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TWI709591B - Polyimide, polyimide, polyimide solution, and polyimide film - Google Patents

Polyimide, polyimide, polyimide solution, and polyimide film Download PDF

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TWI709591B
TWI709591B TW106125449A TW106125449A TWI709591B TW I709591 B TWI709591 B TW I709591B TW 106125449 A TW106125449 A TW 106125449A TW 106125449 A TW106125449 A TW 106125449A TW I709591 B TWI709591 B TW I709591B
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polyimide
repeating unit
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general formula
aforementioned
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TW201821482A (en
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小松伸一
京武亜紗子
田所恵典
引田二郎
塩田大
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日商Ｊｘｔｇ能源股份有限公司
日商東京應化工業股份有限公司
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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Abstract

一種聚醯亞胺薄膜，其含有特定通式表示之重複單位(A)，與特定通式表示之表示之重複單位(B)，且相對於前述重複單位(A)及(B)之總量而言，前述重複單位(A)之含量為5～35莫耳%。A polyimide film that contains a repeating unit (A) represented by a specific general formula, and a repeating unit (B) represented by a specific general formula, relative to the total amount of the aforementioned repeating units (A) and (B) In other words, the content of the aforementioned repeating unit (A) is 5 to 35 mol%.

Description

聚醯亞胺、聚醯胺酸、聚醯胺酸溶液、及聚醯亞胺薄膜Polyimide, polyimide, polyimide solution, and polyimide film

本發明係關於聚醯亞胺、聚醯胺酸、聚醯胺酸溶液以及聚醯亞胺薄膜。The present invention relates to polyimide, polyimide acid, polyimide acid solution and polyimide film.

使用有機電致發光元件之顯示器或液晶顯示器等之顯示器機器的領域等中，作為其基板等所利用的材料，光透過性高、輕且柔軟之材料的出現係受到需求。而作為如此用途等所使用的材料，係著眼於由輕且柔軟之聚醯亞胺所構成的薄膜。關於如此之聚醯亞胺，近年來具有充分光透過性之脂環式聚醯亞胺的開發係有所進展，例如，於國際公開第2011/099518號(專利文獻1)中，揭示具有以特定通式記載之重複單位的聚醯亞胺。 [先前技術文獻] [專利文獻] 　　[專利文獻1]國際公開第2011/099518號In the field of display devices such as displays using organic electroluminescence elements or liquid crystal displays, there is a demand for the emergence of materials with high light permeability, lightness and flexibility as materials used for substrates. As a material used for such applications, the focus is on a film made of light and soft polyimide. With regard to such polyimides, the development of alicyclic polyimides with sufficient light transmittance has progressed in recent years. For example, International Publication No. 2011/099518 (Patent Document 1) discloses Polyimide of repeating unit of specific general formula. [Prior Art Document] [Patent Document] 　　 [Patent Document 1] International Publication No. 2011/099518

[發明所欲解決之課題] 　　上述專利文獻1記載之聚醯亞胺，為充分具有高度之透明性者。但是，上述專利文獻1記載之聚醯亞胺，於以更高度水準地且平衡良好地發揮充分低之黃色度與充分低之線膨脹係數的觀點上，不一定為充足者。如此地，以往之聚醯亞胺，於以更高度水準地且平衡良好地發揮充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數的觀點上，不一定為充足者。 　　本發明係有鑑於上述先前技術所具有的課題而為者，其目的為提供可以更高度水準地且平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數的聚醯亞胺；可效率良好地形成該聚醯亞胺之聚醯胺酸；該聚醯胺酸之溶液；以及由前述聚醯亞胺所構成的聚醯亞胺薄膜。 [用以解決課題之手段] 　　本發明者等人為了達成上述目的而重複努力研究的結果，發現藉由藉由使聚醯亞胺以相對於下述重複單位(A)及(B)之總量而言，重複單位(A)之含有比率成為5～35莫耳%的方式含有該該通式(1)表示之重複單位(A)與該通式(2)表示之重複單位(B)，可以更高度水準地且平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數，而完成本發明。 　　亦即，本發明之聚醯亞胺，為含有下述通式(1)：

Figure 02_image001
[式(1)中，R1 、R2 、R3 係分別獨立地表示選自由氫原子、碳數1～10之烷基及氟原子所成之群的1種，R10 表示具有含氟取代基之碳數6～40之伸芳基，n表示0～12之整數]。 表示之重複單位(A)，與 　　下述通式(2)：
Figure 02_image003
[式(2)中，R10 表示具有含氟取代基之碳數6～40之伸芳基]。 表示之重複單位(B)，且相對於前述重複單位(A)及(B)之總量而言，前述重複單位(A)之含量為5～35莫耳%者。 　　又，上述本發明之聚醯亞胺，較佳前述通式(1)及(2)中之R10 均為下述通式(3)：
Figure 02_image005
[式(3)中，R5 表示碳數1～10之氟烷基]。 表示之基。 　　進一步地，上述本發明之聚醯亞胺，較佳相對於前述重複單位(A)及(B)之總量而言，前述重複單位(A)之含量為5～25莫耳%。 　　又，本發明之聚醯胺酸，為含有下述通式(4)：
Figure 02_image007
[式(4)中，R1 、R2 、R3 係分別獨立地表示選自由氫原子、碳數1～10之烷基及氟原子所成之群的1種，R10 表示具有含氟取代基之碳數6～40之伸芳基，n表示0～12之整數]。 表示之重複單位(C)，與 　　下述通式(5)：
Figure 02_image009
[式(5)中，R10 表示具有含氟取代基之碳數6～40之伸芳基]。 表示之重複單位(D)，且相對於前述重複單位(C)及(D)之總量而言，前述重複單位(C)之含量為5～35莫耳%者。 　　又，本發明之聚醯胺酸溶液，為含有上述本發明之聚醯胺酸與有機溶劑者。 　　進一步地，本發明之聚醯亞胺薄膜，為由上述本發明之聚醯亞胺所構成者。 [發明之效果] 　　依照本發明，可提供可以更高度水準地且平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數的聚醯亞胺；可效率良好地形成該聚醯亞胺之聚醯胺酸；該聚醯胺酸之溶液；以及由前述聚醯亞胺所構成的聚醯亞胺薄膜。[Problem to be Solved by the Invention] The polyimide described in Patent Document 1 mentioned above has sufficiently high transparency. However, the polyimide described in Patent Document 1 is not necessarily sufficient in terms of achieving a sufficiently low yellowness and a sufficiently low linear expansion coefficient at a higher level and in a good balance. In this way, the conventional polyimide is not necessarily sufficient from the viewpoint that the full light transmittance, the low yellowness, and the sufficiently low coefficient of linear expansion are displayed at a higher level and in a well-balanced manner. . The present invention is made in view of the above-mentioned problems of the prior art, and its purpose is to provide a higher level and a well-balanced total light transmittance, a sufficiently low yellowness and a sufficiently low linear expansion coefficient. The polyimide; the polyimide that can efficiently form the polyimide; the solution of the polyimide; and the polyimide film composed of the aforementioned polyimide. [Means to Solve the Problem] The inventors of the present invention have repeatedly studied hard in order to achieve the above-mentioned object, and found that by making polyimide relative to the total of the following repeating units (A) and (B) In terms of quantity, the repeating unit (A) represented by the general formula (1) and the repeating unit (B) represented by the general formula (2) are contained so that the content ratio of the repeating unit (A) becomes 5 to 35 mol% , It is possible to have a higher level and a well-balanced total light transmittance, a sufficiently low yellowness and a sufficiently low linear expansion coefficient to complete the present invention. That is, the polyimide of the present invention contains the following general formula (1):
Figure 02_image001
[In formula (1), R 1 , R 2 , and R 3 each independently represent one kind selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and R 10 represents a fluorine-containing The substituent is an arylene group having 6 to 40 carbon atoms, and n represents an integer of 0-12]. The repeating unit (A) represented by the following general formula (2):
Figure 02_image003
[In formula (2), R 10 represents an arylene group having 6 to 40 carbon atoms having a fluorine-containing substituent]. The repeating unit (B) indicated, and the content of the repeating unit (A) is 5 to 35 mol% relative to the total amount of the repeating units (A) and (B). In addition, in the above-mentioned polyimide of the present invention, it is preferable that R 10 in the aforementioned general formulas (1) and (2) are both the following general formula (3):
Figure 02_image005
[In the formula (3), R 5 represents a fluoroalkyl group having 1 to 10 carbon atoms]. The base of expression. Furthermore, in the polyimide of the present invention, the content of the repeating unit (A) is preferably 5-25 mol% relative to the total amount of the repeating unit (A) and (B). In addition, the polyamide acid of the present invention contains the following general formula (4):
Figure 02_image007
[In formula (4), R 1 , R 2 , and R 3 each independently represent one kind selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and R 10 represents a fluorine-containing The substituent is an arylene group having 6 to 40 carbon atoms, and n represents an integer of 0-12]. The repeating unit (C) represented by the following general formula (5):
Figure 02_image009
[In formula (5), R 10 represents an arylene group having 6 to 40 carbon atoms having a fluorine-containing substituent]. The repeating unit (D) indicated, and the content of the repeating unit (C) is 5 to 35 mol% relative to the total amount of the repeating units (C) and (D). In addition, the polyamide acid solution of the present invention is one containing the above-mentioned polyamide acid of the present invention and an organic solvent. Further, the polyimide film of the present invention is composed of the above-mentioned polyimide film of the present invention. [Effects of the invention] According to the present invention, it is possible to provide a polyimide that can have a higher level and a well-balanced total light transmittance, a sufficiently low yellowness, and a sufficiently low linear expansion coefficient; it can be highly efficient To form the polyimide of the polyimide; the solution of the polyimide; and the polyimide film composed of the aforementioned polyimide.

