TW201946955A - Polyamide-imide block copolymer and polyamide-imide resin film comprising the same - Google Patents
Polyamide-imide block copolymer and polyamide-imide resin film comprising the same Download PDFInfo
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
Description
[相關申請案的交叉參考]
本申請案主張於2018年5月17日在韓國智慧財產局提出申請的韓國專利申請案第10-2018-0056588號、以及於2019年5月9日在韓國智慧財產局提出申請的韓國專利申請案第10-2019-0054492號的申請日期的權益,所述韓國專利申請案的全部揭露內容併入本案供參考。[Cross Reference to Related Applications]
This application claims Korean Patent Application No. 10-2018-0056588 filed with the Korean Intellectual Property Office on May 17, 2018, and Korean Patent Application filed with the Korean Intellectual Property Office on May 9, 2019 Case No. 10-2019-0054492, the entire disclosure of the Korean patent application is incorporated in this case for reference.
本發明是有關於一種聚醯胺醯亞胺樹脂膜。The invention relates to a polyamidamine / imine resin film.
芳族聚醯胺醯亞胺樹脂是主要具有非晶結構的聚合物,且因其剛性鏈結構而表現出優異的耐熱性、耐化學性、電性質及尺寸穩定性。此種聚醯亞胺樹脂廣泛用作用於電氣/電子、航空航天、航空、汽車等的材料。Aromatic polyamidoamine imine resin is a polymer mainly having an amorphous structure, and because of its rigid chain structure, it exhibits excellent heat resistance, chemical resistance, electrical properties, and dimensional stability. Such polyimide resins are widely used as materials for electrical / electronic, aerospace, aviation, automotive, and the like.
然而,儘管全芳族聚醯胺醯亞胺樹脂(wholly aromatic polyamide-imide resin)具有優異的耐熱性,但其大部分是不可溶解且不可熔化的,並且具有差的模製性及可處理性。因此,存在難以使用傳統處理設備來處理樹脂的問題。However, although the wholly aromatic polyamide-imide resin has excellent heat resistance, most of it is insoluble and infusible, and has poor moldability and handleability. . Therefore, there is a problem that it is difficult to process the resin using conventional processing equipment.
因此,已經進行了各種研究以在使聚醯胺醯亞胺樹脂具有優異耐熱性並且使在高溫下機械性質的降低最小化的同時改善熔化成形性(melt formability)。舉例而言,在試圖增加聚醯胺醯亞胺樹脂中的鏈的可撓性時,已經提出了引入-O-、-S-基團等的方法、引入間位取代基或大分子結構的方法等。根據上述提議的聚醯胺醯亞胺樹脂因彎曲的結構或脂肪族環狀化合物而難以表現出足夠的耐熱性,且使用所述聚醯胺醯亞胺樹脂生產的膜仍具有例如機械性質不佳等限制。Therefore, various studies have been conducted to improve melt formability while making the polyamidoamine imine resin excellent in heat resistance and minimizing a decrease in mechanical properties at high temperatures. For example, in an attempt to increase the flexibility of a chain in a polyamidamine / imine resin, a method of introducing -O-, -S- groups, etc., introducing a meta-substituent or a macromolecular structure have been proposed. Method, etc. According to the above-mentioned proposed polyamidoamine imine resin, it is difficult to exhibit sufficient heat resistance due to a curved structure or an aliphatic cyclic compound, and a film produced using the polyamidoamine imine resin still has, for example, mechanical properties. Best restrictions.
此外,當使用聚醯胺醯亞胺樹脂作為可撓性顯示材料時,除了熱性質及機械性質之外,還需要具有優異的光學性質。存在的問題是難以以所需水準同時滿足該些物理性質。In addition, when using a polyamidoamine imine resin as a flexible display material, it is necessary to have excellent optical properties in addition to thermal and mechanical properties. The problem is that it is difficult to simultaneously satisfy these physical properties at the required level.
[技術問題]
本發明的一個目的旨在提供一種聚醯胺醯亞胺嵌段共聚物,所述聚醯胺醯亞胺嵌段共聚物具有優異的機械性質、高彈性及耐折性,同時為無色及透明的,並且還具有高的抗水尺寸穩定性(high dimensional stability against water)。[technical problem]
An object of the present invention is to provide a polyamidoamine imine block copolymer, which has excellent mechanical properties, high elasticity and folding resistance, and is colorless and transparent at the same time. , And also has high dimensional stability against water.
本發明的另一個目的旨在提供一種包含上述聚醯胺醯亞胺嵌段共聚物的聚合物樹脂膜。Another object of the present invention is to provide a polymer resin film including the above-mentioned polyamidofluorine imine block copolymer.
[技術解決方案]
在本發明的一個態樣中,可提供一種聚醯胺醯亞胺嵌段共聚物,在所述聚醯胺醯亞胺嵌段共聚物中,氟元素的含量為10至50重量%,並且在室溫下浸入蒸餾水中20小時並且乾燥之後量測的尺寸變化為12微米(µm)或小於12微米。[Technical solution]
In one aspect of the present invention, a polyamidoamine imine block copolymer may be provided, in which the content of the fluorine element is 10 to 50% by weight, and The dimensional change measured after immersion in distilled water at room temperature for 20 hours and drying was 12 microns (µm) or less.
在本發明的另一態樣中,可提供一種包含上述聚醯胺醯亞胺嵌段共聚物的聚合物樹脂膜。In another aspect of the present invention, a polymer resin film including the polyamidamine / imine block copolymer described above can be provided.
在下文中,將詳細闡述根據本揭露的具體實施例的聚醯胺醯亞胺嵌段共聚物及聚合物樹脂膜。Hereinafter, the polyamidoamine imine block copolymer and the polymer resin film according to the specific examples of the present disclosure will be explained in detail.
除非在本說明書中另有明確規定,否則術語僅用於描述具體實施例,而不旨在限制本發明。Unless explicitly stated otherwise in this specification, the terms are used to describe specific embodiments only, and are not intended to limit the present invention.
除非上下文另外明確指出,否則在本文中使用的單數形式「一(a及an)」及「所述(the)」旨在也包括複數形式。Unless the context clearly indicates otherwise, as used herein, the singular forms "a" and "the" are intended to include the plural forms as well.
當在本文中使用用語「包括(comprises及comprising)」及/或「包含(includes及including)」時,是用於指明所述特徵、區域、整數、步驟、操作、元件、及/或組件的存在,但不排除一或多個其他特徵、區域、整數、步驟、操作、元件、組件及/或其群組的存在或添加。When the terms "comprises and computing" and / or "includes and including" are used herein, they are used to indicate the features, regions, integers, steps, operations, elements, and / or components The presence, but not exclusion, of the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and / or groups thereof.
包括例如「第一」、「第二」等序數的術語僅用於將一個組件與另一組件區分開的目的,而不受序數的限制。例如,在不背離本發明的範圍的情況下,第一組件可被稱為第二組件,或者類似地,第二組件可被稱為第一組件。Terms including ordinal numbers such as "first" and "second" are only used for the purpose of distinguishing one component from another, and are not limited by ordinal numbers. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, or similarly, a second component may be referred to as a first component.
