage of the metal thin film formed on the plastic substrate.
可自厚度為10±2微米的聚醯亞胺膜樣品量測熱膨脹係數。當聚醯亞胺膜的厚度增大或減小一具體值時，自所述聚醯亞胺膜量測的物理性質亦可改變某一值。 The coefficient of thermal expansion can be measured from a polyimide film sample with a thickness of 10 ± 2 microns. When the thickness of the polyimide film increases or decreases by a specific value, the physical properties measured from the polyimide film may also change a certain value.
根據本揭露的聚醯亞胺膜的熱分解溫度(Td_1%)可為539℃或大於539℃、或539℃或大於539℃及545℃或小於545℃。量測熱分解溫度(Td_1%)的方法的實例不受特別限制，但舉例而言，可使用熱重量分析法(thermogravimetry，TGA)在氮氣氣氛中量測所述熱分解溫度。可自厚度為10±2微米的聚醯亞胺膜樣品量測熱分解溫度。當聚醯亞胺膜的厚度增大或減小一具體值時，在所述聚醯亞胺膜中量測的物理性質亦可改變某一值。 The thermal decomposition temperature (Td_1%) of the polyimide film according to the present disclosure may be 539°C or greater than 539°C, or 539°C or greater than 539°C and 545°C or less than 545°C. Examples of methods for measuring the thermal decomposition temperature (Td_1%) are not particularly limited, but for example, thermogravimetry (TGA) can be used to measure the thermal decomposition temperature in a nitrogen atmosphere. The thermal decomposition temperature can be measured from a polyimide film sample with a thickness of 10±2 microns. When the thickness of the polyimide film increases or decreases by a specific value, the physical properties measured in the polyimide film can also change a certain value.
因此，本揭露可使用化學式1的二胺提供具有顯著改善的耐熱性的聚醯亞胺膜。 Therefore, the present disclosure can use the diamine of Chemical Formula 1 to provide a polyimide film with significantly improved heat resistance.
基於JIS K 7105量測的聚醯亞胺膜在450奈米波長下的透射率可為75%或大於75%、或75%或大於75%及85%或小於85%。量測透射率的方法的實例不受特別限制，但舉例而言，可基於JIS K 7105使用透射率計(型號名稱：HR-100，由村上色彩研究實驗室(Murakami Color Research Laboratory)製造)量測在45奈米的波長範圍中的透射率。 The transmittance of the polyimide film measured based on JIS K 7105 at a wavelength of 450 nanometers can be 75% or more than 75%, or 75% or more than 75%, and 85% or less than 85%. Examples of the method of measuring transmittance are not particularly limited, but for example, a transmittance meter (model name: HR-100, manufactured by Murakami Color Research Laboratory) can be used based on JIS K 7105. Measure the transmittance in the 45nm wavelength range.
可自厚度為10±2微米的聚醯亞胺膜樣品量測透射率。當聚醯亞胺膜的厚度增大或減小一具體值時，在所述聚醯亞胺膜中量測的物理性質亦可改變某一值。 The transmittance can be measured from a polyimide film sample with a thickness of 10±2 microns. When the thickness of the polyimide film increases or decreases by a specific value, the physical properties measured in the polyimide film can also change a certain value.
同時，根據本揭露的另一實施例，可提供一種包括聚醯亞胺膜的用於顯示器元件的基板。聚醯亞胺膜的細節可包括以上在一個實施例中所述的所有內容。 At the same time, according to another embodiment of the present disclosure, a substrate for a display device including a polyimide film can be provided. The details of the polyimide film may include all the contents described above in one embodiment.
包括基板的顯示器元件可包括液晶顯示器元件(LCD)、有機發光二極體(OLED)、柔性顯示器、可捲曲顯示器或可折疊顯示器等。 The display element including the substrate may include a liquid crystal display element (LCD), an organic light emitting diode (OLED), a flexible display, a rollable display, a foldable display, and the like.
顯示器元件可根據應用領域及具體形狀具有各種結構，並且可具有包括例如覆蓋塑膠窗、觸控面板、偏振片、阻擋膜、發光元件(例如，OLED元件)、透明基板等的結構。 The display element may have various structures according to application fields and specific shapes, and may have structures including, for example, plastic covering windows, touch panels, polarizers, barrier films, light-emitting elements (for example, OLED elements), transparent substrates, and the like.