以下基於其適合的實施形態詳細說明本發明。 [聚醯亞胺] 　　本發明之聚醯亞胺，為含有下述通式(1)：

Figure 02_image011
[式(1)中，R1 、R2 、R3 係分別獨立地表示選自由氫原子、碳數1～10之烷基及氟原子所成之群的1種，R10 表示具有含氟取代基之碳數6～40之伸芳基，n表示0～12之整數]。 表示之重複單位(A)，與 　　下述通式(2)：
Figure 02_image013
[式(2)中，R10 表示具有含氟取代基之碳數6～40之伸芳基]。 表示之重複單位(B)，且相對於前述重複單位(A)及(B)之總量而言，前述重複單位(A)之含量為5～35莫耳%者。 　　關於前述重複單位(A)，可作為通式(1)中之R1 、R2 、R3 所選擇的烷基，為碳數1～10之烷基。如此之碳數若超過10時，玻璃轉移溫度降低，無法達成利用於各種基板材料等時所必須的充分高度水準之耐熱性。又，如此之可作為R1 、R2 、R3 所選擇的烷基之碳數，就更容易精製的觀點而言，較佳為1～6、更佳為1～5、又更佳為1～4、特佳為1～3。又，如此之可作為R1 、R2 、R3 所選擇的烷基可為直鏈狀亦可為分支鏈狀。再者，就精製容易的觀點而言，如此之烷基更佳為甲基、乙基。 　　又，就製造聚醯亞胺時，可得到更高度之耐熱性的觀點而言，前述通式(1)中之R1 、R2 、R3 ，更佳分別獨立地為氫原子或碳數1～10之烷基，其中就原料獲得容易或精製更為容易的觀點而言，尤以分別獨立地為氫原子、甲基、乙基、n-丙基或異丙基更佳；特佳為氫原子或甲基。又，如此式中之複數個R1 、R2 、R3 ，就精製容易等的觀點而言，特佳為相同者。 　　又，前述通式(1)中之R10 ，為具有含氟取代基之碳數6～40之伸芳基(氟系伸芳基)。此處所稱之含氟取代基，只要係含有氟者即可，並無特殊限制，例如可列舉氟原子本身，或至少一部分被氟原子取代之烷基(氟烷基)等。如此之含氟取代基之中，就可得到更高度之耐熱性的觀點而言，尤以碳數1～10之氟烷基(例如氟化甲基、二氟甲基、三氟甲基、三氟乙基、五氟乙基、七氟-n-丙基、七氟異丙基、九氟-n-丁基、九氟-sec-丁基、九氟異丁基、九氟-t-丁基、全氟戊基、全氟己基、全氟庚基、全氟辛基、全氟壬基、全氟癸基等之氟化烷基)為佳；其中尤以碳數1～5(更佳為1～3)之氟烷基更佳。又，如此之含氟取代基，就原料獲得性之觀點而言，更佳為碳數1～5(更佳為1～3)之氟烷基。如此地，關於前述R10 ，前述伸芳基所具有的含氟取代基，又更佳為碳數1～3(更佳為1～2)之氟烷基(特佳為全氟烷基)。再者，於此，「氟烷基」係指烷基之氫原子的一部分或全部被氟原子取代而成之基(再者，如此之基只要係烷基的至少一部分之氫原子被氟原子取代即可，烷基的一部分之氫原子亦可進一步被氟原子以外之取代基(例如氟原子以外之鹵素原子、羥基、烷氧基、苯氧基、重氫等)取代)，又，「全氟烷基」係指烷基之氫原子全部被氟原子取代而成之基。 　　關於可作為前述通式(1)中之R10 所選擇的具有含氟取代基之伸芳基，前述伸芳基之碳數(再者，該碳數係指伸芳基本身之碳數，前述含氟取代基中之碳數係由該碳數中被除外)為6～40。又，如此之伸芳基之碳數較佳為6～30、更佳為12～20。如此之碳數超過前述上限時有耐熱性降低的傾向。如此之伸芳基，例如可列舉伸苯基、伸聯苯基、聯三苯基、伸萘基、伸蒽基、伸茀基、伸菲基、伸苯并菲基、伸茚基、伸芘基或伸苯并蒽基等，其中就獲得性之觀點而言，尤以伸聯苯基、伸苯基、伸萘基為佳；更佳為伸聯苯基、伸苯基。 　　進一步地，可作為前述通式(1)中之R10 所選擇的具有含氟取代基之伸芳基，就耐熱性或獲得性之觀點而言，較佳為下述通式(3)：
Figure 02_image015
[式(3)中，R5 表示碳數1～10之氟烷基(更佳為全氟烷基)]。 表示之基，其中尤以下述通式(3-I)
Figure 02_image017
表示之基為特佳。 　　再者，本發明之聚醯亞胺中，作為前述重複單位(A)，亦可組合R10 之種類等相異的複數種重複單位(A)來利用。 　　進一步地，關於前述重複單位(B)，前述通式(2)中之R10 ，係與上述通式(1)中之R10 相同意義(其適合者亦與上述通式(1)中之R10 相同)。再者，本發明之聚醯亞胺中，作為前述重複單位(B)，亦可組合R10 之種類等相異的複數種重複單位(B)來利用。 　　再者，本發明之聚醯亞胺中，就為具有充分之水準的耐熱性者，同時以更高度之水準平衡良好地展現充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數的觀點而言，較佳為前述重複單位(A)及(B)中之全部R10 為相同者。 　　又，本發明之聚醯亞胺中，相對於上述通式(1)表示之重複單位(A)及上述通式(2)表示之重複單位(B)之總量而言，前述重複單位(A)之含量，以莫耳量為基準係5～35莫耳%。如此的通式(1)表示之重複單位(A)之含量若未達前述下限，有難以成為具有充分高度之全光線透過率(更佳為83.0%以上之全光線透過率)者之傾向，再者，難以成為具有充分低之線膨脹係數(較佳為-20ppm/K～20ppm/K之線膨脹係數)者，無法成為以高度之水準平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數者。另一方面，前述重複單位(A)之含量超過前述上限時，此時亦無法成為具有充分低之線膨脹係數(較佳為-20ppm/K～20ppm/K之線膨脹係數)者，無法成為以高度之水準平衡良好地具有充分低之黃色度與充分低之線膨脹係數者。 　　進一步地，本發明之聚醯亞胺中，具有充分高度之全光線透過率，同時以更高度之水準平衡良好地具有充分低之黃色度與充分低之線膨脹係數的觀點而言，相對於上述通式(1)表示之重複單位(A)及上述通式(2)表示之重複單位(B)之總量而言，前述重複單位(A)之含有比率更佳為5～25莫耳%、又更佳為10～20莫耳%、特佳為12.5～17.5莫耳%。又，以同樣的觀點，相對於前述重複單位(A)及前述重複單位(B)之總量而言，前述重複單位(B)之含量，以莫耳量為基準必須為95～65莫耳%，更佳為95～75莫耳%、又更佳為90～80莫耳%、特佳為87.5～82.5莫耳%。 　　又，本發明之聚醯亞胺中，於不損及本發明之效果的範圍，亦可含有其他重複單位。如此之其他重複單位，並無特殊限制，可適當利用可構成聚醯亞胺之公知的重複單位。又，本發明之聚醯亞胺中，含有其他重複單位時，上述通式(1)表示之重複單位(A)及上述通式(2)表示之重複單位(B)之總量，較佳相對於聚醯亞胺中之全部重複單位而言，以成為50莫耳%以上(更佳為70莫耳%以上)的方式來含有前述重複單位(A)及(B)。再者，如此之相對於聚醯亞胺中之全部重複單位而言前述重複單位(A)及前述重複單位(B)之總量的含有比例，更佳為80～100莫耳%、又更佳為90～100莫耳%。如此之相對於聚醯亞胺中之全部重複單位而言重複單位(A)及(B)之總量的含有比率若未達前述下限，則有難以成為平衡良好地具有充分低之黃色度與充分低之線膨脹係數者的傾向。再者，就更加效率良好地形成聚醯亞胺之觀點而言，本發明之聚醯亞胺係以實質上由重複單位(A)及(B)所構成(實質上不含其他重複單位，更佳為前述重複單位(A)及前述重複單位(B)之總量為95莫耳%以上、又更佳為98莫耳%以上、特佳為99莫耳%以上)為佳。 　　又，如此之聚醯亞胺，線膨脹係數較佳為-20ppm/K～20ppm/K、更佳為-10～10ppm/K、又更佳為-5～5ppm/K。