TWI735667B - Acid dianhydride and use thereof - Google Patents

Acid dianhydride and use thereof Download PDF

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TWI735667B
TWI735667B TW106133364A TW106133364A TWI735667B TW I735667 B TWI735667 B TW I735667B TW 106133364 A TW106133364 A TW 106133364A TW 106133364 A TW106133364 A TW 106133364A TW I735667 B TWI735667 B TW I735667B
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葉鎮嘉
近藤光正
何邦慶
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日商日產化學工業股份有限公司
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Abstract

[課題] 提供一種賦予不僅耐熱性、柔軟性及透明性優異，亦具有延遲低的特徵之聚醯亞胺膜的聚醯胺酸聚醯胺酸及聚醯亞胺，以及一種該聚醯胺酸及聚醯亞胺之製造中所用之新穎之酸二酐。 　　[解決手段] 一種聚醯胺酸，其係使酸二酐成分與二胺成分反應所得之聚醯胺酸，其特徵為前述酸二酐成分包含下述式(1-1)所示之酸二酐，一種該聚醯胺酸之醯亞胺化物的聚醯亞胺，以及一種包含該聚醯胺酸之聚醯亞胺膜形成用組成物、一種包含該聚醯亞胺之膜形成用組成物，及各自得到的聚醯亞胺膜。

Figure 106133364-A0101-11-0001-1
(式中，R1 至R5 彼此獨立，表示鹵素原子、烷基或烷氧基，R6 及R7 彼此獨立，表示氫原子、鹵素原子、烷基或烷氧基，a及b彼此獨立，表示0~4之整數，c及d彼此獨立，表示0~9之整數，e表示0~2之整數)。[Question] To provide a polyimide film that provides a polyimide film that is not only excellent in heat resistance, flexibility, and transparency, but also has low retardation characteristics, and a polyimide A novel acid dianhydride used in the manufacture of acids and polyimides. [Solution] A polyamide acid, which is a polyamide acid obtained by reacting an acid dianhydride component and a diamine component, characterized in that the acid dianhydride component contains an acid represented by the following formula (1-1) A dianhydride, a polyimide of the polyimide of the polyimide, and a composition for forming a polyimide film containing the polyimide, and a composition for forming a film containing the polyimide The composition, and the polyimide film obtained separately.
Figure 106133364-A0101-11-0001-1
(In the formula, R 1 to R 5 are independent of each other, representing a halogen atom, an alkyl group or an alkoxy group, R 6 and R 7 are independent of each other, representing a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and a and b are independent of each other , Represents an integer from 0 to 4, c and d are independent of each other, represents an integer from 0 to 9, and e represents an integer from 0 to 2).

Description

酸二酐及其利用Acid dianhydride and its utilization

[0001] 本發明係關於新穎之酸二酐及其成為聚醯胺酸及聚醯亞胺的利用。[0001] The present invention relates to novel acid dianhydrides and their use as polyamide acids and polyimines.

[0002] 近年來，伴隨著液晶顯示器或有機電致發光顯示器等電子產品的急速進步，變得要求裝置的薄型化或輕量化，進而要求可撓性化。 　　此等裝置中，雖在玻璃基板上形成各種電子元件，例如，薄膜電晶體或透明電極等，但藉由將此玻璃材料替換成柔軟且輕量之樹脂材料，可期待裝置自身的薄型化或輕量化、可撓性化。 　　然後，作為如此之樹脂材料的候選者，集中注目於聚醯亞胺，過去以來已有關於聚醯亞胺薄膜的各種報告(參照例如專利文獻1，2)。 [先前技術文獻] [專利文獻] 　　[0003] 　　[專利文獻1] 日本特開昭60-188427號公報 　　[專利文獻2] 日本特開昭58-208322號公報 　　[專利文獻3] 國際公開2011/149018號小冊子[0002] In recent years, with the rapid advancement of electronic products such as liquid crystal displays and organic electroluminescence displays, thinner or lighter devices have become required, and further flexibility has been required. In these devices, although various electronic components such as thin film transistors or transparent electrodes are formed on a glass substrate, by replacing this glass material with a soft and lightweight resin material, the device itself can be expected to be thinner or thinner. Lightweight and flexible. "Then, as a candidate for such a resin material, attention has been focused on polyimide, and there have been various reports on polyimide films in the past (see, for example, Patent Documents 1 and 2). [Prior Art Document] [Patent Document] 　　[0003] 　　 [Patent Document 1] Japanese Patent Laid-Open No. 60-188427 [Patent Document 2] Japanese Patent Laid-Open No. 58-208322 [Patent Document 3] International Publication 2011/149018 Booklet

[發明所欲解決之課題] 　　[0004] 此外，使用聚醯亞胺樹脂材料作為顯示器的基板時，其樹脂材料不僅透明性優異，作為要求性能之一的延遲(Retardation)為低的材料為佳。 　　即，所謂延遲(相位差)，係指雙折射(正交的2個折射率的差)與膜厚之積，此數值，特別是厚度方向的延遲為影響視野角特性的重要數值。大的延遲值可能成為招致顯示器之顯示品質降低的原因(參照例如專利文獻3)。可撓性顯示器基板中，在高柔軟性(可撓性)以外，亦追求此等特性。 　　[0005] 本發明係鑑於如此之情事所成者，其目的在於提供一種給予不僅耐熱性、柔軟性及透明性優異，亦具有延遲低的特徵之聚醯亞胺膜的聚醯胺酸及聚醯亞胺，以及用於聚醯胺酸及聚醯亞胺之製造中的新穎之酸二酐。 [解決課題之手段] 　　[0006] 本發明者們，為了解決上述課題深入研究的結果，發現藉由使下述式(1-1)所示之酸二酐化合物，與四環丁酸二酐等之脂環式四羧酸二酐一起，與2,2’-二(三氟甲基)聯苯胺等之芳香族二胺進行共聚合，可得到於有機溶劑顯示良好之溶解性的聚醯胺酸及聚醯亞胺，及由使該聚醯胺酸及聚醯亞胺溶解於有機溶劑所得之組成物(溶液)，可得到不僅耐熱性、柔軟性及透明性優異，亦具有延遲低的特徵之聚醯亞胺膜，遂而完成本發明。 　　[0007] 即，本發明作為第1觀點係關於一種聚醯胺酸，其係使酸二酐成分與二胺成分反應所得之聚醯胺酸， 　　其特徵為前述酸二酐成分包含下述式(1-1)所示之酸二酐，

Figure 02_image004
(式中，R1 、R2 、R3 、R4 及R5 彼此獨立，表示鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基， 　　R6 及R7 彼此獨立，表示氫原子、鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基， 　　a及b彼此獨立，表示0~4之整數， 　　c及d彼此獨立，表示0~9之整數， 　　e表示0~2之整數)。 　　作為第2觀點係關於第1觀點所記載之聚醯胺酸，其中前述二胺成分包含式(A1)所示之二胺，
Figure 02_image006
(式中，B2 表示選自由式(Y-1)~式(Y-34)所成群組中之任一的基)，
Figure 02_image008
Figure 02_image010
Figure 02_image012
Figure 02_image014
(式中，＊表示鍵結處)。 　　作為第3觀點係關於第1觀點或第2觀點所記載之聚醯胺酸，其中前述酸二酐成分進一步包含式(C1)所示之四羧酸二酐，
Figure 02_image016
[式中，B1 表示選自由式(X-1)~式(X-12)所成群組中之任一的基，
Figure 02_image018
(式中，複數的R彼此獨立，表示氫原子或甲基，＊表示鍵結處)]。 　　作為第4觀點係關於一種聚醯亞胺膜形成用組成物，其特徵為包含第1觀點至第3觀點中任一項所記載之聚醯胺酸，與有機溶劑。 　　作為第5觀點係關於一種聚醯亞胺膜，其係使用第4觀點所記載之聚醯亞胺膜形成用組成物所形成者。 　　作為第6觀點係關於一種可撓性裝置用基板，其係由第5觀點所記載之聚醯亞胺膜而成者。 　　作為第7觀點係關於一種聚醯亞胺，其係將第1觀點至第3觀點中任一項所記載之聚醯胺酸進行醯亞胺而得。 　　作為第8觀點係關於一種膜形成用組成物，其包含第7觀點所記載之聚醯亞胺，與有機溶劑。 　　作為第9觀點係關於一種聚醯亞胺膜，其係使用第8觀點所記載之膜形成用組成物所形成者。 　　作為第10觀點係關於一種可撓性裝置用基板，其係由第9觀點所記載之聚醯亞胺膜而成者。 　　作為第11觀點係關於一種酸二酐，其特徵為式(1-1)所示，
Figure 02_image020
(式中，R1 、R2 、R3 、R4 及R5 彼此獨立，表示鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基， 　　R6 及R7 彼此獨立，表示氫原子、鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基， 　　a及b彼此獨立，表示0~4之整數， 　　c及d彼此獨立，表示0~9之整數， 　　e表示0~2之整數)。 　　作為第12觀點係關於第11觀點所記載之酸二酐，其係式(1-2)所示，
Figure 02_image022
(式中，R1 、R2 、R3 、R4 、R5 、R6 、R7 、a、b、c、d及e表示與前述相同的意思)。 　　作為第13觀點係關於第12觀點所記載之酸二酐，其係式(1-3)所示，
Figure 02_image024
作為第14觀點係關於一種四羧酸，其特徵為式(2-1)所示，
Figure 02_image026
(式中，R1 、R2 、R3 、R4 及R5 彼此獨立，表示鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基， 　　R6 及R7 彼此獨立，表示氫原子、鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基， 　　a及b彼此獨立，表示0~4之整數， 　　c及d彼此獨立，表示0~9之整數， 　　e表示0~2之整數)。 　　作為第15觀點係關於第14觀點所記載之四羧酸，其係式(2-2)所示，
Figure 02_image028
(式中，R1 、R2 、R3 、R4 、R5 、R6 、R7 、a、b、c、d及e表示與前述相同的意思)。 　　作為第16觀點係關於第15觀點所記載之四羧酸，其係式(2-3)所示，
Figure 02_image030
[發明效果] 　　[0008] 本發明之聚醯胺酸及聚醯亞胺於有機溶劑顯示良好之溶解性，又該聚醯胺酸及聚醯亞胺可形成耐熱性、柔軟性及透明性優異，進而可實現低延遲之聚醯亞胺膜(樹脂薄膜)。 　　又，本發明之聚醯亞胺膜由於顯示高透明性(高光線透過率、低黃色度)、耐熱性及低延遲，故可適合用於可撓性裝置，特別是作為可撓性顯示器的基板。[Problems to be Solved by the Invention] [0004] In addition, when a polyimide resin material is used as a substrate for a display, the resin material is not only excellent in transparency, but also a material with low Retardation, which is one of the required properties, is preferable . That is, the term retardation (phase difference) refers to the product of birefringence (the difference between two orthogonal refractive indices) and the film thickness, and this value, especially the retardation in the thickness direction, is an important value that affects viewing angle characteristics. A large delay value may cause a decrease in the display quality of the display (see, for example, Patent Document 3). In the flexible display substrate, in addition to high flexibility (flexibility), these characteristics are also pursued. [0005] The present invention was made in view of such circumstances, and its object is to provide a polyimide film that provides a polyimide film that not only has excellent heat resistance, flexibility, and transparency, but also has low retardation characteristics. Amide, and a novel acid dianhydride used in the production of polyimide and polyimide. [Means for Solving the Problem] [0006] As a result of intensive research in order to solve the above problem, the inventors found that the acid dianhydride compound represented by the following formula (1-1) was combined with tetracyclobutyric acid dianhydride Together with other alicyclic tetracarboxylic dianhydrides, copolymerized with aromatic diamines such as 2,2'-bis(trifluoromethyl)benzidine, polyamides showing good solubility in organic solvents can be obtained. Amino acid and polyimide, and a composition (solution) obtained by dissolving the polyimide acid and polyimide in an organic solvent, can obtain not only excellent heat resistance, flexibility, and transparency, but also low delay The characteristic polyimide film, thus completed the present invention. [0007] That is, the first aspect of the present invention relates to a polyamide acid, which is a polyamide acid obtained by reacting an acid dianhydride component and a diamine component, and is characterized in that the acid dianhydride component includes the following formula The acid dianhydride shown in (1-1),
Figure 02_image004
(In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are independent of each other and represent a halogen atom, an alkyl group with 1 to 5 carbon atoms or an alkoxy group with 1 to 5 carbon atoms, R 6 and R 7 are independent of each other, representing a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, a and b are independent of each other, representing an integer from 0 to 4, and c and d are independent of each other , Represents an integer from 0 to 9, and e represents an integer from 0 to 2). As a second viewpoint, the polyamide acid described in the first viewpoint, wherein the diamine component includes a diamine represented by formula (A1),
Figure 02_image006
(In the formula, B 2 represents a base selected from any of the groups formed by the free formula (Y-1) ~ formula (Y-34)),
Figure 02_image008
Figure 02_image010
Figure 02_image012
Figure 02_image014
(In the formula, * represents the bonding point). As a third viewpoint, it relates to the polyamide acid described in the first viewpoint or the second viewpoint, wherein the acid dianhydride component further includes a tetracarboxylic dianhydride represented by formula (C1),
Figure 02_image016
[In the formula, B 1 represents a base selected from any group formed by formula (X-1) ~ formula (X-12),
Figure 02_image018
(In the formula, plural Rs are independent of each other and represent a hydrogen atom or a methyl group, and * represents a bonding site)]. As a fourth viewpoint, it relates to a composition for forming a polyimide film, which is characterized by containing the polyimide acid described in any one of the first viewpoint to the third viewpoint, and an organic solvent. The fifth aspect relates to a polyimide film formed using the composition for forming a polyimide film described in the fourth aspect. The sixth aspect relates to a flexible device substrate, which is formed of the polyimide film described in the fifth aspect. The seventh viewpoint relates to a polyimide obtained by subjecting the polyimide described in any one of the first viewpoint to the third viewpoint to imine. The eighth viewpoint relates to a film forming composition containing the polyimide described in the seventh viewpoint and an organic solvent. The ninth aspect relates to a polyimide film formed using the film-forming composition described in the eighth aspect. The tenth viewpoint relates to a flexible device substrate formed from the polyimide film described in the ninth viewpoint. As the eleventh viewpoint, it relates to an acid dianhydride characterized by the formula (1-1),
Figure 02_image020
(In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are independent of each other and represent a halogen atom, an alkyl group with 1 to 5 carbon atoms or an alkoxy group with 1 to 5 carbon atoms, R 6 and R 7 are independent of each other, representing a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, a and b are independent of each other, representing an integer from 0 to 4, and c and d are independent of each other , Represents an integer from 0 to 9, and e represents an integer from 0 to 2). The 12th viewpoint is the acid dianhydride described in the 11th viewpoint, which is represented by formula (1-2),
Figure 02_image022
(In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , a, b, c, d, and e have the same meaning as described above). The 13th viewpoint is the acid dianhydride described in the 12th viewpoint, which is represented by formula (1-3),
Figure 02_image024
As the 14th viewpoint, it is about a tetracarboxylic acid, which is characterized by the formula (2-1),
Figure 02_image026
(In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are independent of each other and represent a halogen atom, an alkyl group with 1 to 5 carbon atoms or an alkoxy group with 1 to 5 carbon atoms, R 6 and R 7 are independent of each other, representing a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, a and b are independent of each other, representing an integer from 0 to 4, and c and d are independent of each other , Represents an integer from 0 to 9, and e represents an integer from 0 to 2). As the 15th viewpoint, the tetracarboxylic acid described in the 14th viewpoint is represented by the formula (2-2),
Figure 02_image028
(In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , a, b, c, d, and e have the same meaning as described above). The 16th viewpoint is the tetracarboxylic acid described in the 15th viewpoint, which is represented by formula (2-3),
Figure 02_image030
[Effects of the invention] [0008] The polyamide acid and polyimine of the present invention show good solubility in organic solvents, and the polyamide acid and polyimine can form excellent heat resistance, flexibility and transparency , In turn, a low-delay polyimide film (resin film) can be realized. In addition, the polyimide film of the present invention exhibits high transparency (high light transmittance, low yellowness), heat resistance, and low retardation, so it can be suitably used for flexible devices, especially as flexible displays. Substrate.