上述另一實施例的聚醯亞胺膜可用於各種應用(例如，在此類各種顯示器元件中的基板、外部保護膜或覆蓋窗)中，且更具體而言，可應用於基板。 The polyimide film of another embodiment described above can be used in various applications (for example, substrates, external protective films, or cover windows in such various display elements), and more specifically, can be applied to substrates.
舉例而言，用於顯示器元件的基板可具有其中依序堆疊元件保護層、透明電極層、氧化矽層、聚醯亞胺樹脂膜、氧化矽層及硬塗層的結構。 For example, a substrate used for a display device may have a structure in which a device protection layer, a transparent electrode layer, a silicon oxide layer, a polyimide resin film, a silicon oxide layer, and a hard coat layer are sequentially stacked.
透明聚醯亞胺基板可更包括在透明聚醯亞胺樹脂膜與固化層之間形成的氧化矽層，以進一步改善其耐溶劑性、透水性及光學性質，並且可藉由固化聚矽氮烷來製備氧化矽層。 The transparent polyimide substrate can further include a silicon oxide layer formed between the transparent polyimide resin film and the cured layer to further improve its solvent resistance, water permeability and optical properties, and can be cured by curing the polysiloxane Alkane to prepare the silicon oxide layer.
具體而言，可在透明聚醯亞胺樹脂膜的至少一個表面上形成塗層之前藉由在塗佈及乾燥含有聚矽氮烷的溶液之後固化所塗佈的聚矽氮烷來形成氧化矽層。 Specifically, the silicon oxide may be formed by curing the applied polysilazane after coating and drying a solution containing polysilazane before forming a coating on at least one surface of the transparent polyimide resin film. Floor.
根據本揭露的用於顯示器元件的基板可藉由包括上述元 件保護層而提供具有耐溶劑性、光學性質、透水性及耐刮擦性同時具有優異的翹曲性質及耐衝擊性的透明聚醯亞胺覆蓋基板。 The substrate for the display device according to the present disclosure can be provided by including the above-mentioned elements A protective layer to provide a transparent polyimide-covered substrate with solvent resistance, optical properties, water permeability, and scratch resistance, as well as excellent warpage properties and impact resistance.
同時，根據本揭露的另一實施例，可提供一種包括聚醯亞胺膜的光學元件。聚醯亞胺膜的細節可包括以上在一個實施例中所述的所有細節。 At the same time, according to another embodiment of the present disclosure, an optical element including a polyimide film can be provided. The details of the polyimide film may include all the details described above in one embodiment.
光學元件可包括使用由光達成的性質的所有類型的元件，並且可為例如顯示器元件。顯示器元件的具體實例包括液晶顯示器元件(LCD)、有機發光二極體(OLED)、柔性顯示器、可捲曲顯示器或可折疊顯示器等，但並非僅限於此。 The optical element may include all types of elements using properties achieved by light, and may be, for example, a display element. Specific examples of display elements include liquid crystal display elements (LCD), organic light emitting diodes (OLED), flexible displays, rollable displays or foldable displays, etc., but are not limited to these.
光學元件可根據應用領域及具體形狀具有各種結構，並且舉例而言，其可具有包括覆蓋塑膠窗、觸控面板、偏振片、阻擋膜、發光元件(例如OLED元件)、透明基板等的結構。 The optical element may have various structures according to application fields and specific shapes, and for example, it may have structures including covering plastic windows, touch panels, polarizers, barrier films, light-emitting elements (such as OLED elements), transparent substrates, and the like.
上述另一實施例的聚醯亞胺膜可用於各種應用(例如，在各種光學元件中的基板、外部保護膜或覆蓋窗)中，且更具體而言，可應用於基板。 The polyimide film of another embodiment described above can be used in various applications (for example, substrates, external protective films, or cover windows in various optical elements), and more specifically, can be applied to substrates.
將詳細闡述本揭露的實例，以使熟習此項技術者可容易地實施本揭露。本揭露可以各種不同的方式修改，且並非僅限於本文中闡述的實例。 Examples of the disclosure will be described in detail, so that those skilled in the art can easily implement the disclosure. The present disclosure can be modified in various different ways and is not limited to the examples set forth in this article.