如此之線膨脹係數超過前述上限時，與線膨脹係數之範圍為5～20ppm/K之金屬或無機物組合而複合化時，有因熱歷程而容易產生剝離的傾向，作為微電子學之基板而利用時，難以良率良好地製造微電子學之最終產品(例如有機EL顯示器、觸控式面板、半導體用保護膜(緩衝塗層)、層間絕緣膜、光阻、影像感測器用微透鏡等)。另一方面，前述線膨脹係數未達前述下限時，於層合無機物時，有容易產生剝離或捲曲的傾向。再者，於由聚醯亞胺所構成的薄膜之上層或下層製造裝置的情況，裝置為無機化合物時，就抑制薄膜之捲曲或製造時之變形產生的觀點，較佳為使用具有與無機化合物同等程度的充分低之線膨脹係數的聚醯亞胺。由如此之觀點，本發明之聚醯亞胺亦以其線膨脹係數為上述範圍較佳。 　　又，本發明中，聚醯亞胺之線膨脹係數之值係採用以下值。亦即，首先關於作為測定對象之聚醯亞胺，形成由該聚醯亞胺所構成的縱：20mm、橫：5mm、厚度：13μm大小的薄膜。之後，將該薄膜真空乾燥(120℃1小時)，於氮環境下200℃熱處理1小時，得到乾燥薄膜。然後，使用如此所得的乾燥薄膜作為試樣，利用熱機械分析裝置(Rigaku製之商品名「TMA8310」)作為測定裝置，於氮環境下，採用拉伸模式(49mN)、昇溫速度5℃/分之條件，測定於50℃～200℃之前述試樣的縱方向之長度變化，求得於50℃～200℃之溫度範圍內，每1℃(1K)之長度變化的平均值。然後，採用如此所求得的前述平均值，作為本發明之聚醯亞胺之線膨脹係數的值(採用厚度為13μm時的聚醯亞胺薄膜之線膨脹係數的值，作為本發明之聚醯亞胺之線膨脹係數的值)。 　　進一步地，如此之聚醯亞胺，較佳為5%重量減少溫度(Td5%)為400℃以上者、更佳為450～550℃者。如此之5%重量減少溫度若未達前述下限，則有難以得到用以利用作為微電子學之產品用的基板所充分之耐熱性的傾向，另一方面，超過前述上限時，有難以製造具有如此特性之聚醯亞胺的傾向。再者，如此之5%重量減少溫度，可藉由於氮氣環境下，一邊流通氮氣，同時將掃描溫度設定為30℃～550℃，且以昇溫速度：10℃/min.之條件加熱，測定所用之試樣重量減少5%時之溫度來求得。又，如此之測定，例如可利用熱重量分析裝置(SII Nanotechnology股份有限公司製之「TG/DTA220」)作為測定裝置。 　　又，如此之聚醯亞胺，較佳為玻璃轉移溫度(Tg)為300℃以上者、更佳為350～500℃者。如此之玻璃轉移溫度(Tg)若未達前述下限，則有難以得到用以利用作為微電子學之產品用基板所充分的耐熱性(例如，於使用聚醯亞胺作為太陽電池、液晶顯示裝置或有機EL顯示裝置之透明電極用基板時，其產品之製造過程的加熱步驟中，不亦充分抑制該聚醯亞胺(基板)之品質劣化(破裂產生等))的傾向，另一方面，超過前述上限時，有難以製造具有如此特性之聚醯亞胺的傾向。再者，如此之玻璃轉移溫度(Tg)，可使用熱機械分析裝置(Rigaku製之商品名「TMA8311」)作為測定裝置，以與軟化溫度測定相同之方法同時測定。再者，如此之玻璃轉移溫度之測定時，較佳藉由以昇溫速度：5℃/分鐘之條件，於氮環境下，掃描30℃至550℃之範圍來進行測定。 　　又，如此之聚醯亞胺，較佳為軟化溫度(軟化點)為300～550℃者、更佳為320～550℃者、又更佳為340～510℃者。如此之軟化溫度若未達前述下限，則耐熱性降低，例如使用由該聚醯亞胺所構成的薄膜作為太陽電池、液晶顯示裝置或有機EL顯示裝置之透明電極用的基板時，於該產品之製造過程中，有難以充分抑制該薄膜(基板)之品質劣化(破裂產生等)的傾向，另一方面，超過前述上限時，於製造聚醯亞胺時係有在進行聚醯胺酸之熱閉環縮合反應的同時，未進行充分的固相聚合反應，形成薄膜時變脆的傾向。再者，如此之聚醯亞胺之軟化溫度可如以下般測定。亦即，可藉由準備由縱5mm、橫5mm、厚度0.013 mm(13μm)之大小的聚醯亞胺所構成的薄膜作為測定試樣，使用熱機械分析裝置(Rigaku製之商品名「TMA8311」)作為測定裝置，於氮環境下，採用昇溫速度5℃/分鐘之條件，以30℃～550℃之溫度範圍的條件對薄膜將透明石英製針(尖端直徑：0.5mm)以500mN之壓力插針，與玻璃轉移溫度(Tg)同時地測定(可藉由所謂穿透(插針)法來測定)。再者，如此之測定時，係根據JIS K 7196(1991年)記載之方法，基於測定數據計算軟化溫度。 　　進一步地，如此之聚醯亞胺由於難以溶解於溶劑來測定分子量，故較佳以其前驅體的聚醯胺酸(聚醯胺酸)之分子量(數平均分子量或重量平均分子量)或分子量分布為指標，來探討其適合者。如此之聚醯亞胺之前驅體的前述聚醯胺酸(聚醯胺酸)之數平均分子量(Mn)，以聚苯乙烯換算較佳為1000～1000000、更佳為10000～500000。如此之數平均分子量若未達前述下限，則不僅難以達成充分的耐熱性，且有難以效率良好地得到聚醯亞胺之傾向，另一方面，超過前述上限時，黏性增大，過濾步驟需要長時間，或需要大量之黏性調整用的稀釋溶劑，因此有難以加工的傾向。 　　又，如此之聚醯亞胺之前驅體的前述聚醯胺酸(聚醯胺酸)之重量平均分子量(Mw)，以聚苯乙烯換算，較佳為1000～5000000。又，如此之重量平均分子量(Mw)之數值範圍的下限值，更佳為5000、又更佳為10000、特佳為20000。又，重量平均分子量(Mw)之數值範圍的上限值，更佳為5000000、又更佳為500000、特佳為100000。如此之重量平均分子量若未達前述下限，不僅難以達成充分的耐熱性，且有難以效率良好地得到聚醯亞胺之傾向，另一方面，超過前述上限時，黏性增大，過濾步驟需要長時間，或需要大量之黏性調整用的稀釋溶劑，因此有難以加工的傾向。 　　進一步地，如此之聚醯亞胺之前驅體的前述聚醯胺酸(聚醯胺酸)之分子量分布(Mw/Mn)較佳為1.1～5.0、更佳為1.5～3.0。如此之分子量分布若未達前述下限，有難以製造之傾向，另一方面，超過前述上限時，形成薄膜時有難以得到均勻薄膜之傾向。再者，如此之聚醯亞胺之分子量(Mw或Mn)或分子量之分布(Mw/Mn)，可將使用凝膠滲透層析(GPC)測定裝置(TOSOH製EcoSEC HLC-8320GPC，管柱：TOSOH製GPC管柱TSKgel Super AW2500、3000、4000、管柱溫度：40℃、展開溶劑：添加有10mM之LiBr的二甲基乙醯胺溶劑(流速0.5mL/min.))作為測定裝置所測定的數據以聚苯乙烯換算來求得。 　　又，如此之聚醯亞胺，就於與黃色度(YI)之適當值(16以下)的關係，而確保利用於透明顯示器、太陽電池、觸控式面板、擋風玻璃保護膜、透明FPC等玻璃替代可撓透明材料之用途時所要求的高度視覺辨認性之觀點而言，全光線透過率更佳為83%以上(又更佳為85%以上、特佳為87%以上)者。如此之全光線透過率若未達前述下限，則即使黃色度為16以下，依其黃色度之值而利用於各種用途時難以發揮所要求的透明性(視覺辨認性)。 　　又，如此之聚醯亞胺，就得到更高度之透明性的觀點而言，霧度(濁度)更佳為5以下(又更佳為4以下、特佳為3以下)者。 　　進一步地，如此之聚醯亞胺，就得到更高度之透明性的觀點而言，黃色度(YI)更佳為16.0以下(又更佳為11.0以下、特佳為10.5以下)者。再者，如此之黃色度超過前述上限時，難以確保該用途所必須之高度的色相、明度、彩度、輝度、色調、對比、色度、透明性(視覺辨認性)，因此即使全光線透過率為83%以上，亦難以發揮利用於各種用途時所要求的性能。 　　