本文中所使用的重量平均分子量是指藉由GPC方法量測的以聚苯乙烯計的重量平均分子量。在量測藉由GPC方法量測的以聚苯乙烯計的重量平均分子量的過程中,可使用偵測器以及分析柱(例如,眾所周知的分析設備及示差折射率偵測器(differential refractive index detector)),並且可使用通常應用的溫度條件、溶劑及流速(flow rate)。量測條件的具體實例可包括1)30℃的溫度、氯仿(chloroform)溶劑及1毫升/分鐘(mL/min)的流速(flow rate),或2)65℃的溫度、二甲基甲醛(dimethyl formaldehyde,DMF)及1毫升/分鐘的流速(flow rate)。As used herein, the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by the GPC method. Detectors and analytical columns (for example, well-known analytical equipment and differential refractive index detectors) can be used to measure the weight average molecular weight in polystyrene as measured by the GPC method. )), And can use commonly used temperature conditions, solvents and flow rates. Specific examples of measurement conditions may include 1) a temperature of 30 ° C, a chloroform solvent and a flow rate of 1 milliliter / minute (mL / min), or 2) a temperature of 65 ° C, dimethyl formaldehyde ( dimethyl formaldehyde (DMF) and a flow rate of 1 ml / min.
根據本發明的一個實施例,可提供一種聚醯胺醯亞胺嵌段共聚物,在所述聚醯胺醯亞胺嵌段共聚物中,氟元素的含量為10至50重量%,並且在室溫下浸入蒸餾水中20小時並且乾燥之後量測的尺寸變化為12微米或小於12微米。According to an embodiment of the present invention, there can be provided a polyamidamine / imine block copolymer, in which the content of the fluorine element is 10 to 50% by weight, and The dimensional change measured after immersion in distilled water at room temperature for 20 hours and after drying was 12 microns or less.
作為本發明人進一步連續研究的結果,合成了一種聚醯胺醯亞胺嵌段共聚物,在所述聚醯胺醯亞胺嵌段共聚物中,氟元素的含量為10至50重量%,並且即使在將所述聚醯胺醯亞胺嵌段共聚物暴露至水之後尺寸變化也不太高。As a result of further continuous research by the present inventors, a polyamidoamine imine block copolymer was synthesized, in which the content of the fluorine element was 10 to 50% by weight, And even after the polyamidofluorene imine block copolymer is exposed to water, the dimensional change is not so high.
由於此種聚醯胺醯亞胺嵌段共聚物具有優異的機械性質、高彈性及耐折性,同時為無色及透明的,並且還具有高的抗水尺寸穩定性,因此此種聚醯胺醯亞胺嵌段共聚物可適合用於暴露於潮濕環境等的產品及產業,例如顯示器用基板、顯示器用保護膜、觸控面板、可撓性(flexible)或可折疊(foldable)裝置用覆蓋膜等。Because of its excellent mechanical properties, high elasticity and folding resistance, it is colorless and transparent, and it also has high water-resistant dimensional stability.醯 Imine block copolymers are suitable for products and industries exposed to humid environments, such as display substrates, display protective films, touch panels, flexible or foldable device covers Film, etc.
更具體而言,根據示例性實施例的聚醯胺醯亞胺嵌段共聚物具有以下特徵:氟元素的含量為10至50重量%,並且即使在將所述聚醯胺醯亞胺嵌段共聚物暴露至水之後尺寸變化也不太高。此種聚醯胺醯亞胺嵌段共聚物具有以下物理性質,例如對於厚度為50±2微米的樣品,基於ASTM D 1925量測的黃色指數為4.5或小於4.5,並且基於ASTM D 1003量測的霧度為1.1%或小於1.1%,且因此具有無色及透明的光學性質。More specifically, the polyfluoreneimide block copolymer according to an exemplary embodiment has the following characteristics: the content of the fluorine element is 10 to 50% by weight, and even when the polyfluoreneimide block is The dimensional change of the copolymer after exposure to water is also not too high. This polyamidamine / imine block copolymer has the following physical properties. For example, for a sample with a thickness of 50 ± 2 microns, the yellowness index measured based on ASTM D 1925 is 4.5 or less, and measured based on ASTM D 1003. The haze is 1.1% or less, and therefore has colorless and transparent optical properties.
此外,藉由將12.5毫米/分鐘(mm/min)的應變速率(strain rate)施加至厚度為50±2微米的樣品進行量測時,根據示例性實施例的聚醯胺醯亞胺嵌段共聚物可具有為5十億帕(GPa)或大於5 Gpa或5至10 GPa的彈性模數(elastic modulus),且因此具有優異的機械性質、高彈性及耐折性。In addition, when a measurement is performed by applying a strain rate of 12.5 millimeters per minute (mm / min) to a sample having a thickness of 50 ± 2 micrometers, the polyamidoimide block according to the exemplary embodiment is measured. The copolymer may have an elastic modulus of 5 billion Pascals (GPa) or more than 5 Gpa or 5 to 10 GPa, and thus has excellent mechanical properties, high elasticity, and folding resistance.
具體而言,聚醯胺醯亞胺嵌段共聚物可為含有包含氟的官能基的芳族聚醯胺醯亞胺嵌段共聚物。Specifically, the polyamidoamine imine block copolymer may be an aromatic polyamidoamine imine block copolymer containing a functional group containing fluorine.
更具體而言,所述聚醯胺醯亞胺嵌段共聚物可包括:包括醯亞胺重複單元的醯亞胺嵌段,所述醯亞胺重複單元含有芳族四價官能基;以及包括醯胺重複單元的醯亞胺嵌段,所述醯胺重複單元含有芳族二價官能基,其中具有芳族重複單元的所述醯胺重複單元以及含有芳族二價官能基的芳族重複單元中的至少一者可被至少一個含氟官能基取代。More specifically, the polyfluorene imine block copolymer may include a fluorene imine block including a fluorene imine repeat unit, the fluorene imine repeat unit containing an aromatic tetravalent functional group; and Amidine block of amidamine repeating unit, said amidamine repeating unit containing an aromatic divalent functional group, wherein said amidamine repeating unit having an aromatic repeating unit and an aromatic repeat containing an aromatic divalent functional group At least one of the units may be substituted with at least one fluorine-containing functional group.
本實施例的聚醯胺醯亞胺嵌段共聚物的尺寸變化可由以下等式1定義,並且如上所述,根據等式1的定義的尺寸變化可為12微米或小於12微米、或11微米或小於11微米或1微米至11微米。
[等式1]
尺寸變化(微米)= │ L1 - L0 │
其中在等式1中,L0為在將由所述聚醯胺醯亞胺嵌段共聚物製備的厚度為50微米、寬度為0.5公分(cm)且長度為1.5公分的膜樣本浸入25°C的蒸餾水中20小時之後量測的長度,且L1為在量測L0之後在暴露於氮氣12小時的同時乾燥後量測的所述膜樣本的長度。The dimensional change of the polyamidoamine imine block copolymer of this embodiment can be defined by the following Equation 1, and as described above, the dimensional change according to the definition of Equation 1 can be 12 microns or less, or 11 microns Or less than 11 microns or 1 to 11 microns.
[Equation 1]
Dimensional change (micron) = │ L1-L0 │
Wherein, in Equation 1, L0 is obtained by immersing a film sample prepared from the polyamidamine / imine block copolymer with a thickness of 50 μm, a width of 0.5 cm (cm), and a length of 1.5 cm at 25 ° C The length measured after 20 hours in distilled water, and L1 is the length of the film sample measured after measuring L0 while being dried after being exposed to nitrogen for 12 hours.
將更詳細地闡述上述聚醯胺醯亞胺嵌段共聚物。The above-mentioned polyamidofluorene imine block copolymer will be explained in more detail.