[0009] 以下進一步詳細說明本發明。 　　本發明之聚醯胺酸係使含下述式(1-1)所示之酸二酐的酸二酐成分，與二胺成分進行聚縮合反應而得。然後將所得之聚醯胺酸，藉由使用熱或觸媒之脫水閉環反應可成為對應之聚醯亞胺。不僅該聚醯胺酸，該聚醯亞胺亦為本發明之對象。此外，本發明之聚醯胺酸，為包含下述式(1-1)所示之酸二酐的酸二酐成分與二胺成分的反應生成物，又，本發明之聚醯亞胺為前述聚醯胺酸的醯亞胺化物。 　　[0010] 作為該式(1-1)所示之酸二酐，特別是式(1-2)所示之酸二酐較佳，其中，若考慮得到再現性良好地賦予耐熱性、柔軟性及透明性優異，且低延遲之聚醯亞胺膜的聚醯胺酸及對應之聚醯亞胺，較佳為式(1-3)所示之酸二酐。

Figure 02_image032
(式中，R1 、R2 、R3 、R4 及R5 彼此獨立，表示鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基， 　　R6 及R7 彼此獨立，表示氫原子、鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基， 　　a及b彼此獨立，表示0~4之整數， 　　c及d彼此獨立，表示0~9之整數， 　　e表示0~2之整數)。 　　[0011] 作為上述鹵素原子，可舉例氟原子、氯原子、溴原子等。 　　作為上述碳原子數1至5之烷基，可舉例例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基、異戊基、新戊基、tert-戊基、sec-異戊基及環戊基等。 　　又作為碳原子數1至5之烷氧基，可舉例甲氧基、乙氧基、n-丙氧基、異丙氧基、n-丁氧基、異丁氧基、sec-丁氧基、tert-丁氧基、n-戊氧基、異戊氧基、新戊氧基及tert-戊氧基等。 　　[0012] 本發明之上述式(1-1)~(1-3)所示之酸二酐，可分別將下述式(2-1)~(2-3)所示之四羧酸以脫水劑使其於分子內進行脫水而得。
Figure 02_image034
(式中，R1 、R2 、R3 、R4 、R5 、R6 、R7 、a、b、c、d及e表示與上述相同的意思)。 　　[0013] 具體而言，上述式(1-1)所示之酸二酐，作為一例如下述方案所示，可在有機溶劑中，使9,10-[1,2]苯并蒽-1,4-二醇化合物(9,10-[1,2]benzenoanthracene-1,4-diol)(以下稱為苯并蒽二醇化合物)與環己烷三羧酸鹵化酐在鹼或酸吸收劑的存在下進行反應而得[反應式1]。又反應後在去除溶劑後，反應混合物使用再結晶、蒸餾、二氧化矽凝膠管柱層析等公知手法進行純化，可得到目標物之酸二酐。 　　又亦可將[反應式1]之反應物水解，得到中間體(9,10-[1,2]苯并蒽-1,4-二基 雙(環己烷三羧酸酯)化合物)(式(2-1)所示之化合物)[反應式2]，將此中間體以脫水劑使其於分子內進行脫水[反應式3]而得。 　　此外上述式(1-1)~(1-3)所示之酸二酐及其中間體之上述式(2-1)~(2-3)所示之環己烷三羧酸酯(四羧酸化合物)亦為本發明之對象。
Figure 02_image036
(上述反應式中，X表示鹵素原子，R1 、R2 、R3 、R4 、R5 、R6 、R7 、a、b、c、d及e表示與上述相同的意思)。 　　[0014] 上述[反應式1]的反應中，苯并蒽二醇化合物與環己烷三羧酸鹵化酐的進料比，相對於苯并蒽二醇化合物1莫耳而言，為環己烷三羧酸鹵化酐2~4莫耳較佳。 　　作為鹼，適合使用三甲胺、三乙胺、二異丙胺、二異丙基乙胺、N-甲基哌啶、2,2,6,6-四甲基-N-甲基哌啶、吡啶、4-二甲胺基吡啶及N-甲基嗎啉等有機胺類等之有機鹼。又，鹼的使用量，雖只要相對於環己烷三羧酸鹵化酐1莫耳而言為1莫耳以上便無特別限定，但通常為1~5莫耳左右，較佳為1~3莫耳左右。 　　又，為了中和反應中副生的鹽酸等之酸，亦可使用酸吸收劑。作為酸吸收劑，可舉例環氧丙烷等之環氧化合物類。酸吸收劑的使用量，雖只要相對於苯并蒽二醇化合物1莫耳而言為2莫耳以上便無特別限定，但通常為2~10莫耳左右，較佳為2~4莫耳左右。 　　作為有機溶劑，雖只要是對反應沒有影響之溶劑便無特別限定，但可使用苯、甲苯及二甲苯等之芳香族烴類；N,N-二甲基甲醯胺(以下稱為DMF)、N,N-二甲基乙醯胺(以下稱為DMAc)及N-甲基-2-吡咯啶酮(以下稱為NMP)等之醯胺類；二乙基醚、四氫呋喃(以下稱為THF)、1,4-二
Figure 106133364-A0304-12-0015-1
烷、1,2-二甲氧基乙烷、環戊基甲基醚及二乙基醚等之醚類；2-丁酮及4-甲基-2-戊酮等之酮類；乙腈等之腈類以及二甲基亞碸(以下稱為DMSO)等。此等之溶劑可單獨使用，亦可組合2種以上使用。此外，[反應式1]中純化直接目標物之酸二酐(1-1)，取出時，若溶劑中含有很多水分，則引起酯的水解，因此溶劑係使用脫水溶劑，或，進行脫水後再使用較佳。又，經由[反應式2]、[反應式3]取出目標物之酸二酐(1-1)時，可使用亦可不使用脫水溶劑。 　　反應溫度雖可定為0~200℃左右，但20~150℃較佳。 　　反應後，餾去溶劑，藉由純化反應物得到目標物之酸二酐。此純化法為任意，可由再結晶、蒸餾及二氧化矽凝膠管柱層析等公知的手法適當地選擇。又，純化時所使用之有機溶劑，只要是在純化時與生成物不反應之溶劑便無特別限定，與上述反應使用之有機溶劑相同。 　　又，反應後之純化為困難時，藉由將粗生成物直接水解[反應式2]、得到四羧酸後以脫水劑使其脫水環化[反應式3]可得到目標之酸二酐。 　　[0015] 另一方面，上述[反應式2]之反應，雖只要將式(1-1)所示之酸二酐與水混合便無特別限定，但例如藉由將[反應式1]中生成之式(1-1)添加水，視情況添加有機溶劑、酸或鹼，進行加熱回流而水解，可得到式(2-1)所示之環己烷三羧酸酯(四羧酸化合物)。 　　水，相對於式(1-1)所示之酸二酐而言，通常使用2~100質量倍，較佳為使用2~40質量倍，更佳為使用2~6質量倍。 　　又，上述之反應亦可添加有機溶劑。作為有機溶劑，雖只要是對反應沒有影響之溶劑便無特別限定，但可使用苯、甲苯及二甲苯等之芳香族烴類；N,N-二甲基甲醯胺(以下稱為DMF)、N,N-二甲基乙醯胺(以下稱為DMAc)及N-甲基-2-吡咯啶酮(以下稱為NMP)等之醯胺類；二乙基醚、四氫呋喃(以下稱為THF)、1,4-二
Figure 106133364-A0304-12-0015-1
烷、1,2-二甲氧基乙烷、環戊基甲基醚及二乙基醚等之醚類；丙酮、乙酸乙酯、2-丁酮及4-甲基-2-戊酮等之酮類；乙腈等之腈類；以及二甲基亞碸(以下稱為DMSO)等。此等之溶劑可單獨使用，亦可組合2種以上使用。此外，為了效率良好地使水解進行，以極性高的溶劑較佳，例如DMF、DMAc、NMP、THF、1,4-二
Figure 106133364-A0304-12-0015-1
烷、二乙基醚、乙腈、丙酮及乙酸乙酯等較佳。 　　又，上述之反應亦可添加酸。酸雖無特別限定，但作為酸，可舉例磷鉬酸及磷鎢酸等之雜多酸；三甲基硼酸鹽及三苯基膦等之有機酸；鹽酸、硫酸及磷酸等之無機酸；甲酸、乙酸、丙酸及p-甲苯磺酸等之烴酸；以及三氟乙酸等之鹵素系烴酸。較佳為，可舉例鹽酸、硫酸、乙酸及p-甲苯磺酸。 　　酸相對於式(1-1)所示之酸二酐而言通常使用0~100倍莫耳，較佳為使用0.01~10倍莫耳。 　　又，本反應亦可使用鹼性水溶液進行水解。鹼雖無特別限定，但作為鹼，可舉例氫氧化鈉、氫氧化鉀、氫氧化鋰、碳酸鈉、碳酸鉀及碳酸鋰等之鹼金屬類、氫氧化鎂及氫氧化鈣等之鹼土金屬類。其中較佳為，可舉例氫氧化鈉、氫氧化鉀、氫氧化鋰。 　　鹼的使用量相對於式(1-1)所示之酸二酐而言通常使用0~100倍莫耳，較佳為使用0.01~10倍莫耳。 　　反應溫度雖無特別限定，但例如為-90~200℃，較佳為50~130℃。 　　反應時間，通常為0.1至200小時，較佳為0.5至100小時。 　　[0016] 又，上述[反應式3]之反應，雖只要採用公知的方法變無特別限制，但例如，藉由將[反應式2]所得之式(2-1)所示之環己烷三羧酸酯(四羧酸化合物)與脫水劑在溶劑中混合，可得到式(1-1)所示之酸二酐。 　　[0017] 作為脫水劑，雖只要是式(2-1)所示之環己烷三羧酸酯(四羧酸化合物)可與脫水劑接觸者便無特別限定，但例如，脫水可在乙酸酐、丙酸酐、三氟乙酸酐等之脂肪族羧酸酐、1,3-二環己基碳二亞胺、2-氯-1,3-二甲基咪唑啉鎓氯化物等之脫水劑的存在下實施。又，碳數為1~3之低級羧酸酐較佳，更佳為碳數為1~2之低級羧酸酐較佳，其中由無水化後容易去除且經濟上有利的點來看乙酸酐特佳。 　　[0018] 脫水劑的使用量雖無特別限定，但相對於式(2-1)所示之環己烷三羧酸酯(四羧酸化合物)而言，2~50當量較佳，特佳為4~20當量。若為2~50當量，則酐化充分地進行，且所得之式(1-1)所示之酸二酐的溶解量不會增加太多，可以高收率使式(1-1)所示之酸二酐析出。 　　[0019] 上述反應亦可使用不直接參與反應的有機溶劑。可舉例例如甲苯、二甲苯等之烴類、1,2-二氯乙烷、1,2-二氯丙烷等之鹵化烴類、進而1,4-二
Figure 106133364-A0304-12-0015-1
烷等。 　　[0020] 此外，不一定要使式(2-1)所示之環己烷三羧酸酯(四羧酸化合物)完全溶解在均勻系內進行酐化反應，亦可在不均勻系內實施酐化反應。 　　[0021] 反應中加熱的溫度，較佳為30~200℃，更佳為在40~180℃之範圍進行，反應溫度越高反應速度越提升。因此以使用溶劑之回流溫度實施較佳。 　　[0022] 又，反應時間雖可對應使用之脫水劑的種類、溫度等之條件來適當地設定，但為0.5~20小時較佳。 　　[0023] 藉由上述酐化反應，於使用之脫水劑中可得到懸濁有式(1-1)所示之酸二酐之懸濁液。酐化反應之後，藉由過濾所得之懸濁液可回收式(1-1)所示之酸二酐的粉末。又，視需要亦可濃縮上述懸濁液。 　　又，視需要亦可以有機溶劑洗淨上述濾取物。此洗淨溶劑雖只要是不與酐反應，且目標酐的溶解度為低的溶劑便無特別限定，但可舉例例如甲苯、己烷、庚烷、乙腈、丙酮、氯仿、乙酸乙酯、碳酸二甲酯等或此等之混合溶劑等。其中以乙酸乙酯、碳酸二甲酯較佳。 　　進而，藉由利用減壓乾燥等去除脫水劑或溶劑，可得到高純度之式(1-1)所示之酸二酐。又，依需要藉由使用再結晶、蒸餾、二氧化矽凝膠管柱層析等公知的手法進行純化，亦可得到目標物之酸二酐。 　　[0024] 此外，本發明中所得之式(2-1)所示之酸二酐，係文獻未記載之新穎化合物，如上述，可使用於由此可容易地製造式(1-1)所示之酸二酐等之各種用途中。 　　[0025] 又，本發明中所用之苯并蒽二醇化合物，例如，作為一例如下述方案所示，可藉由依循公知的方法，在有機溶劑中，將使蒽化合物與1,4-苯醌化合物進行Diels-Alder反應而得之9,10-[1,2]苯并蒽-13,16(9H,10H)-二酮化合物，在乙酸溶劑中，47%溴化氫存在下，以加熱條件進行處理而得。
Figure 02_image038
(上述方案中，R1 、R2 、R5 、R6 、R7 、a、b及e表示與上述相同的意思)。 　　[0026] 由再現性良好地得到賦予不僅耐熱性、柔軟性及透明性優異，亦具有延遲低的特徵之聚醯亞胺膜的聚醯胺酸(及對應之聚醯亞胺)的觀點來看，用於製造本發明之聚醯胺酸(及對應之聚醯亞胺)的酸二酐成分，上述式(1-1)所示之酸二酐之外，較佳為包含脂環式四羧酸二酐，更佳為包含下述式(C1)所示之酸二酐。
Figure 02_image040
[式中，B1 表示選自由式(X-1)~(X-12)所成群組中之4價基；
Figure 02_image042
(式中，複數的R彼此獨立，表示氫原子或甲基，＊表示鍵結處)]。 　　[0027] 上述式(C1)所示之酸二酐之中，式中之B1 為前述式(X-1)、(X-2)、(X-4)、(X-5)、(X-6)、(X-7)、(X-8)、(X-9)、(X-11)及(X-12)所示之酸二酐較佳，前述B1 為前述式(X-1)、(X-2)、(X-6)、(X-11)及(X-12)所示之酸二酐特佳。 　　又，在不損及本發明效果的範圍內，前述酸二酐成分中，亦可使用上述式(1-1)所示之酸二酐、上述式(C1)所示之酸二酐以外之其他的酸二酐。 　　[0028] 上述酸二酐成分中，與本發明之上述式(1-1)所示之酸二酐同時使用脂環式四羧酸二酐之情形中，上述式(1-1)所示之酸二酐與脂環式四羧酸二酐的比率，通常為上述式(1-1)所示之酸二酐：脂環式四羧酸二酐=1：0.5~1：4。藉由成為如此之範圍，可再現性良好地得到賦予高耐熱性、高柔軟性、高透明性、低延遲之聚醯亞胺的聚醯胺酸。 　　[0029] 由再現性良好地得到賦予不僅耐熱性、柔軟性及透明性優異，亦具有延遲低的特徵之聚醯亞胺膜的聚醯胺酸(及對應之聚醯亞胺)的觀點來看，用於製造本發明之聚醯胺酸(及對應之聚醯亞胺)的二胺成分，較佳為包含芳香族二胺，更佳為包含下述式(A1)所示之二胺。
Figure 02_image044
(式中，B2 表示選自由式(Y-1)~式(Y-34)所成群組中之2價基；
Figure 02_image046
Figure 02_image048
(式中，＊表示鍵結處)。 　　[0030] 上述式(A1)所示之二胺之中，式中之B2 為前述式(Y-12)、(Y-13)、(Y-14)、(Y-15)、(Y-18)、(Y-27)、(Y-28)、(Y-30)及(Y-33)所示之二胺較佳，前述B2 為前述式(Y-12)、(Y-13)、(Y-14)、(Y-15)及(Y-33)所示之二胺特佳。 　　又，在不損及本發明效果的範圍內，前述二胺成分中，亦可使用上述式(A1)所示之二胺以外之其他的二胺化合物。 　　[0031] 由再現性良好地得到賦予高耐熱性、高柔軟性、高透明性、低延遲之聚醯亞胺膜的聚醯胺酸(及對應之聚醯亞胺)的觀點來看，用於製造本發明之聚醯胺酸(及對應之聚醯亞胺)的二胺成分中芳香族二胺的含量，較佳為50mol%以上，更佳為60mol%以上，更加佳為70莫耳%，再更佳為80莫耳%，再更加佳為90莫耳%，最佳為100莫耳%。 　　[0032] 此外，作為上述酸二酐成分使用上述式(1-1)所示之酸二酐與上述(C1)所示之酸二酐，作為上述二胺成分使用上述式(A1)所示之二胺之情形中，聚醯胺酸成為具有下述式(4-1)所示之單體單位與下述式(4-2)所示之單體單位者。
Figure 02_image050
(式中，R1 、R2 、R3 、R4 、R5 、R6 、R7 、a、b、c、d、e、B1 及B2 表示與上述相同的意思)。 　　[0033] 獲得本發明之聚醯胺酸的方法並無特別限定，只要是將前述之酸二酐成分與二胺成分藉由公知的手法使其反應、聚合即可。 　　合成聚醯胺酸時之酸二酐成分之莫耳數與二胺成分之莫耳數的比，為酸二酐成分/二胺成分=0.8~1.2。 　　[0034] 作為用於聚醯胺酸之合成的溶劑，可舉例例如m-甲酚、N-甲基-2-吡咯啶酮(NMP)、N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAc)、N-甲基己內醯胺、二甲基亞碸(DMSO)、四甲脲、吡啶、二甲基碸、六甲基磷醯胺及γ-丁內酯等。此等可單獨使用，亦可混合使用。進而，即使是不溶解聚醯胺酸的溶劑，在得到均勻之溶液的範圍內亦可添加至上述溶劑中使用。 　　聚縮合反應的溫度可選擇-20~150℃，較佳為-5~100 ℃之任意的溫度。 　　[0035] 藉由上述聚醯胺酸之聚合反應所得之含有聚醯胺酸之溶液可直接，或是稀釋或濃縮後，作為後述聚醯亞胺膜形成用組成物來使用。又，該含有聚醯胺酸之溶液中，加入甲醇、乙醇等之不良溶劑使聚醯胺酸沉澱進行單離，使該經單離之聚醯胺酸在適當的溶劑中再溶解作為含有聚醯胺酸之溶液，此可作為聚醯亞胺膜形成用組成物來使用。 　　含有聚醯胺酸之溶液的稀釋用溶劑以及經單離之聚醯胺酸的再溶解用溶劑，只要是使所得之聚醯胺酸溶解者便無特別限定，可舉例例如m-甲酚、2-吡咯啶酮、NMP、N-乙基-2-吡咯啶酮、N-乙烯基-2-吡咯啶酮、DMAc、DMF及γ-丁內酯等。 　　[0036] 又，即使無法單獨溶解聚醯胺酸之溶劑，只要是在聚醯胺酸不析出的範圍亦可添加至上述溶劑中使用。作為其具體例，可舉例乙基溶纖劑、丁基溶纖劑、乙基卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯及乳酸異戊酯等。 　　[0037] 本發明之聚醯亞胺，可將上述說明之聚醯胺酸，藉由加熱進行脫水閉環(熱醯亞胺化)，或使用公知之脫水閉環觸媒化學性地閉環而得。 　　藉由加熱之方法，可以100~300℃，較佳為以120~250℃之任意的溫度進行。 　　化學性地閉環的方法，例如，可在吡啶、三乙胺或1-乙基哌啶等，與乙酸酐等之存在下進行，此時的溫度，可選擇-20~200℃之任意的溫度。 　　[0038] 如此所得之由具有上述式(4-1)所示之單體單位與上述記式(4-2)所示之單體單位的聚醯胺酸所得之聚醯亞胺，為具有下述式(5-1)所示之單體單位與下述式(5-2)所示之單體單位者。
Figure 02_image052
(式中，R1 、R2 、R3 、R4 、R5 、R6 、R7 、a、b、c、d、e、B1 及B2 表示與上述相同的意思)。 　　[0039] 藉由上述聚醯胺酸之閉環反應所得之含有聚醯亞胺之溶液(以下亦稱為聚醯亞胺溶液)，可直接，或是稀釋或濃縮後，作為後述之膜形成用組成物來使用。又，於該含有聚醯亞胺之溶液中，加入甲醇、乙醇等之不良溶劑使聚醯亞胺沉澱將聚醯亞胺進行單離，將該經單離之聚醯亞胺適當地再溶解於溶劑中，可作為後述之膜形成用組成物來使用。 　　再溶解用溶劑，只要是使所得之聚醯亞胺溶解者便無特別限定，可舉例例如m-甲酚、2-吡咯啶酮、NMP、N-乙基-2-吡咯啶酮、N-乙烯基-2-吡咯啶酮、DMAc、DMF及γ-丁內酯等。 　　[0040] 又，即使是單獨不溶解聚醯亞胺之溶劑，只要在聚醯亞胺不析出之範圍可添加至上述溶劑來使用。作為其具體例，可舉例乙基溶纖劑、丁基溶纖劑、乙基卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯及乳酸異戊酯等。 　　[0041] 此外本發明中，聚醯胺酸及對應之聚醯亞胺之數平均分子量，由使所得之薄膜的柔軟性、強度等提升的觀點來看，較佳為5,000以上，更佳為7,000以上，更加佳為10,000以上，又，由確保所得之聚醯胺酸及對應之聚醯亞胺之溶解性的觀點來看，較佳為200,000以下，更佳為100,000以下，更加佳為50,000以下。此外本說明書中，數平均分子量，係藉由GPC(凝膠浸透色層分析)裝置來測定，作為聚苯乙烯換算值所算出之值。 　　[0042] [膜形成用組成物・聚醯亞胺膜形成用組成物] 　　上述之本發明之包含聚醯亞胺與有機溶劑的膜形成用組成物，以及，本發明之包含聚醯胺酸與有機溶劑的聚醯亞胺膜形成用組成物亦為本發明之對象。此處，本發明之膜形成用組成物及聚醯亞胺膜形成用組成物，為均勻者，為未確認到相分離者。 　　[0043] ＜有機溶劑＞ 　　本發明之膜形成用組成物或聚醯亞胺膜形成用組成物，前述聚醯亞胺或聚醯胺酸之外，包含有機溶劑。該有機溶劑並無特別限定，可舉例例如與用於調製上述聚醯胺酸及聚醯亞胺時之反應溶劑的具體例相同者。更具體而言，可舉例N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、1,3-二甲基-2-咪唑啶酮、N-乙基-2-吡咯啶酮、γ-丁內酯等。此外，有機溶劑，可單獨使用1種，亦可組合2種以上使用。 　　此等之中，若考慮到再現性良好地得到平坦性高之膜，以N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、γ-丁內酯較佳。 　　[0044] 本發明之膜形成用組成物或聚醯亞胺膜形成用組成物中之固形分量的調配量，通常為0.5~30質量%左右，較佳為5~25質量%左右。固形分濃度若未達0.5質量%，則在製作膜上製膜效率變低，又，由於膜形成用組成物或聚醯亞胺膜形成用組成物之黏度變低，故難以得到表面均勻的塗膜。又，固形分濃度若超過30質量%，則膜形成用組成物或聚醯亞胺膜形成用組成物之黏度變得過高，仍有成膜效率之惡化或塗膜之表面均勻性欠缺之虞。此外所謂之固形分量，係指有機溶劑以外之成分的總質量，定為即使液狀之單體等亦作為固形分包含於重量中者。 　　此外，膜形成用組成物或聚醯亞胺膜形成用組成物的黏度，雖考慮製作之膜的厚度等來適當地設定，但在以再現性良好地得到特別是5~50μm左右厚度之膜為目的時，通常於25℃為500~50,000mPa・s左右，較佳為1,000~ 20,000mPa・s左右。 　　[0045] 本發明之膜形成用組成物或聚醯亞胺膜形成用組成物中，為了授予加工特性或各種機能性，亦可調配其他各種有機或無機之低分子或高分子化合物。例如，可使用觸媒、消泡劑、流平劑、界面活性劑、染料、塑化劑、微粒子、耦合劑、增感劑等。 　　此外，亦包括包含其他成分之情形，本發明之膜形成用組成物或聚醯亞胺膜形成用組成物的固形分量中，上述聚醯亞胺或聚醯胺酸之比例可定為70~100質量%。 　　本發明之膜形成用組成物或聚醯亞胺膜形成用組成物，可將以上述方法所得之聚醯亞胺或聚醯胺酸溶解於上述有機溶劑中而得，亦可為在調製聚醯亞胺或聚醯胺酸後之反應溶液中，視需要進一步加入前述有機溶劑者。 　　[0046] [膜] 　　將以上說明之本發明之膜形成用組成物或聚醯亞胺膜形成用組成物塗佈於基材後藉由乾燥、加熱去除有機溶劑，可得到具有高耐熱性、高透明性、適度之柔軟性與適度之線膨脹係數，且延遲小的膜(聚醯亞胺膜)。 　　即，藉由將塗佈於基材上之上述膜形成用組成物(含有聚醯亞胺之溶液)加熱，使溶劑蒸發，可得到包含聚醯亞胺之發明之膜，該膜係由上述膜形成用組成物的固形分而成者。 　　或者，藉由將塗佈於基材上之上述聚醯亞胺膜形成用組成物(含有聚醯胺酸之溶液)加熱，使溶劑蒸發同時使其進行醯亞胺化反應，可得到包含聚醯亞胺之本發明之膜，該膜係由上述聚醯亞胺膜形成用組成物之固形分所成，係包含該固形分中之聚醯胺酸的醯亞胺化物者。 　　然後上述膜，即含有上述聚醯亞胺之膜(薄膜)亦為本發明之對象。 　　[0047] 作為用於膜之製造的基材，可舉例例如塑膠(聚碳酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚酯、聚烯烴、環氧、三聚氰胺、三乙醯基纖維素、ABS、AS、降莰烯系樹脂等)、金屬、不鏽鋼鋼(SUS)、木材、紙、玻璃、矽晶圓及板岩等。 　　特別是，應用作為電子裝置之基板材料之情形中，由可利用現有設備的觀點來看，適用之基材為玻璃或矽晶圓較佳，又，由所得之膜顯示良好之剝離性來看以玻璃再更佳。此外，作為適用之基材的線膨脹係數，由塗佈後基材之翹曲的觀點來看，較佳為35ppm/℃以下，更佳為30ppm/℃以下，更加佳為25ppm/℃以下，再更佳為20ppm/℃以下。 　　[0048] 對基材之膜形成用組成物或聚醯亞胺膜形成用組成物的塗佈法雖無特別限定，但可舉例例如鑄塗法、旋轉塗佈法、刮刀塗佈法、浸漬塗佈法、輥塗佈法、棒塗佈法、模具塗佈法、噴墨法、印刷法(凸版、凹版、平版、網板印刷等)等，視目的可適當地使用此等。 　　[0049] 加熱溫度雖通常為40~500℃左右，但300℃以下較佳。若超過300℃，則有所得之膜變脆，特別是不能得到適合顯示器基板用途之膜之情形。 　　又，若考慮所得之膜的耐熱性與線膨脹係數特性，則以經塗佈之膜形成用組成物或聚醯亞胺膜形成用組成物以40℃~100℃加熱5分鐘~2小時後，直接逐步地使加熱溫度上升，最終以超過175℃~280℃加熱30分鐘~2小時為宜。如此，藉由以使溶劑乾燥之階段與促進分子配向之階段的2階段以上的溫度進行加熱，可使其表現低熱膨脹特性。 　　特別是，經塗佈之膜形成用組成物，以40℃~100℃加熱5分鐘~2小時加熱後，以超過100℃~175℃加熱5分鐘~2小時，接著，以超過175℃~280℃加熱5分鐘~2小時較佳。 　　又，含有聚醯胺酸之聚醯亞胺膜形成用組成物之情形中，加熱塗膜，為使溶劑蒸發同時使其進行醯亞胺化反應，例如，可以40~100℃之範圍、100~150℃之範圍、180~300℃之範圍等逐步地加熱。 　　用於加熱之器具，可舉例例如加熱板、烘箱等。加熱氛圍，可為空氣亦可為氮等之惰性氣體下，又，可為常壓下亦可為減壓下，又，加熱之各階段中可適用不同的壓力。 　　[0050] 膜之厚度，特別是作為可撓性顯示器用之基板之情形中，通常為1~60μm左右，較佳為5~50μm左右，調整加熱前之塗膜的厚度形成期望之厚度的膜。 　　此外，作為將如此所形成之膜自基材剝離的方法並無特別限定，可舉例將該膜與基材一起冷卻，於膜切割切口進行剝離的方法或透過輥施予張力進行剝離的方法等。 　　[0051] 然後，由前述膜形成用組成物或聚醯亞胺膜形成用組成物所形成之膜而成之可撓性裝置用基板，即，由前述膜形成用組成物或聚醯亞胺膜形成用組成物之硬化物(膜形成用組成物之固形分的硬化物)或聚醯亞胺膜形成用組成物之硬化物(聚醯亞胺膜形成用組成物之固形分中的聚醯胺酸之醯亞胺化物)而成之可撓性裝置用基板，亦為本發明之對象。 [實施例] 　　[0052] 以下雖舉出實施例更詳細地說明本發明，但本發明並不限定於此等。 　　此外，使用之試藥的簡稱如下 　　TH：三苯荑氫醌(9,10-二氫-9,10-[1,2]苯并蒽-1,4-二醇) 　　HTAC：無水核水添偏苯三甲醯氯(Hydrogenated trimellitic anhydride chloride) 　　TH-HTAC-CA：三苯荑氫醌 HTAC羧酸 　　TH-HTAC：三苯荑氫醌 HTAC 　　THF：四氫呋喃 　　CBDA：1,2,3,4-環丁烷四羧酸二酐 　　TFMB：2,2’-二(三氟甲基)聯苯胺 　　BODAxx：雙環[2,2,2]辛烷-2,3,5,6-四羧酸二酐 　　[0053] 又，試料之調製及物性之分析及用於評估的裝置及其條件如下。 　　1)HPLC分析 　　管柱：Inertsil ODS-3、5μm、4.6mm×250mm 　　烘箱：40℃ 　　檢測波長：254nm 　　流速：1.0mL/分 　　溶析液： 　　TH-HTAC-CA：乙腈/0.5%磷酸水溶液=50/50 樣本注入量：5μL 　　TH-HTAC：乙腈/0.5%磷酸水溶液=50/50 樣本注入量：5μL※ 　　※將TH-HTAC以溶析液稀釋100倍，以70℃攪拌1小時後，作為TH-HTAC-CA來測定 　　2)1 HNMR分析 　　裝置：傅立葉轉換型超導核磁共振裝置(FT-NMR)(INOVA-400(Varian公司)400MHz 　　溶劑：DMSO-d6 　　內標準物質：四甲基矽烷(TMS) 　　[0054] [1]化合物之合成 ＜實施例1-1＞(TH-HTAC-CA之合成)