又，如此之全光線透過率、霧度(濁度)及黃色度(YI)，可採用使用日本電色工業股份有限公司製之商品名「HAZE METER NDH-5000」或日本電色工業股份有限公司製之商品名「分光色彩計SD6000」作為測定裝置(以日本電色工業股份有限公司製之商品名「HAZE METER NDH-5000」測定全光線透過率與霧度，以日本電色工業股份有限公司製之商品名「分光色彩計SD6000」測定黃色度)，且使用厚度10～15μm(較佳為13μm)之由聚醯亞胺所構成的薄膜作為測定用試樣所測定的值。惟，就黃色度(YI)而言，係如以下記載般，採用13μm厚度之薄膜的測定值或換算為13μm厚度之薄膜的值之換算值。亦即，全光線透過率及霧度(濁度)，只要係厚度10～15μm之由聚醯亞胺所構成的薄膜，則厚度充分薄，對測定值不造成影響，故由相同之聚醯亞胺可測定到相同之值。另一方面，就黃色度(YI)而言，由於有受到膜厚之影響的傾向，故本發明中，係利用具有前述範圍(10～15μm)之厚度的薄膜作為測定用之試樣，且作為黃色度(YI)之值係採用換算為13μm厚度之薄膜的值之值(再者，利用13μm厚度之薄膜進行測定時為其測定值)。如此地，本發明中，黃色度(YI)之值係採用13μm厚度之薄膜的測定值或換算為具有13μm厚度之薄膜的值之值。由如此之觀點(黃色度可採用換算為13μm厚度之薄膜的值之值一事)，全光線透過率、霧度(濁度)及黃色度(YI)之測定，可利用具有前述範圍(10～15μm之範圍)之厚度的薄膜(再者，利用具有13μm以外之厚度的薄膜作為測定用試樣來測定YI時，如前所述般必須換算為13μm之厚度的值。因此，就不需要如此之換算的觀點而言，較佳為準備並利用厚度13μm之由聚醯亞胺所構成的薄膜作為測定用試樣)。又，測定試樣之縱、橫的大小，只要係可配置於前述測定裝置之測定部位的尺寸即可，縱、橫之大小亦可適當變更。再者，如此之全光線透過率，係藉由根據JIS K7361-1(1997年發行)進行測定來求得，霧度(濁度)係藉由根據JIS K7136(2000年發行)進行測定來求得，黃色度(YI)係藉由根據ASTM E313-05(2005年發行)進行測定來求得。 　　再者，可適合地利用於製造如此之聚醯亞胺的方法係如後述。 [聚醯胺酸] 　　本發明之聚醯胺酸，為含有下述通式(4)：
Figure 02_image019
[式(4)中，R1 、R2 、R3 係分別獨立地表示選自由氫原子、碳數1～10之烷基及氟原子所成之群的1種，R10 表示具有含氟取代基之碳數6～40之伸芳基，n表示0～12之整數]。 表示之重複單位(C)，與 　　下述通式(5)：
Figure 02_image021
[式(5)中，R10 表示具有含氟取代基之碳數6～40之伸芳基]。 表示之重複單位(D)，且相對於前述重複單位(C)及(D)之總量而言，前述重複單位(C)之含量為5～35莫耳%者。 　　如此之聚醯胺酸，為於製造上述本發明之聚醯亞胺時可適合地利用者(可作為製造本發明之聚醯亞胺時的反應中間體(前驅體)而得到者)。如此之通式(4)中之R1 、R2 、R3 、R10 及n係與上述通式(1)中之R1 、R2 、R3 、R10 及n為相同者，其適合者亦與上述通式(1)中之R1 、R2 、R3 、R10 及n相同。又，如此之通式(5)中之R10 係與上述通式(2)中之R10 相同者(亦即，與上述通式(1)中之R10 相同者)，其適合者亦與上述通式(2)中之R10 相同。 　　又，本發明之聚醯胺酸中，相對於上述通式(4)表示之重複單位(C)及上述通式(5)表示之重複單位(D)之總量而言，前述重複單位(C)之含量以莫耳量為基準係5～35莫耳%。如此之通式(4)表示之重複單位(C)之含量若未達前述下限，則使用該聚醯胺酸製造聚醯亞胺時，有難以成為具有充分高度之全光線透過率(較佳為83.0%以上之全光線透過率)者的傾向，而且難以成為具有充分低之線膨脹係數(較佳為-20ppm/K～20ppm/K之線膨脹係數)者，無法得到以高度之水準平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數的聚醯亞胺。另一方面，前述重複單位(C)之含量超過前述上限時，此情況時亦於使用該聚醯胺酸製造聚醯亞胺時，無法得到具有充分低之線膨脹係數(較佳為-20ppm/K～20ppm/K之線膨脹係數)之聚醯亞胺，無法製造以高度之水準平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數的特性之聚醯亞胺。 　　進一步地，本發明之聚醯胺酸中，就使用該聚醯胺酸，得到以更高度水準地且平衡良好地具有充分低之黃色度與充分低之線膨脹係數的聚醯亞胺之觀點而言，相對於前述重複單位(C)及前述重複單位(D)之總量而言，前述重複單位(C)之含有比率更佳為5～25莫耳%、又更佳為10～20莫耳%、特佳為12.5～17.5莫耳%。 　　又，本發明之聚醯胺酸中，於不損及本發明之效果的範圍，亦可含有其他重複單位。如此之其他重複單位，並無特殊限制，可適當利用可構成聚醯胺酸之公知的重複單位。又，本發明之聚醯胺酸中，含有其他重複單位時，較佳為以通式(4)表示之重複單位(C)及上述通式(5)表示之重複單位(D)之總量，相對於聚醯胺酸中之全部重複單位而言，成為50莫耳%以上(更佳為70莫耳%以上)的方式，來含有重複單位(C)及(D)。再者，相對於如此之聚醯胺酸中之全部重複單位而言，前述重複單位(C)及前述重複單位(D)之總量的含有比例，更佳為80～100莫耳%、又更佳為90～100莫耳%。如此之重複單位(C)及(D)之總量の含有比率若未達前述下限，則有難以製造平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數的聚醯亞胺之傾向。再者，由使用該聚醯胺酸，更加效率良好地形成聚醯亞胺的觀點而言，本發明之聚醯胺酸，較佳為實質上由重複單位(C)及(D)所構成(實質上不含其他重複單位、更佳為前述重複單位(C)及(D)之總量為95莫耳%以上、又更佳為98莫耳%以上、特佳為99莫耳%以上)。 　　又，如此之聚醯胺酸，固有黏度[η]較佳為0.05～3.0dL/g、更佳為0.1～2.0dL/g。如此之固有黏度[η]小於0.05dL/g時，使用其製造薄膜狀之聚醯亞胺時，係有所得之薄膜變脆的傾向，另一方面，超過3.0dL/g時，黏度過高，加工性降低，例如製造薄膜時難以得到均勻的薄膜。又，如此之固有黏度[η]，可由以下方式般測定。亦即，首先，使用四甲基脲(TMU)作為溶劑，於該四甲基脲(TMU)中溶解前述聚醯胺酸使濃度成為0.5g/dL，得到測定試樣(溶液)。接著使用前述測定試樣，於30℃之溫度條件下使用動黏度計，測定前述測定試樣之黏度，採用所求得的值作為固有黏度[η]。再者，如此之動黏度計，係使用離合公司製之自動黏度測定裝置(商品名「VMC-252」)。 　　以下，說明為了製造如此之聚醯胺酸，可適合地利用之方法。 (為了製造聚醯胺酸而可適合地利用之方法) 　　為了製造如此之聚醯胺酸而可適合地利用之方法，並無特殊限制，例如可適合地利用使含有下述通式(10)：
Figure 02_image023
[式(10)中，R1 、R2 、R3 係分別獨立地表示選自由氫原子、碳數1～10之烷基及氟原子所成之群的1種，n表示0～12之整數]。 表示之化合物(A)，及下述通式(11)：
Figure 02_image025
表示之化合物(B)，且相對於前述化合物(A)及(B)之總量而言，前述化合物(A)之含量為5～35莫耳%的四羧酸二酐(化合物(I))；與含有 　　下述通式(12)：
Figure 02_image027