聚醯胺醯亞胺嵌段共聚物可向醯胺嵌段中包含的重複單元中引入特定的結構,藉此同時改善共聚物的熱性質、機械性質及光學性質。具體而言,已發現藉由將二醯基鹵化物(diacyl halide)、二羧酸及二羧酸酯化合物限制為特定結構並且在共聚物的生產期間限制其莫耳比,可一起改善樹脂的光學性質,同時將聚醯胺醯亞胺共聚物的機械性質及耐熱性保持在優異的水準。The polyamidofluorine imine block copolymer can introduce a specific structure into the repeating unit contained in the polyamine block, thereby simultaneously improving the thermal, mechanical, and optical properties of the copolymer. Specifically, it has been found that by limiting diacyl halide, dicarboxylic acid, and dicarboxylic acid ester compounds to a specific structure and limiting their molar ratios during the production of the copolymer, the resin can be improved together Optical properties, while maintaining the mechanical properties and heat resistance of polyamidoamine imine copolymers at an excellent level.
更具體而言,所述聚醯胺醯亞胺嵌段共聚物可包括:醯亞胺嵌段,包括由以下化學式1表示的第一重複單元;以及醯胺嵌段,包括選自由以下化學式2表示的第二重複單元以及由以下化學式3表示的第三重複單元組成的群組中的任一者。
( i )醯亞胺衍生重複單元:第一重複單元
[化學式1]
其中,在化學式1中,
在各重複單元中R1
彼此相同或不同,且各自獨立地為單鍵、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)2
-、-Si(CH3
)2
-、-(CH2
)p
-(其中1≤p≤10)、-(CF2
)q
-(其中1≤q≤10)、-C(CH3
)2
-、-C(CF3
)2
-、-C(=O)NH-或C6至C30二價芳族有機基;
在各重複單元中R2
彼此相同或不同,且各自獨立地為-H、-F、-Cl、-Br、-I、-CF3
、-CCl3
、-CBr3
、-CI3
、-NO2
、-CN、-COCH3
、-CO2
C2
H5
、具有三個C1至C10脂肪族有機基的矽烷基、C1至C10脂肪族有機基或C6至C20芳族有機基;
n1與m1各自獨立地為0至3的整數;
在各重複單元中Y1
彼此相同或不同,並且各自獨立地包括包含至少一個三氟甲基(-CF3
)的C6至C30二價芳族有機基;且所述芳族有機基單獨存在;抑或二或更多個芳族有機基鍵結至彼此以形成二價縮合環;抑或二或更多個芳族有機基藉由以下基團進行連接:單鍵、芴基、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)2
-、-Si(CH3
)2
-、-(CH2
)p
-(其中1≤p≤10)、-(CF2
)q
-(其中1≤q≤10)、-C(CH3
)2
-、-C(CF3
)2
-或-C(=O)NH-;且
各E1
獨立地為單鍵或-NH-。More specifically, the polyfluorene imine block copolymer may include: a fluorene imine block including a first repeating unit represented by the following chemical formula 1; and a fluorene block comprising a selected from the following chemical formula 2 Any one of the group consisting of the second repeating unit represented by and the third repeating unit represented by the following Chemical Formula 3.
( I ) hydrazone-derived repeating unit: first repeating unit
[Chemical Formula 1]
Wherein, in Chemical Formula 1,
R 1 is the same or different from each other in each repeating unit, and each is independently a single bond, -O-, -S-, -C (= O)-, -CH (OH)-, -S (= O) 2 -, -Si (CH 3 ) 2 -,-(CH 2 ) p- (where 1≤p≤10),-(CF 2 ) q- (where 1≤q≤10), -C (CH 3 ) 2 -, -C (CF 3 ) 2- , -C (= O) NH- or C6 to C30 divalent aromatic organic group;
R 2 is the same or different from each other in each repeating unit, and is independently -H, -F, -Cl, -Br, -I, -CF 3 , -CCl 3 , -CBr 3 , -CI 3 , -NO 2, -CN, -COCH 3, -CO 2 C 2 H 5, an alkyl group having three silicon C1 to C10 aliphatic organic group, C1 to C10 aliphatic organic group or a C6 to C20 aromatic organic group;
n1 and m1 are each independently an integer of 0 to 3;
Y 1 is the same or different from each other in each repeating unit, and each independently includes a C6 to C30 divalent aromatic organic group containing at least one trifluoromethyl group (—CF 3 ); and the aromatic organic group exists alone; Or two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; or two or more aromatic organic groups are connected through the following groups: single bond, fluorenyl, -O-,- S-, -C (= O)-, -CH (OH)-, -S (= O) 2- , -Si (CH 3 ) 2 -,-(CH 2 ) p- (where 1≤p≤10 ),-(CF 2 ) q- (where 1≤q≤10), -C (CH 3 ) 2- , -C (CF 3 ) 2 -or -C (= O) NH-; and each E 1 is independent Ground is a single bond or -NH-.
此處,單鍵是指化學式1中的R1 為簡單地連接兩側上的基團的化學鍵的情形。Here, a single bond refers to a chemical formula 1, R 1 is a case where a chemical bond is simply connected groups on both sides.
在各重複單元中R2 彼此相同或不同,且各自可獨立地為-H、-F、-Cl、-Br、-I、-CF3 、-CCl3 、-CBr3 、-CI3 、-NO2 、-CN、-COCH3 、-CO2 C2 H5 、具有三個C1至C10脂肪族有機基的矽烷基、C1至C10脂肪族有機基或C6至C20芳族有機基。R 2 is the same as or different from each other in each repeating unit, and each may independently be -H, -F, -Cl, -Br, -I, -CF 3 , -CCl 3 , -CBr 3 , -CI 3 ,- NO 2 , -CN, -COCH 3 , -CO 2 C 2 H 5 , a silyl group having three C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group.
n1與m1可各自獨立地為0至3的整數。n1 and m1 may be each independently an integer of 0 to 3.
在各重複單元中Y1 彼此相同或不同,並且各自可獨立地為C3至C10脂肪族有機基。Y 1 is the same as or different from each other in each repeating unit, and each may independently be a C3 to C10 aliphatic organic group.
各E1 可獨立地為單鍵或-NH-。Each E 1 may independently be a single bond or -NH-.
此處,單鍵是指化學式1中的相應取代基為簡單地連接兩側上的基團的化學鍵的情形。Here, the single bond refers to a case where the corresponding substituent in Chemical Formula 1 is a chemical bond that simply connects groups on both sides.
較佳地,第一重複單元可包括由以下化學式1-1表示的重複單元:
[化學式1-1]
其中,在化學式1-1中,
R1
、R2
、n1及m1與在化學式1中所定義者相同。Preferably, the first repeating unit may include a repeating unit represented by the following chemical formula 1-1:
[Chemical Formula 1-1]
Among them, in Chemical Formula 1-1,
R 1 , R 2 , n1 and m1 are the same as defined in Chemical Formula 1.
此外,聚醯胺醯亞胺嵌段共聚物可包括醯胺嵌段,所述醯胺嵌段包括選自由以下化學式2表示的第二重複單元以及由以下化學式3表示的第三重複單元組成的群組中的任一者。In addition, the polyamidofluorine imine block copolymer may include a polyamine block comprising a second repeat unit selected from the following chemical formula 2 and a third repeat unit represented by the following chemical formula 3 Anyone in the group.
在所述聚醯胺醯亞胺嵌段共聚物中,所述第二重複單元:所述第三重複單元的莫耳比可為10:90至50:50。In the polyamidamine / imine block copolymer, the molar ratio of the second repeating unit: the third repeating unit may be 10:90 to 50:50.