Figure 02_image054
[0055] 氮氛圍下，將TH(30g)、HTAC(68.1g)溶解於四氫呋喃(THF，300g)中，冷卻至5℃。於此溶液中，耗費30分鐘滴入吡啶(24.9g)與四氫呋喃(90g)之混合溶液，以四氫呋喃(30g)清洗溶液。攪拌19小時後，將反應溶液冷卻至5℃，加入水(1260g)，升溫至25℃後，攪拌30分鐘。將析出物過濾後，以水(90g)洗淨3次，將所得之濾取物(121.4g)以70℃進行減壓乾燥，得到TH-HTAC粗產物82.5g。 　　接著將此TH-HTAC粗產物(82.5g)加至乙酸乙酯(787g)及0.5%磷酸水溶液(787g)的混合溶液中，將此懸濁溶液在回流條件下(78℃)攪拌6小時，使該粗產物完全溶解。將此溶液冷卻至25℃後，去除水層後，於有機層中加入水(700g)，攪拌30分鐘後，去除水層。將所得之有機層濃縮後，以70℃進行減壓乾燥，得到TH-HTAC-CA粗產物82.5g。將此TH-HTAC-CA粗產物(82.5g)加至乙腈(339g)中，升溫至70℃攪拌1小時後，冷卻至5℃。將析出物過濾後，以乙腈(339g)洗淨2次，藉由將所得之濾取物以70℃進行減壓乾燥得到TH-HTAC-CA異構物混合物37.9g(收率：53.0%(2Steps)，HPLC面積百分率(滯留時間：4.9min, 5.1min, 5.6min, 6.2min, 6.4min)：96.5%)。 　　[0056] ＜實施例1-2＞(TH-HTAC之合成) 　　將TH-HTAC-CA(37.9g)加至乙酸酐(114g)中，在回流條件下(130℃)攪拌30分鐘後，將反應液冷卻至25℃。將析出物在氮氣流化過濾後，將過濾物以乙酸酐(38g)洗淨。所得之未乾燥的過濾物中加入己烷，以130℃進行減壓乾燥得到TH-HTAC 31.0g。(收率：86.3%，HPLC面積百分率(滯留時間：4.9min, 5.6min, 6.4min)：96.8%)。 　　此結晶，由藉由1 HNMR分析及HPLC之分析結果，確認為TH-HTAC異構物混合物(35.1：35.5：26.3)。1 HNMR(DMSO-d6、δppm)：7.4(m, 4H)、7.0(m, 4H)、6.9(m, 2H)、5.6(m, 2H)、3.7(m, 2H)、3.4(m, 2H)、3.0(m, 2H)、2.5(m, 2H)、2.2-1.7(m, 10H)。 　　[0057] [2]聚醯亞胺之製造 ＜實施例1-3聚醯亞胺(III)之製造[TH-HTAC：CBDA：BODAxx：TFMB=10：40：50：100(莫耳比)]
Figure 02_image056
具有氮注入/排出口且連接迪恩-斯塔克裝置及機械攪拌器之250mL三口反應燒瓶內，放入TFMB 6.4046g(0.02莫耳)。之後立刻加入γ-丁內酯(GBL)16.474g，開始攪拌。TFMB完全溶解於溶劑後，將BODAxx 2.5g(0.01莫耳)與GBL 14.12g及1-乙基哌啶 1.024g一起加入，在氮氛圍下，加熱至150℃3小時。之後，將TH-HTAC1.2932g(0.002莫耳)與GBL 7.06g一起加入，氮氛圍下，以140℃使其反應1小時。之後，於反應混合物中加入CBDA 1.568g(0.008莫耳)、GBL 9.41g及1-乙基哌啶 0.23g，將溫度上升至180℃使其反應3小時。之後，以固形分濃度成為15質量%之方式加入GBL稀釋反應混合物，使經稀釋之反應混合物進一步反應4小時，之後，以固形分濃度成為12質量%之方式加入GBL。 　　接著，將所得之反應混合物加至500g之甲醇中攪拌30分鐘，藉由過濾回收析出物之聚醯亞胺。此操作重複3次。 　　最後，將所得之聚醯亞胺中的甲醇殘渣藉由真空烘箱，以120℃進行乾燥8小時，得到經乾燥之聚醯亞胺(III)(10.5g，收率：95.1%)。 　　[0058] [3]聚醯亞胺溶液(清漆)之調製及聚醯亞胺膜之製作 　　於室溫，將前述聚醯亞胺(III)3g，以固形分濃度成為12質量%之方式溶解於N-甲基-2-吡咯啶酮(NMP)中，將所得之聚醯亞胺溶液，使用5μm之過濾器進行加壓過濾。 　　之後，將經過濾之聚醯亞胺溶液塗佈於玻璃基板上，大氣下，以50℃30分鐘、140℃30分鐘、200℃60分鐘，依序加熱，得到透明之聚醯亞胺的膜。然後，將所得之聚醯亞胺的膜以機械性切斷剝離後作為評估試料。 　　[0059] 關於以上述程序製作之薄膜(評估試料)的耐熱性及光學特性，即，50℃至200℃及200℃至250℃中之線熱膨脹係數(CTE)、光線透過率(T400nm 、T550nm )、5%重量減少溫度(Td5% )、CIE b＊ 值(黃色評估)、延遲(Rth 、R0 )以及雙折射(Δn)，依循下述程序分別評估。又，關於上述聚醯亞胺之數平均分子量及重量平均分子量，亦依循下述程序進行測定。結果表示於表1。 　　[0060] 1)CIE b值(CIE b＊ ) 　　CIE b值(CIE b＊ )，使用日本電色工業(股)製SA4000光譜儀，於室溫，參考值定為空氣來進行測定。 2)光線透過率(透明性)(T400nm 、T550nm ) 　　波長400nm及550nm之光線透過率(T400nm 、T550nm [%])，使用(股)島津製作所 紫外可視分光光度計UV-Visible 3600，於室溫，參考值定為空氣來進行測定。 3)延遲(Rth 、R0 ) 　　使用王子計測機器(股)製 KOBURA 2100ADH，於室溫測定厚度方向延遲(Rth )及面內延遲(R0 )。 　　此外，厚度方向延遲(Rth )及面內延遲(R0 )記由以下算式來算出。 　　R0 =(Nx-Ny)×d=ΔNxy×d 　　Rth =[(Nx＋Ny)/2-Nz]×d=[(ΔNxz×d)＋(ΔNyz×d)/2 　　Nx、Ny：面內之正交的2個折射率(Nx＞Ny，Nx亦稱為慢軸，Ny亦稱為快軸) 　　Nz：對於面厚度(垂直)方向的折射率 　　d：膜厚 　　ΔNxy：面內之2個折射率的差(Nx-Ny)(雙折射) 　　ΔNxz：面內之折射率Nx與厚度方向之折射率Nz的差(雙折射) 　　ΔNyz：面內之折射率Ny與厚度方向之折射率Nz的差(雙折射) 4)線膨脹係數(CTE) 　　將各評估試料切成寬度5mm、長度16mm之尺寸，將此使用TA Instruments公司製TMA Q400，首先以10℃/min升溫在50℃至300℃加熱(第一加熱)，接著以10℃/min降溫冷卻至30℃後，藉由測定以10℃/min升溫在30℃至410℃加熱(第二加熱)時之第二加熱之50℃至200℃，以及200℃至250℃中之線膨脹係數(CTE[ppm/℃])的值來求得。此外，在第一加熱、冷卻及第二加熱過程中，添加荷重0.05N。 5)5%重量減少溫度(Td5% ) 　　5%重量減少溫度(Td5% [℃])，係藉由使用TA Instruments公司製 TGA Q500，在氮中，將樹脂薄膜約5至10mg以10℃/min在50至800℃升溫進行測定來求得。此外，將150℃中之重量定為重量減少0%。 6)膜厚 　　所得樹脂薄膜之膜厚，藉由(股)TECLOCK製 測厚儀來測定。 7)面內雙折射(Δn) 　　使用由前述之＜3)延遲＞所得之厚度方向延遲(Rth )的值，藉由以下之算式算出。 　　ΔN=[Rth /d(薄膜膜厚)]/1000 8)數平均分子量(Mn)及重量平均分子量(Mw) 　　數平均分子量(以下簡稱Mn)與重量平均分子量(以下簡稱Mw)，係將經以聚四氟乙烯(PTFE)製0.45μm之過濾器過濾之聚合物試料，藉由裝置：昭和電工(股)製 Showdex GPC-101、管柱：KD803及KD805、管柱溫度：50℃、溶出溶劑：DMF、流量：1.5ml/分鐘、校正曲線：標準聚苯乙烯之條件來測定。 　　[0061]
Figure 02_image058
[0062] 如表1所示，使用本發明之新穎之酸二酐製作之聚醯亞胺膜，得到厚度方向之延遲Rth 為未達500nm之值，面內延遲R0 具有未達5之非常低的值之結果。又，波長400nm中之透過率(T400nm )與波長550nm中之透過率(T550nm )，然後50℃-200℃中之CTE值與200℃-250℃中之CTE值，分別為不同之值。然後如Td5% 值所示，確認了具有高耐熱性。 　　本發明之新穎之酸二酐，被認為藉由破壞共軛系帶來為了光傳送之更大的自由體積之龐大構造而具有特異性之序列方向，然後認為該情形在聚醯亞胺膜中，帶來透過率及延遲(相位差)優異的性能。 　　如此，由使用本發明之新穎之酸二酐製造之聚醯亞胺膜，具有高透明性(高光線透過率)及耐熱性，然後低延遲之特性，即為滿足作為可撓性顯示器基板的基膜所必須的要件者，可期待可特別適合用作為可撓性顯示器基板的基膜。[0009] The present invention is described in further detail below. The polyamide acid of the present invention is obtained by polycondensation reaction of an acid dianhydride component containing an acid dianhydride represented by the following formula (1-1) and a diamine component. Then, the obtained polyimide can be converted into the corresponding polyimide by using heat or a catalyst for dehydration and ring-closure reaction. Not only the polyamide acid, but also the polyimide is also the object of the present invention. In addition, the polyimide of the present invention is a reaction product of an acid dianhydride component and a diamine component containing the acid dianhydride represented by the following formula (1-1), and the polyimide of the present invention is The aforementioned polyimide of polyamide. [0010] As the acid dianhydride represented by the formula (1-1), the acid dianhydride represented by the formula (1-2) is particularly preferred, and among them, if good reproducibility is considered, heat resistance and flexibility are imparted The polyimide acid and the corresponding polyimide of the polyimide film having excellent transparency and low retardation are preferably the acid dianhydride represented by formula (1-3).
Figure 02_image032
(In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are independent of each other and represent a halogen atom, an alkyl group with 1 to 5 carbon atoms or an alkoxy group with 1 to 5 carbon atoms, R 6 and R 7 are independent of each other, representing a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, a and b are independent of each other, representing an integer from 0 to 4, and c and d are independent of each other , Represents an integer from 0 to 9, and e represents an integer from 0 to 2). [0011] As the above-mentioned halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. can be exemplified. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, sec-isopentyl and cyclopentyl, etc. As the alkoxy group having 1 to 5 carbon atoms, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group can be exemplified. , Tert-butoxy, n-pentoxy, isopentoxy, neopentoxy and tert-pentoxy, etc. [0012] The acid dianhydrides represented by the above formulas (1-1) to (1-3) of the present invention can be respectively combined with the tetracarboxylic acids represented by the following formulas (2-1) to (2-3) Dehydrating agent is obtained by dehydrating in the molecule.
Figure 02_image034
(In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , a, b, c, d, and e have the same meaning as above). [0013] Specifically, the acid dianhydride represented by the above formula (1-1), as shown in the following scheme, can be used in an organic solvent to make 9,10-[1,2]benzoanthracene-1 ,4-diol compound (9,10-[1,2]benzenoanthracene-1,4-diol) (hereinafter referred to as benzoanthracene diol compound) and cyclohexanetricarboxylic acid halogenated anhydride in alkali or acid absorbent In the presence of the reaction to obtain [Reaction Formula 1]. After the reaction, after the solvent is removed, the reaction mixture is purified by well-known methods such as recrystallization, distillation, silica gel column chromatography, etc., to obtain the target acid dianhydride. It is also possible to hydrolyze the reactant of [Reaction Formula 1] to obtain the intermediate (9,10-[1,2]benzoanthracene-1,4-diyl bis(cyclohexanetricarboxylate) compound) ( The compound represented by the formula (2-1)) [Reaction formula 2], this intermediate is obtained by dehydrating the intermediate in the molecule with a dehydrating agent [Reaction formula 3]. In addition, the acid dianhydrides represented by the above formulas (1-1)~(1-3) and the intermediates of the cyclohexane tricarboxylic acid esters represented by the above formulas (2-1)~(2-3) (four Carboxylic acid compounds) are also objects of the present invention.
Figure 02_image036
(In the above reaction formula, X represents a halogen atom, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , a, b, c, d, and e have the same meaning as above). [0014] In the reaction of the above [Reaction Formula 1], the feed ratio of the benzanthracene diol compound to the cyclohexane tricarboxylic acid halogenated anhydride is cyclohexane relative to 1 mol of the benzoanthracene diol compound. The halogenated anhydride of alkanetricarboxylic acid is preferably 2 to 4 moles. As the base, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, and pyridine are suitably used. , 4-Dimethylaminopyridine and N-methylmorpholine and other organic bases such as organic amines. In addition, the amount of alkali used is not particularly limited as long as it is 1 mol or more with respect to 1 mol of cyclohexanetricarboxylic acid halogenated anhydride, but it is usually about 1 to 5 mol, preferably 1 to 3 Mo Er around. In addition, in order to neutralize acids such as hydrochloric acid by-produced in the reaction, an acid absorbent may also be used. As the acid absorbent, epoxy compounds such as propylene oxide can be exemplified. The amount of the acid absorbent used is not particularly limited as long as it is 2 mol or more relative to 1 mol of the benzoanthracene diol compound, but it is usually about 2-10 mol, preferably 2-4 mol about. The organic solvent is not particularly limited as long as it does not affect the reaction, but aromatic hydrocarbons such as benzene, toluene, and xylene can be used; N,N-dimethylformamide (hereinafter referred to as DMF) , N,N-dimethylacetamide (hereinafter referred to as DMAc) and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and other amides; diethyl ether, tetrahydrofuran (hereinafter referred to as THF), 1,4-bis