[式(12)中，R10 表示具有含氟取代基之碳數6～40之伸芳基]。 表示之化合物的二胺化合物(化合物(II))，於有機溶劑之存在下反應，藉以得到 　　含有前述重複單位(C)及前述重複單位(D)，且相對於前述重複單位(C)及(D)之總量而言，前述重複單位(C)之含量為5～35莫耳%的聚醯胺酸之方法。再者，前述重複單位(C)係源自前述化合物(A)與前述通式(12)表示之化合物而形成，前述重複單位(D)係源自前述化合物(B)與前述通式(12)表示之化合物而形成。 　　如此之聚醯胺酸之製造方法所使用的通式(10)表示之化合物(A)中之R1 、R2 、R3 及n，係與上述通式(1)中之R1 、R2 、R3 及n相同意義(其適合者亦與上述通式(1)中之R1 、R2 、R3 及n相同)又，上述通式(12)表示之化合物中之R10 係與上述通式(1)及(2)中之R10 相同意義(其適合者亦與上述通式(1)及(2)中之R10 相同)。 　　製造如此之通式(10)表示之化合物(A)的方法，並無特殊限制，可適當利用公知之方法(例如國際公開第2011/099518號記載之方法等)。 　　又，用以製造上述通式(11)表示之化合物(B)的方法，並無特殊限制，可適當利用公知之方法。又，如此之化合物(B)，係苯均四酸酐(1,2,4,5-苯四羧酸二酐、苯均四酸酐)，該化合物亦可適當使用市售者。 　　進一步地，用以製造前述通式(12)表示之化合物的方法並無特殊限制，可適當採用公知之方法。又，如此之通式(12)表示之化合物亦可適當使用市售者。 　　又，前述四羧酸二酐(化合物(I))，必須利用相對於該化合物(I)中之前述化合物(A)及(B)之總量而言前述化合物(A)之含量為5～35莫耳%者。如此之化合物(A)之含量未達前述下限時及超過前述上限時，無法使前述重複單位(C)相對於前述重複單位(C)及(D)之總量而言的含量成為所期望之範圍(5～35莫耳%之範圍)。又，由同樣的觀點，上述化合物(I)中，相對於上述化合物(A)及(B)之總量而言，前述化合物(A)之含有比率更佳為5～25莫耳%、又更佳為10～20莫耳%、特佳為12.5～17.5莫耳%。 　　又，作為前述化合物(I)，為了使本發明之聚醯胺酸中含有其他重複單位，亦可混合利用化合物(A)及(B)以外之其他四羧酸二酐。再者，如此之化合物(A)及(B)以外之其他四羧酸二酐，可適當利用可利用於聚醯亞胺之製造的公知之其他四羧酸二酐。此時，化合物(A)及(B)以外之其他四羧酸二酐之使用量，只要以所得之聚醯胺酸中之重複單位(C)及(D)的含量成為所期望之範圍(上述之適合的含量範圍等)的方式適當調整即可。再者，作為前述四羧酸二酐(化合物(I))，就為具有充分之水準的耐熱性者，同時以更高度之水準平衡良好地展現充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數的觀點而言，化合物(I)較佳為實質上由前述化合物(A)及(B)所構成者(化合物(I)實質上不含化合物(A)及(B)以外之其他四羧酸二酐者，於化合物(I)中，更佳為前述化合物(A)及(B)之總量為95莫耳%以上、又更佳為98莫耳%以上、特佳為99莫耳%以上、最佳為100莫耳%)。 　　進一步地，作為前述化合物(II)，為了使本發明之聚醯胺酸中含有其他重複單位，可適當含有前述通式(12)表示之化合物以外之其他二胺化合物(其他之芳香族二胺及脂環式二胺等)。如此之其他二胺化合物，可適當利用可利用於聚醯亞胺之製造的公知之其他二胺化合物。如此之其他二胺化合物，例如可適合地使用兩末端胺基改質矽氧烷等。如此之兩末端胺基改質矽氧烷之具體例子，可列舉1,3-雙(3-胺基丙基)四甲基二矽氧烷、信越化學工業股份有限公司製胺基改質聚矽氧油(例如PAM-E、KF-8010、X-22-161A、X-22-161B、KF-8012、KF-8008、X-22-1660B-3、X-22-9409等)、Gelest公司製二甲基矽氧烷型二胺(例如DMS-A11、DMS-A12、DMS-A15、DMS-A21、DMS-A31、DMS-A32、DMS-A32R、DMS-A35等)等。再者，如此之化合物(II)中之前述通式(12)表示之化合物以外之其他二胺化合物之使用量，必須以所得之聚醯胺酸中的重複單位(C)及(D)之含量成為所期望之範圍(上述之適合的含量範圍等)的方式適當調整。再者，作為二胺化合物(化合物(II))，就為具有充分之水準的耐熱性者，同時以更高度之水準平衡良好地展現充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數的觀點而言，化合物(II)較佳為實質上由前述通式(12)表示之化合物所構成者(化合物(II)實質上不含其他二胺化合物者，於化合物(II)中，更佳為前述通式(12)表示之化合物之總量為95莫耳%以上、又更佳為98莫耳%以上、特佳為99莫耳%以上、最佳為100莫耳%)。 　　又，前述有機溶劑，較佳為可溶解上述四羧酸二酐(化合物(I))與上述二胺化合物(化合物(II))兩者的有機溶劑。如此之有機溶劑例如可列舉N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碸、γ-丁內酯、碳酸伸丙酯、碳酸伸乙酯、四甲基尿素(四甲基脲(TMU))、1,3-二甲基-2-四氫咪唑酮、六甲基磷三醯胺、吡啶等之非質子系極性溶劑；m-甲酚、二甲酚、酚、鹵化酚等之酚系溶劑；四氫呋喃、二噁烷、賽珞蘇、甘醇二甲醚等之醚系溶劑；環戊酮、環己酮或環庚酮等之酮系溶劑；苯、甲苯、二甲苯等之芳香族系溶劑等。如此之有機溶劑可1種單獨或混合2種以上使用。 　　又，上述四羧酸二酐(化合物(I))與上述二胺化合物(化合物(II))之使用比例，相對於上述二胺化合物(化合物(II))所具有之胺基1當量而言，上述四羧酸二酐(化合物(I))中之酸酐基較佳為0.2～2當量、更佳為0.8～1.2當量。如此之使用比例若未達前述下限，則有聚合反應未效率良好地進行，得不到高分子量之聚醯胺酸的傾向，另一方面，超過前述上限時，與前述同樣地有得不到高分子量之聚醯胺酸的傾向。 　　進一步地，前述有機溶劑之使用量，較佳為使上述四羧酸二酐(化合物(I))與上述二胺化合物(化合物(II))之總量相對於反應溶液之全部量而言成為1～50質量%(更佳為10～30質量%)之量。如此之有機溶劑之使用量若未達前述下限，則有無法效率良好地得到聚醯胺酸之傾向，另一方面，超過前述上限時，有因高黏度化而攪拌困難的傾向。 　　又，使上述四羧酸二酐(化合物(I))與上述二胺化合物(化合物(II))反應時，就反應速度提高與得到高聚合度之聚醯胺酸的觀點而言，亦可於前述有機溶劑中進一步添加鹼性化合物。如此之鹼性化合物並無特殊限制，例如可列舉三乙胺、四丁胺、四己胺、1,8-二氮雜雙環[5.4.0]-十一烯-7、吡啶、異喹啉、α-甲吡啶等。又，如此之鹼性化合物之使用量，相對於上述四羧酸二酐(化合物(I))1當量而言，較佳為0.001～10當量、更佳為0.01～0.1當量。如此之鹼化合物之使用量若未達前述下限，則有添加效果降低的傾向，另一方面，超過前述上限時，有成為著色等之原因的傾向。 　　又，使上述四羧酸二酐(化合物(I))與上述二胺化合物(化合物(II))反應時的反應溫度，只要適當調整為可使此等化合物反應之溫度即可，並無特殊限制，較佳為-20℃～200℃。又，使上述四羧酸二酐(化合物(I))與上述二胺化合物(化合物(II))反應的方法，可適當利用可進行四羧酸二酐與二胺化合物之聚合反應的公知方法，並無特殊限制，例如，亦可適當採用於大氣壓中，氮、氦、氬等之不活性環境下，使二胺化合物溶解於溶劑後，於前述反應溫度添加上述四羧酸二酐(化合物(I))，之後，反應10～48小時之方法。