由於所述聚醯胺醯亞胺嵌段共聚物中所含的第二重複單元:第三重複單元的莫耳比為10:90至50:50,因此其可具有能夠改善彈性同時保持高機械性質的聚合物的內部結構(特徵),藉此使得可提供處理性優異且易於形成膜、並且還是無色及透明的並具有優異的機械性質的聚合物材料或膜。此外,由於滿足上述莫耳比,因此在具有與無規共聚物(random copolymer)相同水準的氟含量的同時,可相對大幅度地改善吸水時的尺寸穩定性。
( ii )醯胺衍生重複單元:第二重複單元及第三重複單元
[化學式2]
[化學式3]
其中,在化學式2及化學式3中,
在各重複單元中Y2
與Y2'
彼此相同或不同,並且各自獨立地為包含至少一個三氟甲基(-CF3
)的C6至C30二價芳族有機基;且所述芳族有機基單獨存在;抑或二或更多個芳族有機基鍵結至彼此以形成二價縮合環;抑或二或更多個芳族有機基藉由以下基團進行連接:單鍵、芴基、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)2
-、-Si(CH3
)2
-、-(CH2
)p
-(其中1≤p≤10)、-(CF2
)q
-(其中1≤q≤10)、-C(CH3
)2
-、-C(CF3
)2
-或-C(=O)NH-;且
E2
、E2'
、E3
、E3'
、E4
及E4'
獨立地為單鍵或-NH-。Since the molar ratio of the second repeating unit: the third repeating unit contained in the polyamidoamine imine block copolymer is 10:90 to 50:50, it may have the ability to improve elasticity while maintaining high mechanical The internal structure (characteristics) of a polymer of a natural nature, thereby making it possible to provide a polymer material or film that is excellent in handleability and easily forms a film, and is also colorless and transparent and has excellent mechanical properties. In addition, since the above-mentioned molar ratio is satisfied, the dimensional stability at the time of water absorption can be improved relatively significantly while having a fluorine content of the same level as that of a random copolymer.
( Ii ) Amidine-derived repeating units: second repeating unit and third repeating unit
[Chemical Formula 2]
[Chemical Formula 3]
Among them, in Chemical Formula 2 and Chemical Formula 3,
Y 2 and Y 2 ′ are the same or different from each other in each repeating unit, and are each independently a C6 to C30 divalent aromatic organic group including at least one trifluoromethyl group (—CF 3 ); and the aromatic organic Groups exist alone; or two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; or two or more aromatic organic groups are connected through the following groups: single bond, fluorenyl,- O-, -S-, -C (= O)-, -CH (OH)-, -S (= O) 2- , -Si (CH 3 ) 2 -,-(CH 2 ) p- (where 1 ≤p≤10),-(CF 2 ) q- (where 1≤q≤10), -C (CH 3 ) 2- , -C (CF 3 ) 2 -or -C (= O) NH-; and
E 2, E 2 ', E 3, E 3', E 4 and E 4 'are independently a single bond or -NH-.
第二重複單元及第三重複單元是衍生自醯胺的重複單元,並且在化學式2及化學式3中,-C(=O)-AC(=O)-形式的二價連接基團是衍生自至少一種選自由二醯基鹵化物、二羧酸及二羧酸酯組成的群組的化合物的基團。第二重複單元中的兩個-C(=O)-相對於A()位於間位,並且第三重複單元中的兩個-C(=O)-相對於A()位於對位。The second repeating unit and the third repeating unit are repeating units derived from amidine, and in Chemical Formula 2 and Chemical Formula 3, the divalent linking group of the form -C (= O) -AC (= O)-is derived from A group of at least one compound selected from the group consisting of a difluorenyl halide, a dicarboxylic acid, and a dicarboxylic acid ester. Two -C (= O)-relative to A ( ) Is in meta position, and two -C (= O)-in the third repeating unit are relative to A ( ) Is in opposition.
較佳地,第二重複單元可包括由以下化學式2-1表示的重複單元。
[化學式2-1]
Preferably, the second repeating unit may include a repeating unit represented by the following Chemical Formula 2-1.
[Chemical Formula 2-1]
較佳地,第三重複單元可包括由以下化學式3-1表示的重複單元。
[化學式3-1]
Preferably, the third repeating unit may include a repeating unit represented by the following Chemical Formula 3-1.
[Chemical Formula 3-1]
另一方面,在上述聚醯胺醯亞胺嵌段共聚物中,第二重複單元與第三重複單元之間的莫耳比為10:90至50:50,且藉由滿足以上莫耳比,可同時改善共聚物的熱性質、機械性質及光學性質,且可相對大幅度地改善吸水時的尺寸穩定性。On the other hand, in the polyamidamine / imine block copolymer described above, the molar ratio between the second repeating unit and the third repeating unit is 10:90 to 50:50, and by satisfying the above molar ratio , Can simultaneously improve the thermal, mechanical and optical properties of the copolymer, and can relatively significantly improve the dimensional stability when absorbing water.
當第二重複單元與第三重複單元之間的莫耳比超出上述範圍時,可能存在霧度(haziness)增加或發生黃化的問題。When the molar ratio between the second repeating unit and the third repeating unit exceeds the above range, there may be a problem that haziness increases or yellowing occurs.
更具體而言,在聚醯胺醯亞胺嵌段共聚物中,醯亞胺嵌段:醯胺嵌段的莫耳比較佳地可為3:7至6:4。藉由同時滿足上述莫耳比以及第二重複單元與第三重複單元的莫耳比,聚醯胺醯亞胺樹脂膜的機械性質、熱性質及光學性質可被改善至高水準,並且可相對大幅度地改善吸水時的尺寸穩定性。More specifically, in the polyamidofluorene imine block copolymer, the mole of the fluoreneimine block: aminium block may be preferably 3: 7 to 6: 4. By satisfying the above-mentioned molar ratios and the molar ratios of the second repeating unit and the third repeating unit at the same time, the mechanical properties, thermal properties, and optical properties of the polyimide resin film can be improved to a high level and can be relatively large. Significantly improves dimensional stability when absorbing water.
此外,在聚醯胺醯亞胺嵌段共聚物中,當醯亞胺嵌段:醯胺嵌段的莫耳比為3:7至4:6時,第二重複單元:第三重複單元的莫耳比可為20:80至50:50或30:70至45:55,且更佳地約為40:60。當同時滿足上述範圍時,聚醯胺醯亞胺樹脂膜的機械性質、熱性質及光學性質可被改善至高水準,並且可相對大幅度地改善吸水時的尺寸穩定性。In addition, in the polyfluorene imine block copolymer, when the molar ratio of the fluorene imine block: fluorene block is 3: 7 to 4: 6, the second repeating unit: the third repeating unit The molar ratio may be 20:80 to 50:50 or 30:70 to 45:55, and more preferably about 40:60. When the above range is satisfied at the same time, the mechanical properties, thermal properties, and optical properties of the polyamidamine / imide resin film can be improved to a high level, and the dimensional stability when water is absorbed can be relatively greatly improved.
此外,在聚醯胺醯亞胺嵌段共聚物中,當醯亞胺嵌段:醯胺嵌段的莫耳比為4.5:5.5至4:6時,第二重複單元:第三重複單元的莫耳比可為20:80至40:60。當同時滿足上述範圍時,聚醯胺醯亞胺樹脂膜的機械性質、熱性質及光學性質可被改善至高水準,並且可相對大幅度地改善吸水時的尺寸穩定性。In addition, in the polyfluorene imine block copolymer, when the molar ratio of the fluorene imine block: fluorene block is 4.5: 5.5 to 4: 6, the second repeating unit: the third repeating unit The mole ratio can be from 20:80 to 40:60. When the above range is satisfied at the same time, the mechanical properties, thermal properties, and optical properties of the polyamidamine / imide resin film can be improved to a high level, and the dimensional stability when water is absorbed can be relatively greatly improved.