Figure 106133364-A0304-12-0015-1
Ethers such as alkane, 1,2-dimethoxyethane, cyclopentyl methyl ether and diethyl ether; ketones such as 2-butanone and 4-methyl-2-pentanone; acetonitrile, etc. The nitriles and dimethyl sulfoxide (hereinafter referred to as DMSO) and so on. These solvents can be used alone or in combination of two or more kinds. In addition, the direct target acid dianhydride (1-1) in [Reaction formula 1] is purified. When taking out, if the solvent contains a lot of water, it will cause the hydrolysis of the ester. Therefore, the solvent is a dehydration solvent, or after dehydration It is better to use again. In addition, when extracting the target acid dianhydride (1-1) through [Reaction Formula 2] and [Reaction Formula 3], a dehydration solvent may or may not be used. Although the reaction temperature can be set at about 0 to 200°C, 20 to 150°C is preferred. After the reaction, the solvent is distilled off, and the target acid dianhydride is obtained by purifying the reactant. This purification method is arbitrary, and can be appropriately selected from known methods such as recrystallization, distillation, and silica gel column chromatography. In addition, the organic solvent used in the purification is not particularly limited as long as it is a solvent that does not react with the product during purification, and is the same as the organic solvent used in the above-mentioned reaction. In addition, when purification after the reaction is difficult, the target acid dianhydride can be obtained by directly hydrolyzing the crude product [Reaction Formula 2] to obtain the tetracarboxylic acid and then dehydrating and cyclizing it with a dehydrating agent [Reaction Formula 3]. [0015] On the other hand, the reaction of the above-mentioned [Reaction formula 2] is not particularly limited as long as the acid dianhydride represented by the formula (1-1) is mixed with water, but for example, by mixing in [Reaction formula 1] The resulting formula (1-1) is added with water, optionally with organic solvents, acids or bases, and heated to reflux for hydrolysis to obtain the cyclohexane tricarboxylic acid ester (tetracarboxylic acid compound) represented by formula (2-1) ). With respect to the acid dianhydride represented by the formula (1-1), water is generally used at 2-100 mass times, preferably 2-40 mass times, and more preferably 2-6 mass times. In addition, an organic solvent may be added to the above-mentioned reaction. The organic solvent is not particularly limited as long as it does not affect the reaction, but aromatic hydrocarbons such as benzene, toluene, and xylene can be used; N,N-dimethylformamide (hereinafter referred to as DMF) , N,N-dimethylacetamide (hereinafter referred to as DMAc) and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and other amides; diethyl ether, tetrahydrofuran (hereinafter referred to as THF), 1,4-bis
Figure 106133364-A0304-12-0015-1
Ethers such as alkane, 1,2-dimethoxyethane, cyclopentyl methyl ether and diethyl ether; acetone, ethyl acetate, 2-butanone and 4-methyl-2-pentanone, etc. Ketones; nitriles such as acetonitrile; and dimethyl sulfoxide (hereinafter referred to as DMSO) and so on. These solvents can be used alone or in combination of two or more kinds. In addition, in order to efficiently carry out the hydrolysis, it is better to use a solvent with high polarity, such as DMF, DMAc, NMP, THF, 1,4-bis
Figure 106133364-A0304-12-0015-1
Alkanes, diethyl ether, acetonitrile, acetone, ethyl acetate, etc. are preferred. In addition, acid may be added to the above-mentioned reaction. Although the acid is not particularly limited, examples of the acid include heteropoly acids such as phosphomolybdic acid and phosphotungstic acid; organic acids such as trimethylborate and triphenylphosphine; inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; Hydrocarbon acids such as formic acid, acetic acid, propionic acid and p-toluenesulfonic acid; and halogen-based hydrocarbon acids such as trifluoroacetic acid. Preferably, hydrochloric acid, sulfuric acid, acetic acid, and p-toluenesulfonic acid can be exemplified. With respect to the acid dianhydride represented by the formula (1-1), the acid is usually used at 0 to 100 times mol, preferably 0.01 to 10 times mol. In addition, this reaction can also be hydrolyzed using an alkaline aqueous solution. Although the base is not particularly limited, examples of the base include alkali metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate and lithium carbonate, and alkaline earth metals such as magnesium hydroxide and calcium hydroxide. . Among them, preferred are sodium hydroxide, potassium hydroxide, and lithium hydroxide. The usage amount of the base is usually 0-100 times mol, preferably 0.01-10 times mol relative to the acid dianhydride represented by the formula (1-1). Although the reaction temperature is not particularly limited, it is, for example, -90 to 200°C, preferably 50 to 130°C. The reaction time is usually 0.1 to 200 hours, preferably 0.5 to 100 hours. [0016] In addition, the reaction of the above [Reaction Formula 3] is not particularly limited as long as a known method is used, but for example, the cyclohexane represented by the formula (2-1) obtained by [Reaction Formula 2] The tricarboxylic acid ester (tetracarboxylic acid compound) and the dehydrating agent are mixed in a solvent to obtain the acid dianhydride represented by the formula (1-1). [0017] As the dehydrating agent, although it is not particularly limited as long as the cyclohexane tricarboxylic acid ester (tetracarboxylic acid compound) represented by the formula (2-1) can be contacted with the dehydrating agent, for example, the dehydration may be in ethyl alcohol. The presence of aliphatic carboxylic acid anhydrides such as acid anhydride, propionic anhydride, trifluoroacetic anhydride, 1,3-dicyclohexylcarbodiimide, 2-chloro-1,3-dimethylimidazolinium chloride, etc. Next implementation. In addition, lower carboxylic acid anhydrides having 1 to 3 carbon atoms are preferred, and lower carboxylic acid anhydrides having carbon numbers 1 to 2 are more preferred. Among them, acetic anhydride is particularly preferred from the point of view that it is easy to remove after anhydrous and is economically advantageous. . [0018] Although the amount of the dehydrating agent used is not particularly limited, it is preferably 2-50 equivalents relative to the cyclohexanetricarboxylic acid ester (tetracarboxylic acid compound) represented by formula (2-1). It is 4-20 equivalents. If it is 2-50 equivalents, the anhydride will proceed sufficiently, and the amount of the acid dianhydride represented by the formula (1-1) obtained will not increase too much, and the formula (1-1) can be made in a high yield. The acid dianhydride shown is precipitated. [0019] The above reaction can also use organic solvents that do not directly participate in the reaction. Examples include hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as 1,2-dichloroethane, 1,2-dichloropropane, and 1,4-dichloropropane.
Figure 106133364-A0304-12-0015-1
Ethane etc. [0020] In addition, it is not necessary to completely dissolve the cyclohexane tricarboxylic acid ester (tetracarboxylic acid compound) represented by the formula (2-1) in a homogeneous system to carry out the anhydride reaction, and it may be carried out in a heterogeneous system. Anhydride reaction. [0021] The heating temperature in the reaction is preferably 30 to 200°C, more preferably in the range of 40 to 180°C. The higher the reaction temperature, the higher the reaction rate. Therefore, it is better to use the reflux temperature of the solvent. [0022] In addition, although the reaction time can be appropriately set according to the type of dehydrating agent used, temperature and other conditions, it is preferably 0.5 to 20 hours. [0023] Through the above anhydride reaction, a suspension of the acid dianhydride represented by formula (1-1) can be obtained in the dehydrating agent used. After the anhydride reaction, the powder of the acid dianhydride represented by formula (1-1) can be recovered by filtering the resulting suspension. In addition, the above-mentioned suspension may be concentrated if necessary. Furthermore, if necessary, the above-mentioned filtrate may be washed with an organic solvent. Although the cleaning solvent is not particularly limited as long as it does not react with the anhydride, and the solubility of the target anhydride is low, it can be exemplified by toluene, hexane, heptane, acetonitrile, acetone, chloroform, ethyl acetate, and dicarbonate. Methyl esters, etc. or mixed solvents of these, etc. Among them, ethyl acetate and dimethyl carbonate are preferred. Furthermore, by removing the dehydrating agent or solvent by vacuum drying or the like, a high-purity acid dianhydride represented by formula (1-1) can be obtained. In addition, if necessary, the target acid dianhydride can be obtained by performing purification by using known methods such as recrystallization, distillation, silica gel column chromatography, and the like. [0024] In addition, the acid dianhydride represented by the formula (2-1) obtained in the present invention is a novel compound not described in the literature. As described above, it can be used to easily produce the formula (1-1) Shown in various uses such as acid dianhydride. [0025] In addition, the benzanthracene diol compound used in the present invention, for example, as shown in the following scheme, the anthracene compound can be combined with 1,4-benzene in an organic solvent by following a known method. The 9,10-[1,2]benzanthracene-13,16(9H,10H)-dione compound obtained by the Diels-Alder reaction of the quinone compound, in the presence of 47% hydrogen bromide in an acetic acid solvent, The heating conditions are processed.