<比較例1> <Comparative Example 1>
在氮氣流下將有機溶劑DEAc填充到了反應器中，且然後在將反應器溫度保持在25℃的同時添加了0.821莫耳的TFMB(2,2'-雙(三氟甲基)聯苯胺)並在相同的溫度下溶解。在相同的溫 度下將0.821莫耳的PMDA添加到了添加有TFMB的溶液中並攪拌了24小時，以獲得聚醯亞胺前驅物組成物。 The organic solvent DEAc was filled into the reactor under a nitrogen stream, and then 0.821 mol of TFMB (2,2'-bis(trifluoromethyl)benzidine) was added while maintaining the reactor temperature at 25°C. Dissolve at the same temperature. At the same temperature 0.821 mol of PMDA was added to the solution added with TFMB and stirred for 24 hours to obtain a polyimide precursor composition.
<比較例2> <Comparative Example 2>
在氮氣流下將有機溶劑DEAc填充到了反應器中，且然後在將反應器溫度保持在25℃的同時添加了0.902莫耳的TFMB(2,2'-雙(三氟甲基)聯苯胺)並在相同的溫度下溶解。在相同的溫度下將0.902莫耳的BPDA添加到了添加有TFMB的溶液中並攪拌了24小時，以獲得聚醯亞胺前驅物組成物。 The organic solvent DEAc was filled into the reactor under a nitrogen stream, and then 0.902 mol of TFMB (2,2'-bis(trifluoromethyl)benzidine) was added while maintaining the reactor temperature at 25°C. Dissolve at the same temperature. At the same temperature, 0.902 mol of BPDA was added to the TFMB-added solution and stirred for 24 hours to obtain a polyimide precursor composition.
<比較例3> <Comparative Example 3>
在氮氣流下將有機溶劑DEAc填充到了反應器中，且然後在將反應器溫度保持在25℃的同時添加了0.793莫耳的化學式1的二胺並在相同的溫度下溶解。在相同的溫度下將0.793莫耳的PMDA添加到了添加有化學式1的二胺的溶液中並攪拌了24小時，以獲得聚醯亞胺前驅物組成物。 The organic solvent DEAc was filled into the reactor under a nitrogen stream, and then 0.793 mol of the diamine of Chemical Formula 1 was added and dissolved at the same temperature while maintaining the reactor temperature at 25°C. 0.793 mol of PMDA was added to the solution to which the diamine of Chemical Formula 1 was added and stirred for 24 hours at the same temperature to obtain a polyimide precursor composition.
<比較例4> <Comparative Example 4>
在氮氣流下將有機溶劑DEAc填充到了反應器中，且然後在將反應器溫度保持在25℃的同時添加了0.3965莫耳的化學式1的二胺及0.3965莫耳的TFMB(2,2'-雙(三氟甲基)聯苯胺)並在相同的溫度下溶解。在相同的溫度下將0.6344莫耳的6-FDA及0.1586莫耳的PMDA添加到了添加有化學式1的二胺及TFMB的溶液中並攪拌了24小時，以獲得聚醯亞胺前驅物組成物。 The organic solvent DEAc was filled into the reactor under nitrogen flow, and then 0.3965 mol of the diamine of chemical formula 1 and 0.3965 mol of TFMB (2,2'-bis (Trifluoromethyl)benzidine) and dissolve at the same temperature. At the same temperature, 0.6344 mol of 6-FDA and 0.1586 mol of PMDA were added to the solution containing the diamine of chemical formula 1 and TFMB and stirred for 24 hours to obtain a polyimide precursor composition.
<實例1> <Example 1>
在氮氣流下將有機溶劑DEAc填充到了反應器中，且然後在將反應器溫度保持在25℃的同時添加了0.735莫耳的化學式1的二胺並在相同的溫度下溶解。在相同的溫度下將0.735莫耳的BPDA添加到了添加有化學式1的二胺的溶液中並攪拌了24小時，以獲得聚醯亞胺前驅物組成物。 The organic solvent DEAc was filled into the reactor under a nitrogen stream, and then 0.735 mol of the diamine of Chemical Formula 1 was added and dissolved at the same temperature while maintaining the reactor temperature at 25°C. At the same temperature, 0.735 mol of BPDA was added to the solution to which the diamine of Chemical Formula 1 was added and stirred for 24 hours to obtain a polyimide precursor composition.