另一方面,除了醯亞胺嵌段及醯胺嵌段之外,聚醯胺醯亞胺嵌段共聚物可更包括由以下化學式4表示的第四重複單元:
[化學式4]
其中,在化學式4中,
各重複單元中的R1'
彼此相同或不同,並且各自獨立地為C6至C30二價芳族有機基;且所述芳族有機基單獨存在;抑或二或更多個芳族有機基鍵結至彼此以形成二價縮合環;抑或二或更多個芳族有機基可藉由以下基團進行連接:單鍵、芴基、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)2
-、-Si(CH3
)2
-、-(CH2
)p
-(其中1≤p≤10)、-(CF2
)q
-(其中1≤q≤10)、-C(CH3
)2
-、-C(CF3
)2
-或-C(=O)NH-。On the other hand, in addition to the fluorene imine block and the fluoramine block, the polyfluorene fluorene imine block copolymer may further include a fourth repeating unit represented by the following chemical formula 4:
[Chemical Formula 4]
Among them, in Chemical Formula 4,
R 1 ′ in each repeating unit is the same or different from each other, and each is independently a C6 to C30 divalent aromatic organic group; and the aromatic organic group exists alone; or two or more aromatic organic groups are bonded To each other to form a divalent condensed ring; or two or more aromatic organic groups may be connected through the following groups: single bond, fluorenyl, -O-, -S-, -C (= O)-, -CH (OH)-, -S (= O) 2- , -Si (CH 3 ) 2 -,-(CH 2 ) p- (where 1≤p≤10),-(CF 2 ) q- (where 1≤q≤10), -C (CH 3 ) 2- , -C (CF 3 ) 2- , or -C (= O) NH-.
在各重複單元中R2' 彼此相同或不同,且各自可獨立地為-H、-F、-Cl、-Br、-I、-CF3 、-CCl3 、-CBr3 、-CI3 、-NO2 、-CN、-COCH3 、-CO2 C2 H5 、具有三個C1至C10脂肪族有機基的矽烷基、C1至C10脂肪族有機基或C6至C20芳族有機基。R 2 ′ is the same or different from each other in each repeating unit, and each may independently be -H, -F, -Cl, -Br, -I, -CF 3 , -CCl 3 , -CBr 3 , -CI 3 , -NO 2 , -CN, -COCH 3 , -CO 2 C 2 H 5 , a silyl group having three C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group.
n3與m3可各自獨立地為0至3的整數。n3 and m3 may be each independently an integer of 0 to 3.
在各重複單元中Y1' 彼此相同或不同,並且各自獨立地為包括至少一個三氟甲基(-CF3 )的C6至C30二價芳族有機基;且所述芳族有機基單獨存在;抑或二或更多個芳族有機基可鍵結至彼此以形成二價縮合環;抑或二或更多個芳族有機基可藉由以下基團進行連接:單鍵、芴基、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)2 -、-Si(CH3 )2 -、-(CH2 )p -(其中1≤p≤10)、-(CF2 )q -(其中1≤q≤10)、-C(CH3 )2 -、-C(CF3 )2 -或-C(=O)NH-。Y 1 ′ is the same or different from each other in each repeating unit, and each is independently a C6 to C30 divalent aromatic organic group including at least one trifluoromethyl group (—CF 3 ); and the aromatic organic group exists alone ; Or two or more aromatic organic groups may be bonded to each other to form a divalent condensed ring; or two or more aromatic organic groups may be connected through the following groups: single bond, fluorenyl, -O -, -S-, -C (= O)-, -CH (OH)-, -S (= O) 2- , -Si (CH 3 ) 2 -,-(CH 2 ) p- (where 1≤ p≤10),-(CF 2 ) q- (where 1≤q≤10), -C (CH 3 ) 2- , -C (CF 3 ) 2 -or -C (= O) NH-.
各E1' 可獨立地為單鍵或-NH-。Each E 1 ′ may be independently a single bond or -NH-.
如上所述,在包括醯亞胺嵌段及醯胺嵌段兩者的聚醯胺醯亞胺嵌段共聚物中,藉由滿足在特定範圍內第二重複單元與第三重複單元之間的莫耳比以及醯亞胺嵌段與醯胺嵌段之間的莫耳比,可大幅度地改善吸水時的尺寸穩定性以及共聚物的機械性質、熱性質及光學性質。As described above, in the polyamidoimine block copolymer including both the amidoimide block and the amidate block, by satisfying the relationship between the second repeating unit and the third repeating unit within a specific range. The molar ratio and the molar ratio between the fluorene imine block and the fluoramine block can greatly improve the dimensional stability during water absorption and the mechanical, thermal, and optical properties of the copolymer.
聚醯胺醯亞胺嵌段共聚物可具有10,000克/莫耳(g/mol)至1,000,000克/莫耳、較佳地15,000克/莫耳至800,000克/莫耳的重量平均分子量。The polyamidamine imine block copolymer may have a weight average molecular weight of 10,000 g / mol (g / mol) to 1,000,000 g / mol, preferably 15,000 g / mol to 800,000 g / mol.
另一方面,聚醯胺醯亞胺嵌段共聚物可藉由包括以下步驟的製備方法提供:在合適的溶劑中混合形成第一重複單元的化合物以起始反應的步驟;向以上步驟的反應混合物中加入形成重複單元的化合物以進行反應的步驟;向以上步驟的反應混合物中加入形成第三重複單元的化合物以進行反應的步驟;以及向以上步驟的反應混合物中加入例如乙酸、乙酸酐(acetic anhydride)及吡(pyridine)啶等化合物以誘發化學醯亞胺化反應或藉由共沸蒸餾(azeotropic distillation)誘發醯胺酸的熱醯亞胺化反應的步驟。On the other hand, the polyamidoamine imine block copolymer can be provided by a preparation method including the steps of: mixing a compound forming a first repeating unit in a suitable solvent to initiate the reaction; and reacting to the above steps A step of adding a compound forming a repeating unit to perform a reaction is added to the mixture; a step of adding a compound forming a third repeating unit to perform a reaction is added to the reaction mixture of the above step; and adding, for example, acetic acid, acetic anhydride ( acetic anhydride, pyridine and other compounds to induce chemical amidine imidation reaction or azeotropic distillation to induce the thermal amidine reaction of amidine acid.
更具體而言,聚醯胺醯亞胺嵌段共聚物可藉由聚醯胺醯亞胺嵌段共聚物的包括以下步驟的合成製程提供:使二胺化合物與芳族四羧酸或其酸酐反應的起始步驟;以及使所述起始步驟的所得產物與含有莫耳比為10:90至50:50的間苯二甲酸或其衍生物與對苯二甲酸衍生物的混合物及芳族二胺反應的步驟。More specifically, the polyamidoamine imine block copolymer can be provided by a synthetic process of the polyamidoamine imine block copolymer including the following steps: a diamine compound and an aromatic tetracarboxylic acid or an anhydride thereof A starting step of the reaction; and a mixture of the product obtained from the starting step with isophthalic acid or a derivative thereof and a terephthalic acid derivative having a molar ratio of 10:90 to 50:50 and an aromatic Diamine reaction step.