如此之反應溫度或反應時間若未達前述下限，則有難以充分反應之傾向，另一方面，超過前述上限時，使聚合物劣化之物質(氧等)的混入機率提高，有分子量降低之傾向。 　　如此地，藉由於有機溶劑之存在下，使上述四羧酸二酐(化合物(I))與上述二胺化合物(化合物(II))反應，可得到上述本發明之聚醯胺酸。如此地調製聚醯胺酸後，由前述有機溶劑中單離上述本發明之聚醯胺酸時，其單離方法並無特殊限制，可適當採用可單離聚醯胺酸之公知方法，例如，亦可採用作為再沈澱物而單離之方法等。 [聚醯胺酸溶液] 　　本發明之聚醯胺酸溶液，為含有上述本發明之聚醯胺酸與有機溶劑者。如此之聚醯胺酸溶液所使用的有機溶劑，可適合地利用與為了製造上述聚醯胺酸而可適合地利用之方法所用的有機溶劑相同者。因此，亦可藉由實施為了製造上述聚醯胺酸而可適合地利用的方法，將反應後所得之反應液直接作為聚醯胺酸溶液以調製本發明之聚醯胺酸溶液。亦即，本發明之聚醯胺酸溶液，亦可藉由於前述有機溶劑之存在下，使上述四羧酸二酐(化合物(I))與上述二胺化合物(化合物(II))反應，調製聚醯胺酸，得到含有前述聚醯胺酸與前述有機溶劑之溶液來製造。 　　如此之聚醯胺酸溶液中之前述聚醯胺酸之含量並無特殊限制，較佳為1～50質量%、更佳為10～30質量%。如此之含量若未達前述下限，有聚醯胺酸之分子量降低的傾向，另一方面，超過前述上限時，有聚醯亞胺之製造變困難的傾向。再者，如此之聚醯胺酸溶液，可適合地利用於上述本發明之聚醯亞胺之製造。 　　再者，如此之聚醯胺酸溶液，當將其利用於聚醯亞胺之製造時，亦可適當添加而利用可利用於調製聚醯亞胺的各種添加劑(高分子量化或醯亞胺化之促進劑、劣化防止劑、抗氧化劑、光安定劑、紫外線吸收劑、改質劑、抗靜電劑、難燃劑、可塑劑、造核劑、安定劑、密合提高劑、潤滑劑、脫模劑、染料、發泡劑、消泡劑、表面改質劑、硬塗劑、調平劑、界面活性劑、填充劑(玻璃纖維、填料、滑石、雲母、二氧化矽等)等)。又，關於使用如此之添加劑時，聚醯胺酸溶液中之添加劑的含量並無特殊限制，較佳為0.0001～80質量%(更佳為0.1～50質量%)左右。 (為了製造聚醯亞胺而可適合利用之方法) 　　為了製造本發明之聚醯亞胺而可適合利用之方法，並無特殊限制，可適合地利用藉由使上述本發明之聚醯胺酸醯亞胺化，而得到 　　含有前述重複單位(A)與前述重複單位(B)，且相對於前述重複單位(A)及(B)之總量而言，前述重複單位(A)之含量為5～35莫耳%的聚醯亞胺之方法。再者，前述重複單位(A)係源自前述重複單位(C)而形成、前述重複單位(B)係源自前述重複單位(D)而形成者。 　　如此之聚醯胺酸的醯亞胺化方法，只要係可將聚醯胺酸醯亞胺化之方法即可，並無特殊限制，可適當採用公知方法，例如，較佳為採用藉由將上述本發明之聚醯胺酸於60～450℃(更佳為80～400℃)之溫度條件下實施加熱處理而醯亞胺化之方法，或使用所謂「醯亞胺化劑」進行醯亞胺化之方法。 　　於採用藉由實施如此之加熱處理而醯亞胺化之方法時，前述加熱溫度未達60℃時係有反應進行緩慢的傾向，另一方面，超過前述上限時，係有著色或發生熱分解致分子量降低等的傾向。又，採用藉由實施加熱處理而醯亞胺化之方法時的反應時間(加熱時間)較佳為0.5～5小時。如此之反應時間若未達前述下限，則有難以充分醯亞胺化之傾向，另一方面，超過前述上限時，係有著色或發生熱分解致分子量降低等的傾向。再者，上述本發明之聚醯胺酸，即使於如大氣中般之含有氧的條件下加熱而醯亞胺化，亦可製造平衡良好地具有充分低之黃色度與充分低之線膨脹係數的聚醯亞胺，因此加熱時的環境條件並無特殊限制，可為惰性氣體中亦可為大氣中。又，於大氣中加熱製造時，不僅可於更簡便之設備等製造聚醯亞胺，且可不需控制環境氣體即製造聚醯亞胺，因此亦可更加提高最終產品之製造效率。又，加熱而醯亞胺化時，為了促進高分子量化或醯亞胺化，亦可利用所謂的促進劑(添加劑)。如此之促進劑，可適當利用公知之反應促進劑(例如咪唑系化合物、吡啶系化合物、三乙胺等之3級胺系化合物、胺基酸系化合物等)。如此之促進劑之使用量，並無特殊限制，例如，相對於聚醯胺酸溶液中之固體成分(聚醯胺酸)100質量份而言，為1～60質量份、較佳為5～50質量份。 　　又，採用利用所謂的「醯亞胺化劑」將聚醯胺酸醯亞胺化之方法時，較佳為於醯亞胺化劑之存在下，於溶劑中使上述本發明之聚醯胺酸醯亞胺化。如此之溶劑可適合地使用與上述本發明之聚醯亞胺酸之製造方法所用的有機溶劑相同者。 　　如此之醯亞胺化劑，可適當利用公知之醯亞胺化劑，例如可列舉乙酸酐、丙酸酐、三氟乙酸酐等之酸酐；吡啶、柯林鹼、二甲基吡啶、三乙胺、N-甲基哌啶等之3級胺等。又，添加醯亞胺化劑進行醯亞胺化時之醯亞胺化時的反應溫度較佳為0～200℃、更佳為30～150℃。又，反應時間較佳為0.1～48小時。如此之反應溫度或時間若未達前述下限，則有難以充分醯亞胺化之傾向，另一方面，超過前述上限時，使聚合物劣化之物質(氧等)的混入確率提高，有分子量降低或色相惡化之傾向。又，如此之醯亞胺化劑之使用量，並無特殊限制，只要相對於聚醯胺酸中之上述通式(5)表示之重複單位1莫耳而言，為數毫莫耳～數莫耳(較佳為0.01～4.0莫耳左右)即可。 　　又，為了製造本發明之聚醯亞胺而可適合利用之方法，較佳為包含下述步驟之方法： 　　使上述四羧酸二酐(化合物(I))與上述二胺化合物(化合物(II))於有機溶劑之存在下反應，藉以得到含有前述重複單位(C)及前述重複單位(D)，且相對於前述重複單位(C)及(D)之總量而言，前述重複單位(C)之含量為5～35莫耳%的聚醯胺酸(上述本發明之聚醯胺酸)之步驟(I)；與 　　藉由使前述聚醯胺酸醯亞胺化，得到含有前述重複單位(A)與前述重複單位(B)，且相對於前述重複單位(A)及(B)之總量而言，前述重複單位(A)之含量為5～35莫耳%的聚醯亞胺(上述本發明之聚醯亞胺)之步驟(II)。 　　如此地，採用包含步驟(I)及步驟(II)之方法作為製造本發明之聚醯亞胺之方法時，能夠以一系列之步驟製造聚醯亞胺。 　　再者，利用包含如此之步驟(I)及步驟(II)之方法時，且於前述醯亞胺化時，採用藉由實施加熱處理而醯亞胺化之方法時，亦可採用如下方法：於實施前述步驟(I)之後，不經單離上述本發明之聚醯胺酸，即將於有機溶劑中使上述四羧酸二酐(化合物(I))與上述二胺化合物(化合物(II))反應所得之反應液(含有上述本發明之聚醯胺酸的反應液)直接使用或添加前述促進劑來使用，對該反應液實施將溶劑蒸發去除之處理(溶劑去除處理)以去除溶劑後，藉由實施前述加熱處理而醯亞胺化。藉由實施將如此之溶劑蒸發去除之處理，可將上述本發明之聚醯胺酸以薄膜狀等之形態單離，之後，實施加熱處理等。如此之將溶劑蒸發去除之處理的方法中之溫度條件較佳為0～180℃、更佳為30～150℃。如此之將溶劑蒸發去除之處理中的溫度條件若未達前述下限，則有難以將溶劑充分蒸發去除之傾向，另一方面，超過前述上限時，有溶劑沸騰而成為含有氣泡或孔隙之薄膜的傾向。此時，例如製造薄膜狀之聚醯亞胺時，只要將所得之反應液直接塗佈於基材(例如玻璃板)上，實施前述將溶劑蒸發去除之處理及加熱處理即可，能夠以簡便的方法來製造薄膜狀之聚醯亞胺。再者，如此之反應液之塗佈方法並無特殊限制，可適當採用公知方法(流延法等)。又，由前述反應液單離上述本發明之聚醯胺酸來利用時，其單離方法並無特殊限制，可適當採用可單離聚醯胺酸之公知方法，例如亦可採用作為再沈澱物而單離之方法等。 　　