Figure 02_image038
(In the above scheme, R 1 , R 2 , R 5 , R 6 , R 7 , a, b, and e have the same meaning as above). [0026] From the viewpoint of obtaining polyimide films (and corresponding polyimides) that are not only excellent in heat resistance, flexibility, and transparency, but also have low retardation characteristics with good reproducibility It can be seen that the acid dianhydride component used to manufacture the polyamide acid (and the corresponding polyimide) of the present invention, in addition to the acid dianhydride represented by the above formula (1-1), preferably contains an alicyclic The tetracarboxylic dianhydride more preferably contains an acid dianhydride represented by the following formula (C1).
Figure 02_image040
[In the formula, B 1 represents a 4-valent base selected from the group formed by the free formulas (X-1)~(X-12);
Figure 02_image042
(In the formula, plural Rs are independent of each other and represent a hydrogen atom or a methyl group, and * represents a bonding site)]. [0027] Among the acid dianhydrides represented by the above formula (C1), B 1 in the formula is the above formula (X-1), (X-2), (X-4), (X-5), ( The acid dianhydrides represented by X-6), (X-7), (X-8), (X-9), (X-11) and (X-12) are preferred, and the aforementioned B 1 is the aforementioned formula ( The acid dianhydrides represented by X-1), (X-2), (X-6), (X-11) and (X-12) are particularly preferred. In addition, within the range that does not impair the effect of the present invention, among the acid dianhydride components, other than the acid dianhydride represented by the above formula (1-1) and the acid dianhydride represented by the above formula (C1) may also be used. Other acid dianhydrides. [0028] Among the above acid dianhydride components, when an alicyclic tetracarboxylic dianhydride is used together with the acid dianhydride represented by the above formula (1-1) of the present invention, the above formula (1-1) is The ratio of the acid dianhydride to the alicyclic tetracarboxylic dianhydride is usually the acid dianhydride shown in the above formula (1-1): alicyclic tetracarboxylic dianhydride=1:0.5~1:4. By being in such a range, the polyimide imparting polyimide with high heat resistance, high flexibility, high transparency, and low delay can be obtained with good reproducibility. [0029] From the viewpoint that the polyimide film (and the corresponding polyimide) is provided with a polyimide film that is not only excellent in heat resistance, flexibility, and transparency, but also has low retardation characteristics with good reproducibility It can be seen that the diamine component used to manufacture the polyamide acid (and the corresponding polyimide) of the present invention preferably contains an aromatic diamine, and more preferably contains a diamine represented by the following formula (A1) .
Figure 02_image044
(In the formula, B 2 represents a divalent base selected from the group formed by the free formula (Y-1) ~ formula (Y-34);
Figure 02_image046
Figure 02_image048
(In the formula, * represents the bonding point). [0030] Among the diamines represented by the above formula (A1), B 2 in the formula is the above formula (Y-12), (Y-13), (Y-14), (Y-15), (Y -18), (Y-27), (Y-28), (Y-30) and (Y-33) are preferably diamines, and the aforementioned B 2 is the aforementioned formula (Y-12), (Y- 13) The diamines shown in (Y-14), (Y-15) and (Y-33) are particularly preferred. Moreover, in the range which does not impair the effect of this invention, other diamine compounds other than the diamine represented by the said formula (A1) can also be used for the said diamine component. [0031] From the viewpoint of obtaining a polyimide film with high heat resistance, high flexibility, high transparency, and low retardation with good reproducibility (and the corresponding polyimide), use The content of aromatic diamine in the diamine component of the polyamide acid (and corresponding polyimide) of the present invention is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol %, still more preferably 80 mol%, still more preferably 90 mol%, and most preferably 100 mol%. [0032] In addition, the acid dianhydride represented by the above formula (1-1) and the acid dianhydride represented by the above (C1) are used as the above acid dianhydride component, and the above formula (A1) is used as the above diamine component In the case of diamine, polyamide acid has a monomer unit represented by the following formula (4-1) and a monomer unit represented by the following formula (4-2).
Figure 02_image050
(In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , a, b, c, d, e, B 1 and B 2 have the same meaning as above). [0033] The method for obtaining the polyamide acid of the present invention is not particularly limited, as long as the aforementioned acid dianhydride component and diamine component are reacted and polymerized by a known method. The ratio of the molar number of the acid dianhydride component to the molar number of the diamine component when synthesizing polyamide acid is the acid dianhydride component/diamine component=0.8~1.2. [0034] As a solvent used in the synthesis of polyamide acid, for example, m-cresol, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF) , N,N-dimethylacetamide (DMAc), N-methylcaprolactam, dimethyl sulfide (DMSO), tetramethylurea, pyridine, dimethyl sulfide, hexamethylphosphoramide And γ-butyrolactone and so on. These can be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve polyamic acid, it can add to the said solvent and use within the range which obtains a uniform solution. The temperature of the polycondensation reaction can be selected from -20 to 150°C, preferably any temperature from -5 to 100°C. [0035] The polyimide-containing solution obtained by the polymerization reaction of the above-mentioned polyimide acid can be used as a composition for forming a polyimide film described later as it is, or after being diluted or concentrated. In addition, in the solution containing polyamide, poor solvents such as methanol and ethanol are added to precipitate the polyamide for isolation, and the isolated polyamide is re-dissolved in a suitable solvent as the polyamide containing A solution of amide acid, which can be used as a composition for forming a polyimide film. The solvent for diluting the solution containing polyamide and the solvent for redissolving the isolated polyamide acid are not particularly limited as long as they dissolve the obtained polyamide acid. Examples include m-cresol, 2-pyrrolidone, NMP, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, DMAc, DMF and γ-butyrolactone, etc. [0036] In addition, even if the solvent cannot dissolve the polyamic acid alone, it can be added to the above-mentioned solvent as long as it is in a range where the polyamic acid does not precipitate. As specific examples thereof, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2- Propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol- 1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, Ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. [0037] The polyimide of the present invention can be obtained by performing dehydration ring closure (thermal imidization) of the polyimide described above by heating, or chemically closing the ring using a known dehydration ring-closing catalyst. The heating method can be performed at a temperature of 100 to 300°C, preferably 120 to 250°C. The method of chemically closing the ring, for example, can be carried out in the presence of pyridine, triethylamine or 1-ethylpiperidine, etc., and acetic anhydride, etc. The temperature at this time can be selected from any temperature of -20~200℃ . [0038] The thus obtained polyimide obtained from the polyamide acid having the monomer unit represented by the above formula (4-1) and the monomer unit represented by the above formula (4-2) has A monomer unit represented by the following formula (5-1) and a monomer unit represented by the following formula (5-2).
Figure 02_image052
(In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , a, b, c, d, e, B 1 and B 2 have the same meaning as above). [0039] The polyimide-containing solution (hereinafter also referred to as polyimide solution) obtained by the above-mentioned polyimide ring-closing reaction can be used directly, or after dilution or concentration, for the film formation described below Composition to use. In addition, in the solution containing polyimine, poor solvents such as methanol and ethanol are added to precipitate the polyimine to separate the polyimine, and the separated polyimine is appropriately re-dissolved In a solvent, it can be used as a film forming composition described later. The solvent for re-dissolution is not particularly limited as long as it dissolves the obtained polyimide. Examples include m-cresol, 2-pyrrolidone, NMP, N-ethyl-2-pyrrolidone, and N- Vinyl-2-pyrrolidone, DMAc, DMF and γ-butyrolactone, etc. [0040] Also, even if it is a solvent that does not dissolve polyimine alone, it can be added to the above-mentioned solvent for use as long as the polyimine does not precipitate out. As specific examples thereof, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2- Propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol- 1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, Ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. [0041] In addition, in the present invention, the number average molecular weight of polyamide acid and the corresponding polyimide is preferably 5,000 or more from the viewpoint of improving the flexibility and strength of the resulting film, and more preferably 7,000 or more, more preferably 10,000 or more, and from the viewpoint of ensuring the solubility of the obtained polyamide acid and the corresponding polyimide, it is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 the following. In addition, in this specification, the number average molecular weight is measured by a GPC (Gel Permeation Chromatography) apparatus, and is a value calculated as a polystyrene conversion value. [0042] [Film-forming composition·Polyimide film-forming composition] The