另一方面,二胺化合物及芳族四羧酸或其酸酐的具體實例不受限制,並且可使用能夠形成上述化學式1的重複單元的二胺化合物(例如,在化學式1中含有Y1 的二胺)、或芳族四羧酸或其酸酐(例如,在化學式1中含有不同於-Y1 -E1 -的化學結構的四羧酸或其酸酐)。On the other hand, specific examples of the diamine compound and the aromatic tetracarboxylic acid or its anhydride are not limited, and a diamine compound capable of forming the repeating unit of the above Chemical Formula 1 (for example, a diamine containing Y 1 in Chemical Formula 1 may be used) Amine), or an aromatic tetracarboxylic acid or an anhydride thereof (for example, a tetracarboxylic acid or an anhydride thereof having a chemical structure different from -Y 1 -E 1 -in Chemical Formula 1).
另一方面,可藉由以下步驟來形成聚醯胺醯亞胺嵌段共聚物:使所形成的醯亞胺嵌段與含有莫耳比為10:90至50:50的間苯二甲酸或其衍生物與對苯二甲酸衍生物的混合物及芳族二胺反應。On the other hand, the polyamidofluorene imine block copolymer can be formed by the following steps: forming the polyamidoamine imine block copolymer with isophthalic acid containing a molar ratio of 10:90 to 50:50 or Its derivatives react with a mixture of terephthalic acid derivatives and aromatic diamines.
合成聚醯胺醯亞胺嵌段共聚物的步驟可包括使起始步驟的所得產物經受化學醯亞胺化或熱醯亞胺化的步驟。更具體而言,可執行藉由向起始步驟的所得產物中加入例如乙酸酐(acetic anhydride)或吡啶(pyridine)等化合物而誘發化學醯亞胺化反應、或藉由共沸蒸餾(azeotropic distillation)來誘發醯胺酸的熱醯亞胺化等步驟。熱醯亞胺化步驟可在100°C或高於100℃的溫度下、或者在100°C至350°C的溫度下、或者在150°C至250°C的溫度下執行。The step of synthesizing the polyfluorene-imide block copolymer may include a step of subjecting the resulting product of the initial step to chemical hydration or thermal hydration. More specifically, it is possible to induce a chemical amidine reaction by adding a compound such as acetic anhydride or pyridine to the product obtained in the initial step, or by azeotropic distillation ) To induce the step of hot amidine imidation. The thermal arsine imidization step may be performed at a temperature of 100 ° C or higher, or at a temperature of 100 ° C to 350 ° C, or at a temperature of 150 ° C to 250 ° C.
此外,當聚醯胺醯亞胺嵌段共聚物更包括第四重複單元時,可執行以下步驟:在適當的溶劑中混合形成第一重複單元的化合物以起始反應的步驟;向以上步驟的反應混合物中加入形成第二重複單元的化合物以進行反應的步驟;向以上步驟的反應混合物中加入形成第三重複單元的化合物以進行反應的步驟;向以上步驟的反應混合物中加入形成第四重複單元的化合物以進行反應的步驟;以及向以上步驟的所得產物中加入例如乙酸酐(acetic anhydride)或吡啶(pyridine)等化合物以誘發化學醯亞胺化反應或藉由共沸蒸餾(azeotropic distillation)誘發醯胺酸的熱醯亞胺化反應的步驟。In addition, when the polyamidamine / imine block copolymer further includes a fourth repeating unit, the following steps may be performed: a step of mixing a compound forming the first repeating unit in an appropriate solvent to initiate the reaction; A step of adding a compound forming a second repeating unit to the reaction mixture to perform the reaction; a step of adding a compound forming a third repeating unit to the reaction mixture to perform the reaction; a step of adding a fourth repeat to the reaction mixture of the above step A unit compound to perform a reaction step; and adding a compound such as acetic anhydride or pyridine to the product obtained in the above step to induce a chemical amidine reaction or by azeotropic distillation A step of inducing the thermal amidation reaction of amidine.
此外,如通常已知的,可使用低溫溶液聚合(low-temperature solution polymerization)、界面聚合(interfacial polymerization)、熔融聚合(melt polymerization)、固相聚合(solid phase polymerization)等用於生產聚醯胺醯亞胺嵌段共聚物。In addition, as is generally known, low-temperature solution polymerization, interfacial polymerization, melt polymerization, solid phase polymerization, and the like can be used for producing polyamide.醯 Imine block copolymer.
根據本揭露的另一實施例,可提供一種含有聚醯胺醯亞胺嵌段共聚物的聚合物樹脂膜。According to another embodiment of the present disclosure, a polymer resin film containing a polyamidamine / imine block copolymer may be provided.
所述聚合物樹脂膜可具有5微米至300微米或10微米至100微米的厚度。The polymer resin film may have a thickness of 5 to 300 microns or 10 to 100 microns.
可藉由例如乾式方法或濕式方法等傳統方法使用聚醯胺醯亞胺共聚物來生產實施例的聚合樹脂膜。舉例而言,可藉由將含有共聚物的溶液塗佈於任意支撐件上以形成膜、且然後自所述膜蒸發溶劑以使所述膜乾燥的方法來獲得聚醯亞胺系膜。必要時,可執行對所述聚醯亞胺系膜的拉伸及熱處理。The polymer resin film of the examples can be produced by using a polyamidamine / imine copolymer by a conventional method such as a dry method or a wet method. For example, a polyimide-based film can be obtained by coating a solution containing a copolymer on an arbitrary support to form a film, and then evaporating a solvent from the film to dry the film. If necessary, stretching and heat treatment of the polyfluorene-imide-based film may be performed.
如上所述,可藉由在預定溫度下(例如,在100℃或高於100℃的溫度下)熱處理上述聚醯胺醯亞胺嵌段共聚物以製備膜、然後對所述膜進行拉伸來生產聚醯胺醯亞胺樹脂膜。As described above, a film can be prepared by heat-treating the above polyamidene / imide block copolymer at a predetermined temperature (for example, at a temperature of 100 ° C or higher) to prepare a film, and then stretch the film. To produce polyimide resin.
拉伸的具體方法及條件以及使用的設備不受特別限制。舉例而言,在使聚醯胺醯亞胺嵌段共聚物在150℃至280℃的溫度下經受初級熱處理之後,可在150℃至280℃的溫度下藉由施加約0.1%/秒(%/sec)的速率以預定拉伸比(例如,約5%的拉伸比)進行拉伸以提供經拉伸的聚醯胺醯亞胺樹脂膜。The specific method and conditions for stretching and the equipment used are not particularly limited. For example, after subjecting the polyamidofluorene imine block copolymer to a primary heat treatment at a temperature of 150 ° C to 280 ° C, it may be applied at a temperature of 150 ° C to 280 ° C by applying about 0.1% / second (% / sec) is stretched at a predetermined stretch ratio (for example, a stretch ratio of about 5%) to provide a stretched polyamidamineimide resin film.
[有利效果]
根據本發明,可提供一種包含聚醯胺醯亞胺嵌段共聚物的聚合物樹脂膜,所述聚醯胺醯亞胺嵌段共聚物具有優異的機械性質、高彈性及耐折性,同時為無色及透明的,並且還具有高的抗濕氣尺寸穩定性。[Beneficial effect]
According to the present invention, it is possible to provide a polymer resin film including a polyamidoimine block copolymer, which has excellent mechanical properties, high elasticity, and folding resistance, and It is colorless and transparent, and also has high moisture dimensional stability.