又，利用包含步驟(I)及步驟(II)之方法時，且採用利用「醯亞胺化劑」而醯亞胺化之方法時，由更加效率良好地形成薄膜狀之聚醯亞胺的觀點而言，可適合地採用如下方法：直接使用於有機溶劑中使上述四羧酸二酐(化合物(I))與上述二胺化合物(化合物(II))反應而得的反應液(於實施步驟(I)後不由前述反應液單離上述本發明之聚醯胺酸，即直接使用前述反應液)，對前述反應液添加醯亞胺化劑，於醯亞胺化尚未充分進行時，將前述反應液塗佈於玻璃等之基板，於基板上實施醯亞胺化。 [聚醯亞胺薄膜] 　　本發明之聚醯亞胺薄膜，為由上述本發明之聚醯亞胺所構成者。 　　如此之聚醯亞胺薄膜之形態，只要係薄膜狀即可，並無特殊限制，可適當設計為各種形狀(圓盤狀、圓筒狀(將薄膜加工為筒狀者)等)。 　　進一步地，本發明之聚醯亞胺薄膜之厚度並無特殊限制，較佳為1～500μm、更佳為10～200μm。如此之厚度若未達前述下限，係有強度降低，操作變困難之傾向，另一方面，超過前述上限時，係有產生必須進行複數次塗佈的情況，或產生加工複雜化的情況之傾向。 　　如此之聚醯亞胺薄膜，可藉由採用作為為了製造上述聚醯亞胺而可適合利用之方法所說明的方法，同時適當調整塗佈方法等，使所得聚醯亞胺之形態成為所期望之形狀(薄膜狀)而製造。 　　以上，說明了本發明之聚醯亞胺、聚醯胺酸、聚醯胺酸溶液及聚醯亞胺薄膜，如此之本發明之聚醯亞胺及聚醯亞胺薄膜，由於為以高度之水準平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數者，故即使層合於金屬基板等時，亦可充分抑制因熱而產生薄膜剝離等，而且兼具充分的視覺辨認性，因而特別有用於作為各種用途，例如可撓配線基板用薄膜、耐熱絕緣膠帶、電線漆包、半導體之保護塗覆劑、液晶配向膜、有機EL用透明導電性薄膜、顯示器之基板材料(TFT基板、透明電極基板(例如有機EL用透明電極基板、電子紙之透明電極基板等)等之顯示器用基板)、太陽電池用透明電極基板、有機EL照明用薄膜、可撓基板薄膜、可撓有機EL用基板薄膜、可撓透明導電性薄膜、有機薄膜型太陽電池用透明導電性薄膜、色素增感型太陽電池用透明導電性薄膜、可撓氣體障壁性薄膜、觸控式面板用之基板材料(觸控式面板用薄膜等)、可撓顯示器用擋風玻璃保護膜、可撓顯示器用背膜、複印機用無縫聚醯亞胺帶(所謂的轉印帶)、層間絕緣膜、感測器基板等之材料。進一步地，本發明之聚醯亞胺，源自其線膨脹係數，於如上述之用途中，尤以使用於顯示器之基板材料(TFT基板、透明電極基板等之顯示器用基板)或觸控式面板用之基板材料(觸控式面板用薄膜等)等之用途時，可更加改善最終產品(例如有機EL元件等)之良率。 　　又，由於如此之本發明之聚醯亞胺之特性，例如於微電子學(有機EL顯示器、液晶顯示器、觸控式面板、可撓顯示器面板、高輝度LED晶圓、極薄矽晶圓、三次元半導體封裝、半導體用保護膜(緩衝塗層)、層間絕緣膜、光阻、影像感測器用微透鏡等)之產品所利用的基板材料上使用了本發明之聚醯亞胺時，不僅可對應於裝置之大型化，源自其線膨脹係數，亦可充分防止於製造時之加熱步驟中的破裂或捲曲等，達成最終產品之高良率，進而可貢獻於生產效率提高、處理能力提高，因此亦可低成本地製造產品。 [實施例] 　　以下，基於實施例及比較例更具體說明本發明，但本發明不限定於以下實施例。 　　首先說明於各實施例、各比較例中得到之聚醯亞胺薄膜等之特性的評估方法。 ＜分子構造之鑑定＞ 　　各實施例及各比較例中得到之化合物之分子構造的鑑定，係使用IR測定機(日本分光股份有限公司製、商品名：FT/IR-4100)藉由IR測定來進行。 ＜固有黏度[η]之測定＞ 　　各實施例及各比較例中作為中間體所得到的聚醯胺酸之固有黏度[η]之值(單位：dL/g)，係使用離合公司製之自動黏度測定裝置(商品名「VMC-252」)，使用以四甲基脲(TMU)為溶劑之濃度0.5g/dL的測定試樣於30℃之溫度條件下測定。 ＜玻璃轉移溫度(Tg)及軟化溫度之測定＞ 　　各實施例及各比較例中得到之聚醯亞胺的玻璃轉移溫度(Tg)及軟化溫度之值(單位：℃)，係藉由使用由各實施例及各比較例中製造之聚醯亞胺所構成的薄膜，準備縱5mm、橫5mm、厚度0.013mm(13μm)大小之測定試樣，使用熱機械分析裝置(Rigaku製之商品名「TMA8311」作為測定裝置，於氮環境下，以昇溫速度5℃/分、30℃～550℃之溫度範圍(掃描溫度)的條件將透明石英製針(尖端直徑：0.5mm)以500mN壓力對薄膜插針而測定(以所謂穿透(插針)法之測定)。再者，軟化溫度之測定時，除了利用上述測定試樣以外，係根據JIS K7196(1991年)記載之方法，基於測定數據計算軟化溫度(軟化點)。 ＜5%重量減少溫度(Td5%)之測定＞ 　　各實施例及各比較例中得到之聚醯亞胺的5%重量減少溫度(Td5%)之值(單位：℃)，係藉由使用各實施例及各比較例中製造之聚醯亞胺薄膜，使用熱重量分析裝置(SII Nanotechnology股份有限公司製之「TG/DTA220」)，將掃描溫度設定為30℃～550℃，於氮環境下，一邊流通氮氣同時以10℃/min.之條件加熱，測定所使用之試樣的重量減少5%之溫度而求得。 ＜全光線透過率、霧度(濁度)及黃色度(YI)之測定＞ 　　各實施例及各比較例中得到之聚醯亞胺的全光線透過率之值(單位：%)、霧度(濁度：HAZE)及黃色度(YI)，係藉由將各實施例等中得到之薄膜直接使用作為測定用之試樣，使用日本電色工業股份有限公司製之商品名「HAZE METER NDH-5000」或日本電色工業股份有限公司製之商品名「分光色彩計SD6000」作為測定裝置，分別進行測定而求得。再者，係以日本電色工業股份有限公司製之商品名「HAZE METER NDH-5000」測定全光線透過率與霧度，以日本電色工業股份有限公司製之商品名「分光色彩計SD6000」測定黃色度。又，全光線透過率，係藉由進行根據JIS K7361-1(1997年發行)之測定來求得，霧度(濁度)係藉由進行根據JIS K7136(2000年發行)之測定來求得，色度(YI)係藉由進行根據ASTM E313-05(2005年發行)之測定來求得。 ＜線膨脹係數(CTE)之測定＞ 　　線膨脹係數，係藉由自各實施例及各比較例中得到之聚醯亞胺(薄膜形狀之聚醯亞胺)形成縱：20mm、橫：5mm、厚度：13μm大小之薄膜後，將該薄膜真空乾燥(120℃、1小時(Hr))，於氮環境下、200℃進行1小時(Hr)熱處理，分別使用所得之試樣(乾燥薄膜)，利用熱機械分析裝置(Rigaku製之商品名「TMA8310」)作為測定裝置，於氮環境下，採用拉伸模式(49mN)、昇溫速度5℃/分之條件，測定於50℃～200℃之前述試樣的長度變化，求得於100℃～200℃之溫度範圍中每1℃之長度變化的平均值來測定。 (實施例1) ＜CpODA之準備步驟＞ 　　根據國際公開第2011/099518號之合成例1、實施例1及實施例2記載之方法，準備下述通式(13)：
Figure 02_image029
表示之化合物(降莰烷-2-螺-α-環戊酮-α’-螺-2＂-降莰烷-5,5＂,6,6＂-四羧酸二酐：CpODA)。 ＜聚醯胺酸之調製步驟＞ 　　首先，將30ml之三口燒瓶以熱風機(heat gun)加熱使充分乾燥。接著，將充分乾燥之前述三口燒瓶內的環境氣體以氮取代，使前述三口燒瓶內成為氮環境。接著，於前述三口燒瓶內，添加作為芳香族二胺(二胺化合物)之下述通式(14)：
Figure 02_image031