<實例2> <Example 2>
在氮氣流下將有機溶劑DEAc填充到了反應器中，且然後在將反應器溫度保持在25℃的同時添加了0.668莫耳的化學式1的二胺及0.067莫耳的化學式4-1的二胺，並在相同的溫度下溶解。在相同的溫度下將0.735莫耳的BPDA添加到了添加有化學式1及化學式4-1的二胺的溶液中並攪拌了24小時，以獲得聚醯亞胺前驅物組成物。 The organic solvent DEAc was filled into the reactor under a nitrogen stream, and then 0.668 mol of the diamine of chemical formula 1 and 0.067 mol of the diamine of chemical formula 4-1 were added while maintaining the temperature of the reactor at 25°C, And dissolve at the same temperature. At the same temperature, 0.735 mol of BPDA was added to the solution added with the diamine of Chemical Formula 1 and Chemical Formula 4-1 and stirred for 24 hours to obtain a polyimide precursor composition.
<實例3> <Example 3>
在氮氣流下將有機溶劑DEAc填充到了反應器中，且然 後在將反應器溫度保持在25℃的同時添加了0.668莫耳的化學式1的二胺及0.067莫耳的化學式4-2的二胺，並在相同的溫度下溶解。在相同的溫度下將0.735莫耳的BPDA添加到了添加有化學式1及化學式4-2的二胺的溶液中並攪拌了24小時，以獲得聚醯亞胺前驅物組成物。 The organic solvent DEAc was filled into the reactor under nitrogen flow, and then Then, while keeping the reactor temperature at 25°C, 0.668 mol of the diamine of Chemical Formula 1 and 0.067 mol of the diamine of Chemical Formula 4-2 were added and dissolved at the same temperature. At the same temperature, 0.735 mol of BPDA was added to the solution added with the diamine of Chemical Formula 1 and Chemical Formula 4-2 and stirred for 24 hours to obtain a polyimide precursor composition.
<實例4> <Example 4>
在氮氣流下將有機溶劑DEAc填充到了反應器中，且然後在將反應器溫度保持在25℃的同時添加了0.668莫耳的化學式1的二胺及0.067莫耳的化學式4-3的二胺，並在相同的溫度下溶解。在相同的溫度下將0.735莫耳的BPDA添加到了添加有化學式1及化學式4-3的二胺的溶液中並攪拌了24小時，以獲得聚醯亞胺前驅物組成物。 The organic solvent DEAc was filled into the reactor under nitrogen flow, and then 0.668 mol of the diamine of chemical formula 1 and 0.067 mol of the diamine of chemical formula 4-3 were added while keeping the temperature of the reactor at 25°C, And dissolve at the same temperature. At the same temperature, 0.735 mol of BPDA was added to the solution added with the diamine of Chemical Formula 1 and Chemical Formula 4-3 and stirred for 24 hours to obtain a polyimide precursor composition.
[化學式4-3]
<實驗例1> <Experimental example 1>
將在實例1至實例4以及比較例1至比較例3中製備的聚醯亞胺前驅物組成物中的每一者旋塗在了玻璃基板上。將塗佈有聚醯亞胺前驅物組成物的玻璃基板放入烘箱中並以5℃/分鐘的速率加熱，並且藉由在80℃下保持30分鐘及在300℃下保持30分鐘而執行了固化製程，藉此製備聚醯亞胺膜。 Each of the polyimide precursor compositions prepared in Example 1 to Example 4 and Comparative Example 1 to Comparative Example 3 was spin-coated on a glass substrate. The glass substrate coated with the polyimide precursor composition was put into an oven and heated at a rate of 5°C/min, and performed by keeping it at 80°C for 30 minutes and 300°C for 30 minutes Curing process to prepare polyimide film.
量測了每個膜的物理性質並將所述性質示於下表1中。 The physical properties of each film were measured and the properties are shown in Table 1 below.