包含聚醯胺醯亞胺嵌段共聚物的聚合物樹脂膜由於上述性質可用於顯示器用基板、顯示器用保護膜、觸控面板、可撓性(flexible)或可折疊(foldable)裝置用覆蓋膜等。The polymer resin film containing a polyamidamine imine block copolymer can be used for a display substrate, a display protective film, a touch panel, a cover film for a flexible or foldable device due to the above-mentioned properties. Wait.
以下,提供較佳實例以有助於理解本發明。然而,提供以下實例僅用於說明性目的,且本發明的範圍並非旨在限於該些實例或受該些實例限制。
[ 實例 1 及比較例 1 :製備聚醯胺醯亞胺嵌段共聚物 ]
實例 1 In the following, preferred examples are provided to help understand the present invention. However, the following examples are provided for illustrative purposes only, and the scope of the present invention is not intended to be limited to or limited by these examples.
[ Example 1 and Comparative Example 1 : Preparation of polyamidoamine imine block copolymer ]
Example 1
將2,2'-雙(三氟甲基)聯苯胺(2,2'-bis(trifluoromethyl)benzidine、4,4'-(六氟伸異丙基)二鄰苯二甲酸酐(4,4'-(hexafluoroisopropylidene)diphthalic anhydride)及二甲基乙醯胺(dimethylacetamide)置於配備有迪安-斯達克(Dean-Stark)設備及冷凝器的圓底燒瓶中,並在室溫下起始了反應。在0℃下使用油浴在氮氣氣氛下將反應混合物攪拌了4小時。Add 2,2'-bis (trifluoromethyl) benzidine (2,2'-bis (trifluoromethyl) benzidine, 4,4 '-(hexafluoroisopropyl) diphthalic anhydride (4,4 '-(hexafluoroisopropylidene) diphthalic anhydride) and dimethylacetamide were placed in a round bottom flask equipped with a Dean-Stark device and a condenser, and started at room temperature The reaction was stirred. The reaction mixture was stirred under a nitrogen atmosphere using an oil bath at 0 ° C for 4 hours.
在4小時之後,將反應產物取出並使其返回到室溫,向其中添加了2,2'-雙(三氟甲基)聯苯胺(2,2'-bis(trifluoromethyl)benzidine)、間苯二甲醯氯(isophthaloyl chloride,IPC)、4,4'-聯苯二甲醯氯(4,4'-biphenyldicarbonyl chloride,BPC)及二甲基乙醯胺(dimethylacetamide),且在氮氣氣氛下在室溫下起始了反應。After 4 hours, the reaction product was taken out and returned to room temperature, and 2,2'-bis (trifluoromethyl) benzidine, m-benzene was added thereto. Isophthaloyl chloride (IPC), 4,4'-biphenyldicarbonyl chloride (BPC), and dimethylacetamide. The reaction was initiated at room temperature.
在藉由反應4小時而形成聚醯胺酸聚合物之後,向反應混合物中添加了乙酸酐(acetic anhydride)及吡啶(pyridine),且在油浴(oil bath)中在40℃下將混合物攪拌了15小時以實施化學醯亞胺化反應。After the polyamic acid polymer was formed by the reaction for 4 hours, acetic anhydride and pyridine were added to the reaction mixture, and the mixture was stirred at 40 ° C. in an oil bath. It took 15 hours to perform a chemical amidine reaction.
在反應完成後,用水及乙醇(1:1(v/v))沉澱混合物以獲得包括第一重複單元、第二重複單元及第三重複單元(重量平均分子量約為200,000克/莫耳)的聚醯亞胺-嵌段共聚物A-1。所獲得的聚醯胺醯亞胺嵌段共聚物具有第一重複單元:第二重複單元與第三重複單元的總和為50:50的莫耳比(①),以及第二重複單元:第三重複單元為20:80的莫耳比(②)。
[第一重複單元]-醯亞胺重複單元
[第二重複單元]-醯胺重複單元(衍生自IPC)
[第三重複單元]-醯胺重複單元(衍生自BPC)
實例 2 至實例 4 After the reaction was completed, the mixture was precipitated with water and ethanol (1: 1 (v / v)) to obtain a first repeating unit, a second repeating unit, and a third repeating unit (weight average molecular weight approximately 200,000 g / mole). Polyfluorene imine-block copolymer A-1. The obtained polyamidamine / imine block copolymer has a first repeating unit: the sum of the second repeating unit and the third repeating unit is 50:50 in a molar ratio (①), and the second repeating unit: the third The repeating unit is a Morse ratio of 20:80 (②).
[First repeating unit] -Amidine repeating unit
[Second repeating unit]-Amidine repeating unit (derived from IPC)
[Third repeating unit]-Amidine repeating unit (derived from BPC)
Examples 2 to 4
除調整相應單體的添加比以滿足下表1中所示的莫耳比以外,以與實例1相同的方式製備了聚醯胺醯亞胺共聚物。
比較例 1 A polyamidofluorene imine copolymer was prepared in the same manner as in Example 1 except that the addition ratio of the corresponding monomers was adjusted to satisfy the molar ratio shown in Table 1 below.
Comparative Example 1
將2,2'-雙(三氟甲基)聯苯胺(2,2'-bis(trifluoromethyl)benzidine)、4,4'-(六氟伸異丙基)二鄰苯二甲酸酐(4,4'-(hexafluoroisopropylidene)diphthalic anhydride)、4,4'-聯苯二甲醯氯(4,4'-biphenyldicarbonyl chloride,BPC)、間苯二甲醯氯(isophthaloyl dichloride)及二甲基乙醯胺(dimethylacetamide)(70毫升)置於配備有迪安-斯達克(Dean-Stark)設備及冷凝器的250毫升圓底燒瓶中,並在室溫下起始了反應。Add 2,2'-bis (trifluoromethyl) benzidine (2,2'-bis (trifluoromethyl) benzidine), 4,4 '-(hexafluoroisopropyl) diphthalic anhydride (4, 4 '-(hexafluoroisopropylidene) diphthalic anhydride), 4,4'-biphenyldicarbonyl chloride (BPC), isophthaloyl dichloride, and dimethylacetamide (Dimethylacetamide) (70 ml) was placed in a 250 ml round bottom flask equipped with a Dean-Stark apparatus and a condenser, and the reaction was initiated at room temperature.
向所述反應混合物中添加了乙酸酐(acetic anhydride)及吡啶(pyridine),且接著在油浴(oil bath)中在40°C下將所述混合物攪拌了15小時以實施化學醯亞胺化反應。To the reaction mixture, acetic anhydride and pyridine were added, and then the mixture was stirred at 40 ° C. for 15 hours in an oil bath to perform chemical hydrazone imidization. reaction.
在反應完成之後,使用水及乙醇對混合物進行了沉澱,以獲得包括以下重複單元的聚醯亞胺系無規共聚物(重量平均分子量為400,000克/莫耳)。
[表1]
*醯胺(amide)重複單元比②表示第二重複單元(或2-2重複單元):第三重複單元(或2-2重複單元)的莫耳比。
實驗例 After the reaction was completed, the mixture was precipitated with water and ethanol to obtain a polyfluorene-based random copolymer including the following repeating units (weight average molecular weight: 400,000 g / mole).
[Table 1]
* Amide (amide) repeating unit ratio ② represents the molar ratio of the second repeating unit (or 2-2 repeating unit): the third repeating unit (or 2-2 repeating unit).