above-mentioned film-forming composition of the present invention comprising polyimide and an organic solvent, and the present invention comprising polyimide acid The composition for forming a polyimide film with an organic solvent is also an object of the present invention. Here, the composition for forming a film of the present invention and the composition for forming a polyimide film are uniform, and no phase separation is confirmed. [0043] <Organic solvent> The film-forming composition or polyimide film-forming composition of the present invention contains an organic solvent in addition to the aforementioned polyimide or polyimide acid. The organic solvent is not particularly limited, and, for example, the same as the specific examples of the reaction solvent when the polyamide acid and polyimide are prepared. More specifically, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2- Imidazolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, etc. Moreover, an organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types. Among these, in consideration of obtaining a film with high flatness with good reproducibility, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone are preferred. [0044] The blending amount of the solid content in the film-forming composition or polyimide film-forming composition of the present invention is usually about 0.5-30% by mass, preferably about 5-25% by mass. If the solid content concentration is less than 0.5% by mass, the film forming efficiency on the film will be low, and the viscosity of the film-forming composition or the polyimide film-forming composition will become low, making it difficult to obtain a uniform coating on the surface. membrane. In addition, if the solid content concentration exceeds 30% by mass, the viscosity of the film-forming composition or the polyimide film-forming composition becomes too high, and the film-forming efficiency is still deteriorated or the surface uniformity of the coating film is insufficient. Yu. In addition, the so-called solid content refers to the total mass of components other than the organic solvent, and it is determined that even liquid monomers, etc. are included in the weight as solid content. In addition, the viscosity of the film-forming composition or the polyimide film-forming composition is appropriately set in consideration of the thickness of the film to be produced, but it is particularly good to obtain a film with a thickness of about 5-50μm with good reproducibility. For the purpose, it is usually about 500 to 50,000 mPa·s at 25°C, preferably about 1,000 to 20,000 mPa·s. [0045] In the film-forming composition or polyimide film-forming composition of the present invention, in order to impart processing characteristics or various functions, other various organic or inorganic low-molecular or high-molecular compounds can also be blended. For example, catalysts, defoamers, leveling agents, surfactants, dyes, plasticizers, particles, coupling agents, sensitizers, etc. can be used. In addition, other components are also included. In the solid content of the film-forming composition or the polyimide film-forming composition of the present invention, the ratio of the above-mentioned polyimide or polyimide can be set to 70~ 100% by mass. The film-forming composition or the polyimide film-forming composition of the present invention can be obtained by dissolving the polyimide or polyimide obtained by the above-mentioned method in the above-mentioned organic solvent. In the reaction solution after imine or polyamide, if necessary, the aforementioned organic solvent is further added. [Film] The film-forming composition of the present invention or the polyimide film-forming composition described above is applied to a substrate and then dried and heated to remove the organic solvent to obtain high heat resistance. High transparency, moderate flexibility, moderate linear expansion coefficient, and low retardation film (polyimide film). That is, by heating the above-mentioned film-forming composition (a solution containing polyimide) coated on a substrate to evaporate the solvent, a film of the invention containing polyimide can be obtained, and the film is composed of the above It is made from the solid content of the composition for film formation. Alternatively, by heating the polyimide film-forming composition (a solution containing polyamide acid) coated on a substrate to evaporate the solvent while allowing the imidization reaction to proceed, the polyimide film-forming composition containing polyimide can be obtained. The film of the present invention of the imine is composed of the solid content of the composition for forming the polyimide film, and contains the amide of the polyimide in the solid content. Then the above-mentioned film, that is, the film (thin film) containing the above-mentioned polyimide is also the object of the present invention. [0047] As the substrate used for the production of the film, for example, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resins, etc.), metals, stainless steel (SUS), wood, paper, glass, silicon wafers and slate, etc. In particular, in the case of application as a substrate material for electronic devices, from the viewpoint that existing equipment can be used, the suitable substrate is preferably glass or silicon wafer, and the resulting film shows good peelability. It is better to use glass. In addition, as the linear expansion coefficient of the applicable substrate, from the viewpoint of the warpage of the substrate after coating, it is preferably 35 ppm/°C or less, more preferably 30 ppm/°C or less, and even more preferably 25 ppm/°C or less, More preferably, it is 20 ppm/°C or less. [0048] Although the coating method of the composition for forming a film of the substrate or the composition for forming a polyimide film is not particularly limited, examples thereof include cast coating, spin coating, knife coating, and dipping. Coating method, roll coating method, bar coating method, die coating method, inkjet method, printing method (relief, gravure, lithography, screen printing, etc.), etc., can be used appropriately depending on the purpose. [0049] Although the heating temperature is usually about 40 to 500°C, it is preferably below 300°C. If it exceeds 300°C, the resulting film may become brittle, and in particular, a film suitable for display substrate applications may not be obtained. In addition, considering the heat resistance and linear expansion coefficient characteristics of the resulting film, the coated film-forming composition or polyimide film-forming composition is heated at 40°C to 100°C for 5 minutes to 2 hours. , Directly increase the heating temperature step by step, and finally heat it over 175℃~280℃ for 30 minutes~2 hours. In this way, it is possible to exhibit low thermal expansion characteristics by heating at a temperature of two or more stages of the stage of drying the solvent and the stage of promoting molecular alignment. In particular, the coated film-forming composition is heated at 40°C to 100°C for 5 minutes to 2 hours, then heated at over 100°C to 175°C for 5 minutes to 2 hours, and then heated at over 175°C to 280°C. It is better to heat it at ℃ for 5 minutes to 2 hours. In addition, in the case of a composition for forming a polyimide film containing polyamide acid, the coating film is heated to evaporate the solvent while causing the imidization reaction to proceed. For example, it may be in the range of 40-100°C, The range of ~150℃, the range of 180~300℃, etc. are heated gradually. Examples of appliances used for heating include heating plates, ovens, and the like. The heating atmosphere can be air or inert gas such as nitrogen, and can be under normal pressure or under reduced pressure, and different pressures can be applied in each stage of heating. [0050] The thickness of the film, especially when used as a substrate for a flexible display, is usually about 1 to 60 μm, preferably about 5 to 50 μm. The thickness of the coating film before heating is adjusted to form a film with a desired thickness. . In addition, there is no particular limitation on the method of peeling the film formed in this way from the base material. Examples include a method of cooling the film together with the base material and peeling at a cut slit of the film, or a method of applying tension through a roller to peel off. . [0051] Then, a flexible device substrate formed of the film formed from the aforementioned film-forming composition or polyimide film-forming composition, that is, from the aforementioned film-forming composition or polyimide The cured product of the film-forming composition (the cured product of the solid content of the film-forming composition) or the cured product of the polyimide film-forming composition (the polyimide in the solid content of the polyimide film-forming composition) Flexible device substrates made of amide acid (imide compounds) are also the object of the present invention. [Examples] [0052] Although the present invention will be explained in more detail with examples below, the present invention is not limited to these. In addition, the abbreviation of the reagent used is as follows: TH: Triphenyl hydroquinone (9,10-dihydro-9,10-[1,2]benzoanthracene-1,4-diol) HTAC: anhydrous nuclear water Hydrogenated trimellitic anhydride chloride (Hydrogenated trimellitic anhydride chloride) TH-HTAC-CA: Tribenzohydroquinone HTAC carboxylic acid TH-HTAC: Tribenzohydroquinone HTAC THF: Tetrahydrofuran CBDA: 1,2,3,4-cyclobutane Alkyltetracarboxylic dianhydride TFMB: 2,2'-bis(trifluoromethyl)benzidine BODAxx: Bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride [0053 ] In addition, the preparation of the sample, the analysis of the physical properties, the equipment used for the evaluation, and the conditions are as follows. 1) HPLC analysis column: Inertsil ODS-3, 5μm, 4.6mm×250mm Oven: 40℃ Detection wavelength: 254nm Flow rate: 1.0mL/Analysis solution: TH-HTAC-CA: Acetonitrile/0.5% phosphoric acid aqueous solution=50 /50 Sample injection volume: 5μL TH-HTAC: Acetonitrile/0.5% phosphoric acid aqueous solution=50/50 Sample injection volume: 5μL※ ※TH-HTAC is diluted 100 times with eluent and stirred at 70°C for 1 hour, and it is regarded as TH -HTAC-CA to measure 2) 1 HNMR analysis device: Fourier transform superconducting nuclear magnetic resonance (FT-NMR) (INOVA-400 (Varian) 400MHz Solvent: DMSO-d6 Internal standard substance: Tetramethylsilane (TMS) [0054] [1] Synthesis of compound <Example 1-1> (Synthesis of TH-HTAC-CA)