<量測透射率> <Measure transmittance>
基於JIS K 7105使用透射率計(型號名稱HR-100，村上色彩研究實驗室)量測了在450奈米波長下的透射率。 Based on JIS K 7105, a transmittance meter (model name HR-100, Murakami Color Research Laboratory) was used to measure the transmittance at a wavelength of 450 nm.
<量測折射率> <Measure Refractive Index>
剝離了所製備的聚醯亞胺膜，並且使用稜鏡耦合器在532奈米的波長下量測了折射率。 The prepared polyimide film was peeled off, and the refractive index was measured at a wavelength of 532 nanometers by using a coupler.
<熱解溫度(Td1%)> <Pyrolysis temperature (Td1%)>
使用TGA量測了聚合物在氮氣氣氛中的重量損失率為 1%時的溫度。 Using TGA to measure the weight loss rate of the polymer in a nitrogen atmosphere The temperature at 1%.
<熱膨脹係數(CTE)及玻璃轉變溫度(Tg)> <Coefficient of Thermal Expansion (CTE) and Glass Transition Temperature (Tg)>
製備了大小為5×20毫米的膜，且然後使用附件裝載了樣品。將要實際量測的膜的長度設定為等於16毫米。將拉動膜的力設定為0.02牛，在100℃或大於100℃及350℃或小於350℃的溫度範圍中以5℃/分鐘的加熱速率執行了初級加熱步驟，且然後在350℃至100℃的溫度範圍中以4℃/分鐘的冷卻速率執行了冷卻。使用TMA(Q400，TA儀器公司)量測了熱膨脹變化的態樣。 A membrane with a size of 5×20 mm was prepared, and then the sample was loaded using the accessory. The length of the film to be actually measured is set equal to 16 mm. The force of pulling the film was set to 0.02 N, the primary heating step was performed at a heating rate of 5°C/min in a temperature range of 100°C or more than 100°C and 350°C or less than 350°C, and then at 350°C to 100°C Cooling was performed at a cooling rate of 4°C/min in the temperature range of. TMA (Q400, TA Instruments) was used to measure the state of thermal expansion changes.
自表1中的結果可看出，根據本揭露的聚醯亞胺膜在面內方向上顯示出高折射率，並且相較於其他比較例的聚醯亞胺膜可顯著改善折射率。此外，根據本揭露的聚醯亞胺膜顯示出低的CTE值，此可意指由於加熱引起的膜的收縮行為或變化極小，由此可看出，根據本揭露的聚醯亞胺膜具有優異的耐熱性。 It can be seen from the results in Table 1 that the polyimide film according to the present disclosure shows a high refractive index in the in-plane direction, and can significantly improve the refractive index compared to the polyimide film of other comparative examples. In addition, the polyimide film according to the present disclosure shows a low CTE value, which may mean that the shrinkage behavior or change of the film caused by heating is minimal. It can be seen that the polyimide film according to the present disclosure has Excellent heat resistance.
儘管已參照本發明的具體實施例具體示出並描述了本發明，但對熟習此項技術者而言顯而易見的是，此具體描述僅為較佳的實施例，並且本發明的範圍並非受限於此。因此，旨在使本發明的範圍由所附的申請專利範圍及其等效範圍限定。 Although the present invention has been specifically illustrated and described with reference to specific embodiments of the present invention, it is obvious to those skilled in the art that this specific description is only a preferred embodiment, and the scope of the present invention is not limited Here. Therefore, it is intended that the scope of the present invention is limited by the scope of the attached patent application and its equivalent scope.
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| CN108864426A (en) * | 2018-06-12 | 2018-11-23 | 中国科学院化学研究所 | A kind of super-low expansion fluorinated polyimide film and the preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202033619A (en) | 2020-09-16 |
| CN112204085A (en) | 2021-01-08 |
| CN112204084B (en) | 2023-04-11 |
| TWI722786B (en) | 2021-03-21 |
| CN112204086A (en) | 2021-01-08 |
| TWI732439B (en) | 2021-07-01 |
| TW202033618A (en) | 2020-09-16 |
| CN112204077B (en) | 2023-10-24 |
| CN112204084A (en) | 2021-01-08 |
| CN112204077A (en) | 2021-01-08 |
| CN112204085B (en) | 2023-04-07 |
| CN112204086B (en) | 2023-04-14 |
| TW202033636A (en) | 2020-09-16 |
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