Experimental example
將在以上實例及比較例中的每一個中獲得的聚醯胺醯亞胺共聚物溶解在二甲基乙醯胺(dimethylacetamide)中以製備約10重量%的溶液。藉由棒塗佈機(bar coater)將溶液澆鑄在玻璃板上,並依次將乾燥溫度控制在120℃及200℃。結果,產生了厚度為50微米的聚醯胺醯亞胺膜。The polyamidoamine imine copolymer obtained in each of the above examples and comparative examples was dissolved in dimethylacetamide to prepare a solution of about 10% by weight. The solution was cast on a glass plate by a bar coater, and the drying temperature was controlled to 120 ° C and 200 ° C in this order. As a result, a polyaminium-imide film having a thickness of 50 micrometers was produced.
藉由以下方法對在實例及比較例中獲得的聚合物膜的物理性質進行了評估,且結果示於下表2中。
實驗例 1 :黃色指數( Yellow Index , Y.I ) The physical properties of the polymer films obtained in the examples and comparative examples were evaluated by the following methods, and the results are shown in Table 2 below.
Experimental Example 1: The yellow index (Yellow Index, YI)
根據測試方法ASTM D1925使用COH-400光譜儀(spectrophotometer)(日本電色工業株式會社(NIPPON DENSHOKU INDUSTRIES))量測了在以上實例及比較例中生產的聚醯胺醯亞胺膜樣品(厚度為50±2微米)的黃色指數,並且結果示於下表2中。
實驗例 2 :霧度( Hazeness ) According to the test method ASTM D1925, a COH-400 spectrophotometer (NIPPON DENSHOKU INDUSTRIES) was used to measure the polyimide / imide film samples (thickness: 50) produced in the above examples and comparative examples. ± 2 microns) and the results are shown in Table 2 below.
Experimental Example 2: Haze (Hazeness)
根據測試方法ASTM D1003使用COH-400光譜儀(spectrophotometer)(日本電色工業株式會社(NIPPON DENSHOKU INDUSTRIES))量測了在以上實例及比較例中生產的聚醯胺醯亞胺膜樣品(厚度為50±2微米)的霧度,並且結果示於下表2中。
實驗例 3 :彈性模數( Elastic Modulus , GPa ) According to the test method ASTM D1003, a sample of the polyamidamine / imide film (thickness of 50) was measured using a COH-400 spectrophotometer (NIPPON DENSHOKU INDUSTRIES). ± 2 microns), and the results are shown in Table 2 below.
Experimental Example 3 : Elastic Modulus ( GPa )
在應變速率(strain rate)為12.5毫米/分鐘(mm/min)的條件下使用斯威茲/羅爾(Zwich/Roell)z005(5kN)量測了在以上實例及比較例中生產的聚醯胺醯亞胺膜樣品(厚度為50±2微米)的彈性模數(Elastic Modulus)(GPa),並且結果示於下表2中。
[表2]
[Table 2]
如上表2所示,已證實由實例1至實例4的聚醯胺醯亞胺樹脂生產的膜具有高彈性模數,同時具有低黃色指數及低霧度值(haze value)。因此,證實實例的聚醯胺醯亞胺嵌段共聚物具有改善的光學性質以及優異的熱性質及機械性質。
實驗例 4 :量測聚合物樹脂膜中氟元素( F )含量 As shown in Table 2 above, it has been confirmed that the films produced from the polyamidoamine imine resins of Examples 1 to 4 have a high elastic modulus, and at the same time have a low yellow index and a low haze value. Therefore, it was confirmed that the polyfluorene imine block copolymer of the example has improved optical properties as well as excellent thermal properties and mechanical properties.
Experimental Example 4 : Measurement of fluorine element ( F ) content in polymer resin film
藉由元素分析(element analysis,EA)量測了在實例1及比較例1中獲得的聚合物樹脂膜中的每一者的氟元素(F)的含量。連接並使用AQF-2100H裝置(製造商:三菱化學分析技術公司(Mitsubishi Chemical Analytech))及ICS-5000裝置(製造商:戴安(Dionex)),並自在實例及比較例中的每一者中獲得的聚合物膜收集了0.01克(g)並用作樣品。The content of the fluorine element (F) in each of the polymer resin films obtained in Example 1 and Comparative Example 1 was measured by element analysis (EA). Connect and use the AQF-2100H device (manufacturer: Mitsubishi Chemical Analytech) and the ICS-5000 device (manufacturer: Dionex) in each of the examples and comparative examples The obtained polymer film collected 0.01 g (g) and was used as a sample.
對在以上實例及比較例中的每一者中獲得的聚合物膜中所含的氟元素的含量總共進行了兩次量測並取平均值。結果,證實比較例為22.6重量%(wt%),且實例為22.1重量%。
實驗例 5 :量測聚合物樹脂膜的抗水尺寸穩定性 The total content of the fluorine element contained in the polymer film obtained in each of the above examples and comparative examples was measured twice and averaged. As a result, it was confirmed that the comparative example was 22.6% by weight (wt%), and the example was 22.1% by weight.
Experimental example 5 : Measurement of water resistance dimensional stability of a polymer resin film
使用TMA/SDTA 840(熱機械分析(Thermomechanical Analysis),由梅特勒托利多(Mettler Toledo)製造)量測了在實例1及比較例中的每一者中獲得的聚合物樹脂膜的抗水尺寸穩定性。The water resistance of the polymer resin film obtained in each of Example 1 and Comparative Example was measured using TMA / SDTA 840 (Thermomechanical Analysis, manufactured by Mettler Toledo). Dimensional stability.
自在實例及比較例中的每一者中獲得的聚合物膜獲得了寬度為0.5公分*長度為1.5公分的樣本。將此樣本浸入25℃的蒸餾水中達20小時,然後在25℃及0.05牛頓(拉伸(tensile)方向)的條件下量測了初始尺寸。在使氮氣流動12小時後,最後將樣本乾燥12小時。量測了樣本的尺寸以獲得水尺寸穩定性資料。根據以下等式1獲得的在實例及比較例中的每一者中獲得的聚合物膜的尺寸變化對於比較例證實為12.7微米,而對於實例證實為10.5微米。
[等式1]
尺寸變化(微米)= │ L1 - L0 │
其中在等式1中,L0為在將由所述聚醯胺醯亞胺嵌段共聚物製備的厚度為50微米、寬度為0.5公分且長度為1.5公分的膜樣本浸入25°C的蒸餾水中20小時之後量測的長度(膜的面內(in-plane)方向),且L1為在量測L0之後在暴露於氮氣12小時的同時乾燥後量測的所述膜樣本的長度(膜的面內(in-plane)方向)。
[表3]
[Equation 1]
Dimensional change (micron) = │ L1-L0 │
Wherein, in Equation 1, L0 is immersed in a sample of a film having a thickness of 50 micrometers, a width of 0.5 cm, and a length of 1.5 cm prepared from the polyamidofluorine imine block copolymer in a distilled water of 25 ° C. 20 The length measured in hours (in-plane direction of the film), and L1 is the length of the film sample (the surface of the film) measured after drying after measuring L0 while being exposed to nitrogen for 12 hours while drying In-plane direction).
[table 3]
如表3所示,證實了在實例中獲得的聚醯胺醯亞胺嵌段共聚物具有極高的抗水尺寸穩定性,同時具有與比較例的聚醯胺醯亞胺無規共聚物相同水準的氟含量。As shown in Table 3, it was confirmed that the polyamidoamine imine block copolymer obtained in the example has extremely high dimensional stability against water, while having the same properties as the polyamidoamine imine random copolymer of the comparative example. Level of fluorine content.
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