Figure 02_image054
[0055] Under a nitrogen atmosphere, TH (30 g) and HTAC (68.1 g) were dissolved in tetrahydrofuran (THF, 300 g) and cooled to 5°C. In this solution, a mixed solution of pyridine (24.9g) and tetrahydrofuran (90g) was dropped over 30 minutes, and the solution was washed with tetrahydrofuran (30g). After stirring for 19 hours, the reaction solution was cooled to 5°C, water (1260 g) was added, and the temperature was raised to 25°C, followed by stirring for 30 minutes. After filtering the precipitate, it was washed with water (90 g) three times, and the obtained filtrate (121.4 g) was dried under reduced pressure at 70°C to obtain 82.5 g of a TH-HTAC crude product. Then the TH-HTAC crude product (82.5g) was added to a mixed solution of ethyl acetate (787g) and 0.5% phosphoric acid aqueous solution (787g), and the suspension solution was stirred under reflux conditions (78°C) for 6 hours. The crude product was completely dissolved. After cooling this solution to 25°C, after removing the water layer, water (700 g) was added to the organic layer, and after stirring for 30 minutes, the water layer was removed. After concentrating the obtained organic layer, it was dried under reduced pressure at 70°C to obtain 82.5 g of TH-HTAC-CA crude product. The TH-HTAC-CA crude product (82.5g) was added to acetonitrile (339g), the temperature was raised to 70°C and stirred for 1 hour, and then cooled to 5°C. After filtering the precipitate, it was washed twice with acetonitrile (339g), and the obtained filtrate was dried under reduced pressure at 70°C to obtain 37.9g of a TH-HTAC-CA isomer mixture (yield: 53.0% ( 2Steps), HPLC area percentage (retention time: 4.9min, 5.1min, 5.6min, 6.2min, 6.4min): 96.5%). <Example 1-2> (Synthesis of TH-HTAC) TH-HTAC-CA (37.9g) was added to acetic anhydride (114g), and after stirring for 30 minutes under reflux conditions (130°C), the The reaction liquid was cooled to 25°C. After filtrating the precipitate under nitrogen fluidization, the filtrate was washed with acetic anhydride (38 g). Hexane was added to the obtained undried filtrate and dried under reduced pressure at 130°C to obtain 31.0 g of TH-HTAC. (Yield: 86.3%, HPLC area percentage (retention time: 4.9 min, 5.6 min, 6.4 min): 96.8%). This crystal was confirmed to be a TH-HTAC isomer mixture (35.1:35.5:26.3) from the results of 1 HNMR analysis and HPLC analysis. 1 HNMR(DMSO-d6, δppm): 7.4(m, 4H), 7.0(m, 4H), 6.9(m, 2H), 5.6(m, 2H), 3.7(m, 2H), 3.4(m, 2H) ), 3.0(m, 2H), 2.5(m, 2H), 2.2-1.7(m, 10H). [2] Production of polyimines<Example 1-3 Production of polyimines (III) [TH-HTAC: CBDA: BODAxx: TFMB=10:40:50:100 (mole ratio) ]
Figure 02_image056
6.4046g (0.02 mol) of TFMB is placed in a 250mL three-necked reaction flask with a nitrogen injection/discharge port connected to a Dean-Stark device and a mechanical stirrer. Immediately afterwards, 16.474 g of γ-butyrolactone (GBL) was added, and stirring was started. After TFMB was completely dissolved in the solvent, BODAxx 2.5g (0.01 mol) was added together with GBL 14.12g and 1-ethylpiperidine 1.024g, and heated to 150°C for 3 hours under a nitrogen atmosphere. Then, TH-HTAC 1.2932g (0.002 mol) was added together with GBL 7.06g, and it was made to react at 140 degreeC under nitrogen atmosphere for 1 hour. After that, CBDA 1.568 g (0.008 mol), GBL 9.41 g, and 1-ethylpiperidine 0.23 g were added to the reaction mixture, and the temperature was raised to 180° C. to react for 3 hours. After that, GBL was added to dilute the reaction mixture so that the solid content concentration became 15% by mass, and the diluted reaction mixture was allowed to react for a further 4 hours, and then GBL was added so that the solid content concentration became 12% by mass. Next, the obtained reaction mixture was added to 500 g of methanol and stirred for 30 minutes, and the precipitated polyimide was recovered by filtration. This operation was repeated 3 times. Finally, the methanol residue in the obtained polyimine was dried in a vacuum oven at 120° C. for 8 hours to obtain a dried polyimine (III) (10.5 g, yield: 95.1%). [3] Preparation of polyimide solution (varnish) and production of polyimide film. At room temperature, 3 g of the aforementioned polyimide (III) was dissolved so that the solid content concentration became 12% by mass In N-methyl-2-pyrrolidone (NMP), the obtained polyimide solution was filtered under pressure using a 5 μm filter. Afterwards, the filtered polyimide solution was coated on the glass substrate and heated in sequence at 50°C for 30 minutes, 140°C for 30 minutes, and 200°C for 60 minutes under the atmosphere to obtain a transparent polyimide film . Then, the obtained polyimide film was mechanically cut and peeled and used as an evaluation sample. [0059] Regarding the heat resistance and optical properties of the film (evaluation sample) produced by the above procedure, that is, the coefficient of linear thermal expansion (CTE) and light transmittance (T 400nm , T 550nm ), 5% weight loss temperature (Td 5% ), CIE b * value (yellow evaluation), retardation (R th , R 0 ), and birefringence (Δn) were evaluated separately according to the following procedures. In addition, the number average molecular weight and weight average molecular weight of the above-mentioned polyimine were also measured according to the following procedure. The results are shown in Table 1. [0060] 1) CIE b value (CIE b * ) CIE b value (CIE b * ) was measured using a SA4000 spectrometer manufactured by Nippon Denshoku Industries Co., Ltd. at room temperature and the reference value set to air. 2) Light transmittance (transparency) (T 400nm , T 550nm ) Light transmittance at wavelengths of 400nm and 550nm (T 400nm , T 550nm [%]), using (stock) Shimadzu UV-Visible Spectrophotometer UV-Visible 3600 , At room temperature, the reference value is set to air for measurement. 3) Retardation (R th , R 0 ) Using KOBURA 2100ADH manufactured by Oji Measuring Instruments Co., Ltd., the thickness direction retardation (R th ) and the in-plane retardation (R 0 ) were measured at room temperature. In addition, the thickness direction retardation (R th ) and the in-plane retardation (R 0 ) are calculated by the following formulas. R 0 =(Nx-Ny)×d=ΔNxy×d R th =[(Nx＋Ny)/2-Nz]×d=[(ΔNxz×d)＋(ΔNyz×d)/2 Nx, Ny: In-plane Two orthogonal refractive indexes (Nx>Ny, Nx is also called slow axis, Ny is also called fast axis) Nz: the refractive index in the direction of the surface thickness (vertical) d: film thickness ΔNxy: 2 refraction in the surface ΔNxz: the difference between the refractive index Nx in the plane and the refractive index Nz in the thickness direction (birefringence) ΔNyz: the difference between the refractive index Ny in the plane and the refractive index Nz in the thickness direction (Birefringence) 4) Coefficient of Linear Expansion (CTE) Cut each evaluation sample into a size of 5mm in width and 16mm in length, and use TMA Q400 manufactured by TA Instruments. First, heat at 50°C to 300°C at a temperature of 10°C/min. (First heating), and then cooling down to 30°C at 10°C/min, by measuring the heating at 30°C to 410°C at 10°C/min, the second heating is 50°C to 200°C (second heating) ℃, and the value of the coefficient of linear expansion (CTE [ppm/℃]) between 200℃ and 250℃. In addition, in the first heating, cooling, and second heating processes, a load of 0.05N was added. 5) 5% weight reduction temperature (Td 5% ) 5% weight reduction temperature (Td 5% [℃]), using TGA Q500 manufactured by TA Instruments, in nitrogen, the resin film is about 5 to 10 mg to 10 °C/min is determined by measuring the temperature at 50 to 800°C. In addition, the weight at 150°C is defined as a weight loss of 0%. 6) Film thickness The film thickness of the obtained resin film is measured with a thickness gauge made by TECLOCK. 7) In-plane birefringence (Δn) is calculated by the following formula using the value of the thickness direction retardation (R th) obtained from the aforementioned <3) retardation>. ΔN=[R th /d(film thickness)]/1000 8) Number average molecular weight (Mn) and weight average molecular weight (Mw) Number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw), the system will The polymer sample filtered with a 0.45μm filter made of polytetrafluoroethylene (PTFE), with equipment: Showdex GPC-101 made by Showa Denko Corporation, column: KD803 and KD805, column temperature: 50°C, Dissolution solvent: DMF, flow rate: 1.5ml/min, calibration curve: standard polystyrene. [0061]
Figure 02_image058
[0062] As shown in Table 1, the polyimide film made by using the novel acid dianhydride of the present invention, the thickness direction retardation R th is less than 500 nm, and the in-plane retardation R 0 is less than 5 The result of a very low value. In addition, the transmittance at a wavelength of 400nm (T 400nm ) and the transmittance at a wavelength of 550nm (T 550nm ), then the CTE value at 50℃-200℃ and the CTE value at 200℃-250℃ are different values respectively . Then, as shown by the Td 5% value, it was confirmed that it has high heat resistance. The novel acid dianhydride of the present invention is considered to have a specific sequence direction by destroying the conjugated system to bring about a larger free volume for light transmission. It is then considered that this situation is in the polyimide film , Brings excellent performance in transmittance and retardation (phase difference). In this way, the polyimide film made by using the novel acid dianhydride of the present invention has high transparency (high light transmittance) and heat resistance, and then low retardation characteristics, which is satisfactory as a flexible display substrate Those required for the base film are expected to be particularly suitable for use as a base film for flexible display substrates.

Figure 106133364-A0101-11-0003-2
Figure 106133364-A0101-11-0003-2

Claims (16)

一種聚醯胺酸，其係使酸二酐成分與二胺成分反應所得之聚醯胺酸，其特徵為前述酸二酐成分包含下述式(1-1)所示之酸二酐與脂環式四羧酸二酐，且前述二胺成分包含芳香族二胺；
Figure 106133364-A0305-02-0045-1
 (式中，R1、R2、R3、R4及R5彼此獨立，表示鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基，R6及R7彼此獨立，表示氫原子、鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基，a及b彼此獨立，表示0~4之整數，c及d彼此獨立，表示0~9之整數，e表示0~2之整數)。 A polyamide acid, which is a polyamide acid obtained by reacting an acid dianhydride component and a diamine component, and is characterized in that the acid dianhydride component comprises an acid dianhydride represented by the following formula (1-1) and a lipid Cyclic tetracarboxylic dianhydride, and the aforementioned diamine component includes an aromatic diamine;
Figure 106133364-A0305-02-0045-1
 (In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are independent of each other and represent a halogen atom, an alkyl group with 1 to 5 carbon atoms or an alkoxy group with 1 to 5 carbon atoms, R 6 and R 7 are independent of each other, representing a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, a and b are independent of each other, representing an integer from 0 to 4, and c and d are independent of each other , Represents an integer from 0 to 9, and e represents an integer from 0 to 2). 如請求項1之聚醯胺酸，其中前述芳香族二胺包含式(A1)所示之二胺，H 2 N-B 2 -NH 2 (A1)(式中，B2表示選自由式(Y-1)~式(Y-34)所成群組中之任一的基)，
Figure 106133364-A0305-02-0046-2
Figure 106133364-A0305-02-0047-3
 (式中，＊表示鍵結處)。 The polyamide acid according to claim 1, wherein the aforementioned aromatic diamine comprises a diamine represented by formula (A1), H 2 NB 2 -NH 2 (A1) (where B 2 represents selected from the formula (Y- 1)~The base of any one of the groups formed by formula (Y-34)),
Figure 106133364-A0305-02-0046-2
Figure 106133364-A0305-02-0047-3
 (In the formula, * represents the bonding point). 如請求項1或請求項2之聚醯胺酸，其中前述脂環式四羧酸二酐成分包含式(C1)所示之四羧酸二酐，
Figure 106133364-A0305-02-0047-4
 [式中，B1表示選自由式(X-1)~式(X-12)所成群組中之任一的基，
Figure 106133364-A0305-02-0047-5
 (式中，複數的R彼此獨立，表示氫原子或甲基，＊表示鍵結處)]。 Such as the polyamide acid of claim 1 or claim 2, wherein the aforementioned alicyclic tetracarboxylic dianhydride component comprises the tetracarboxylic dianhydride represented by formula (C1),
Figure 106133364-A0305-02-0047-4
 [In the formula, B 1 represents a base selected from any group formed by formula (X-1) ~ formula (X-12),
Figure 106133364-A0305-02-0047-5
 (In the formula, plural Rs are independent of each other and represent a hydrogen atom or a methyl group, and * represents a bonding site)]. 一種聚醯亞胺膜形成用組成物，其包含如請求項1至請求項3中任一項之聚醯胺酸，與有機溶劑。 A composition for forming a polyimide film, which comprises the polyimide acid of any one of claims 1 to 3, and an organic solvent. 一種聚醯亞胺膜，其係使用如請求項4之聚醯亞胺膜形成用組成物所形成者。 A polyimide film formed by using the composition for forming a polyimide film according to claim 4. 一種可撓性裝置用基板，其係由如請求項5之聚醯亞胺膜而成者。 A substrate for a flexible device, which is made of the polyimide film of claim 5. 一種聚醯亞胺，其係將如請求項1至請求項3中任一項之聚醯胺酸進行醯亞胺化而得者。 A polyimide obtained by imidizing the polyimide of any one of claim 1 to claim 3. 一種膜形成用組成物，其包含如請求項7之聚醯亞胺，與有機溶劑。 A composition for film formation, which comprises the polyimide of claim 7 and an organic solvent. 一種聚醯亞胺膜，其係使用如請求項8之膜形成用組成物所形成者。 A polyimide film formed using the film forming composition of claim 8. 一種可撓性裝置用基板，其係由如請求項9之聚醯亞胺膜而成者。 A substrate for a flexible device, which is made of the polyimide film of claim 9. 一種酸二酐，其特徵為式(1-1)所示，
Figure 106133364-A0305-02-0048-6
 (式中，R1、R2、R3、R4及R5彼此獨立，表示鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基，R6及R7彼此獨立，表示氫原子、鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基，a及b彼此獨立，表示0~4之整數，c及d彼此獨立，表示0~9之整數，e表示0~2之整數)。 An acid dianhydride characterized by the formula (1-1),
Figure 106133364-A0305-02-0048-6
 (In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are independent of each other and represent a halogen atom, an alkyl group with 1 to 5 carbon atoms or an alkoxy group with 1 to 5 carbon atoms, R 6 and R 7 are independent of each other, representing a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, a and b are independent of each other, representing an integer from 0 to 4, and c and d are independent of each other , Represents an integer from 0 to 9, and e represents an integer from 0 to 2). 如請求項11之酸二酐，其係式(1-2)所示，
Figure 106133364-A0305-02-0049-7
 (式中，R1、R2、R3、R4、R5、R6、R7、a、b、c、d及e表示與前述相同的意思)。 For example, the acid dianhydride of claim 11 is shown in formula (1-2),
Figure 106133364-A0305-02-0049-7
 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , a, b, c, d, and e have the same meaning as described above). 如請求項12之酸二酐，其係式(1-3)所示，
Figure 106133364-A0305-02-0049-8
 For example, the acid dianhydride of claim 12 is represented by formula (1-3),
Figure 106133364-A0305-02-0049-8
 一種四羧酸，其特徵為式(2-1)所示，
Figure 106133364-A0305-02-0050-9
 (式中，R1、R2、R3、R4及R5彼此獨立，表示鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基，R6及R7彼此獨立，表示氫原子、鹵素原子、碳原子數1至5之烷基或碳原子數1至5之烷氧基，a及b彼此獨立，表示0~4之整數，c及d彼此獨立，表示0~9之整數，e表示0~2之整數)。 A tetracarboxylic acid characterized by the formula (2-1),
Figure 106133364-A0305-02-0050-9
 (In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are independent of each other and represent a halogen atom, an alkyl group with 1 to 5 carbon atoms or an alkoxy group with 1 to 5 carbon atoms, R 6 and R 7 are independent of each other, representing a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, a and b are independent of each other, representing an integer from 0 to 4, and c and d are independent of each other , Represents an integer from 0 to 9, and e represents an integer from 0 to 2). 如請求項14之四羧酸，其係式(2-2)所示，
Figure 106133364-A0305-02-0050-10
 (式中，R1、R2、R3、R4、R5、R6、R7、a、b、c、d及e表示與前述相同的意思)。 For example, the tetracarboxylic acid of claim 14 is represented by formula (2-2),
Figure 106133364-A0305-02-0050-10
 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , a, b, c, d, and e have the same meaning as described above). 如請求項15之四羧酸，其係式(2-3)所示，
Figure 106133364-A0305-02-0050-11
 For example, the tetracarboxylic acid of claim 15 is shown in formula (2-3),
Figure 106133364-A0305-02-0050-11
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WO2009101885A1 (en) * 2008-02-14 2009-08-20 Kyowa Hakko Chemical Co., Ltd. Polyimide
WO2014207559A2 (en) * 2013-06-06 2014-12-31 King Abdullah University Of Science And Technlology Triptycene-based dianhydrides, polyimides, methods of making each, and methods of use

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WO2009101885A1 (en) * 2008-02-14 2009-08-20 Kyowa Hakko Chemical Co., Ltd. Polyimide
WO2014207559A2 (en) * 2013-06-06 2014-12-31 King Abdullah University Of Science And Technlology Triptycene-based dianhydrides, polyimides, methods of making each, and methods of use
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