表示之2,2’-雙(三氟甲基)聯苯胺(TFMB)4.8035g (15.00 mmol：Seika股份有限公司製)後，進一步添加四甲基脲(TMU)33.8g(使反應液中之聚醯胺酸濃度成為20mass%(質量%)之量)，攪拌藉以於前述四甲基脲中溶解芳香族二胺(TFMB)，得到溶解液。 　　接著，於含有前述溶解液之三口燒瓶內，於氮環境下添加作為四羧酸二酐之上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(苯均四酸酐：PMDA：東京化成工業股份有限公司製)2.7810g(12.75mmol)之混合物，於氮環境下，室溫(25℃)攪拌12小時得到反應液。如此地於反應液中形成聚醯胺酸。 　　再者，利用該反應液(聚醯胺酸之四甲基脲溶液：聚醯胺酸溶液)之一部分，調製聚醯胺酸之濃度為0.5g/dL的四甲基脲溶液，如上述地，測定反應中間體之聚醯胺酸的固有黏度[η]後，聚醯胺酸之固有黏度[η]為0.76dL/g。 ＜由聚醯亞胺所構成的薄膜之調製步驟：步驟(i)～(iii)＞ (步驟(i)：溶劑去除處理) 　　準備無鹼玻璃(康寧公司製之商品名「Eagle XG」、縱：100mm、橫100mm、厚度0.7mm)作為玻璃基板，將如上述般所得到之反應液(聚醯胺酸溶液)，於前述玻璃基板之表面上以加熱硬化後之塗膜厚度成為13μm的方式旋轉塗佈，於前述玻璃基板上形成塗膜。之後，將形成有前述塗膜之玻璃基板載置於60℃之加熱板上靜置2小時，由前述塗膜蒸發去除溶劑(溶劑去除處理)。 (步驟(ii)：實施溶劑去除處理後之加熱步驟) 　　如上述般實施過溶劑去除處理後，將形成有前述塗膜之玻璃基板投入以3L/分之流量流通有氮的惰性氣體烘箱中，於惰性氣體烘箱內、氮環境下，以25℃之溫度條件靜置0.5小時後，以135℃之溫度條件加熱0.5小時，進一步地，最終以350℃之溫度條件(以下依情況稱「最終加熱溫度條件」)加熱1小時，使前述塗膜硬化，得到於前述玻璃基板上塗覆有由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)之聚醯亞胺塗覆玻璃。 (步驟(iii)：薄膜之回收步驟) 　　接著，將如此方式所得到的聚醯亞胺塗覆玻璃浸漬於90℃之熱水中，由前述玻璃基板剝離聚醯亞胺薄膜，藉以回收聚醯亞胺薄膜(縱：100mm、橫100mm、厚度13μm大小之薄膜)，得到由聚醯亞胺所構成的薄膜。 　　再者，為了鑑定形成如此方式所得到的薄膜之化合物的分子構造，使用IR測定機(日本分光股份有限公司製、商品名：FT/IR-4100)測定IR光譜。將IR光譜示於圖1作為如此之測定結果。由圖1所示結果亦明顯可知，於構成實施例1中所形成之薄膜的化合物中，在1715.3cm-1 觀察到醯亞胺羰基之C=O伸縮振動。由基於如此之結果等所鑑定之分子構造，確認到所得之薄膜係由聚醯亞胺所構成者。 　　如此方式所得到的聚醯亞胺，由所用之單體之種類或其量比，其係含有相當於前述通式(1)表示之重複單位之重複單位(相當於重複單位(A)之重複單位)與相當於前述通式(2)表示之重複單位之重複單位(相當於重複單位(B)之重複單位)者，且該等重複單位之含有比率以莫耳比([相當於重複單位(A)之重複單位]：[相當於重複單位(B)之重複單位])計為15：85。又，關於所得之聚醯亞胺，特性之評估結果(藉由上述特性之評估方法所求得的Tg或軟化溫度等)示於表1。 (實施例2) 　　作為四羧酸二酐，使用上述通式(13)表示之化合物(CpODA)1.1534g(3.00mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.6172g(12.00mmol)之混合物，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為34.30g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 　　又，所得到的聚醯亞胺，由所用之單體之種類或其量比，其係含有相當於前述通式(1)表示之重複單位之重複單位(相當於重複單位(A)之重複單位)與相當於前述通式(2)表示之重複單位之重複單位(相當於重複單位(B)之重複單位)者，且該等重複單位之含有比率以莫耳比([相當於重複單位(A)之重複單位]：[相當於重複單位(B)之重複單位])計為20：80。 (實施例3) 　　作為四羧酸二酐，使用上述通式(13)表示之化合物(CpODA)0.5766g(1.50mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.9446g(13.50mmol)之混合物，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為33.30g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 　　又，所得到的聚醯亞胺，由所用之單體之種類或其量比，其係含有相當於前述通式(1)表示之重複單位之重複單位(相當於重複單位(A)之重複單位)與相當於前述通式(2)表示之重複單位之重複單位(相當於重複單位(B)之重複單位)者，且該等重複單位之含有比率以莫耳比([相當於重複單位(A)之重複單位]：[相當於重複單位(B)之重複單位])計為10：90。 (實施例4) 　　作為四羧酸二酐，使用上述通式(13)表示之化合物(CpODA)1.7297g(4.50mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.2903g(10.50mmol)之混合物，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物，且使用反應液中之聚醯胺酸濃度成為20mass%之量的TMU以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 　　又，所得到的聚醯亞胺，由所用之單體之種類或其量比，其係含有相當於前述通式(1)表示之重複單位之重複單位(相當於重複單位(A)之重複單位)與相當於前述通式(2)表示之重複單位之重複單位(相當於重複單位(B)之重複單位)者，且該等重複單位之含有比率以莫耳比([相當於重複單位(A)之重複單位]：[相當於重複單位(B)之重複單位])計為30：70。 (實施例5) 　　將由聚醯亞胺所構成的薄膜之調製步驟的步驟(ii)中所採用之最終加熱溫度條件由350℃變更為300℃以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 (實施例6) 　　將由聚醯亞胺所構成的薄膜之調製步驟的步驟(i)中所用之反應液(聚醯胺酸溶液)，變更為於實施聚醯胺酸之調製步驟所得到之反應液42.25g(聚醯胺酸20mass%溶液)中溶解由下述通式(15)：
Figure 02_image033
表示之咪唑系化合物所構成的促進劑(東京應化工業股份有限公司製)0.8450g(相對於聚醯胺酸溶液中之固體成分(聚醯胺酸)100質量份而言為10質量份之量)所得到的溶解液(添加有前述促進劑之反應液(聚醯胺酸溶液))， 　　進一步地，將由聚醯亞胺所構成的薄膜之調製步驟的步驟(ii)中所採用之最終加熱溫度條件由350℃變更為300℃以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 (實施例7) 　　將由聚醯亞胺所構成的薄膜之調製步驟的步驟(i)中所用之反應液(聚醯胺酸溶液)，變更為於實施聚醯胺酸之調製步驟所得到之反應液42.25g(聚醯胺酸20mass%溶液)中溶解由上述通式(15)表示之咪唑系化合物所構成的促進劑(東京應化工業股份有限公司製)0.8450g(相對於聚醯胺酸溶液中之固體成分(聚醯胺酸)100質量份而言為10質量份之量)所得到的溶解液(添加有前述促進劑之反應液(聚醯胺酸溶液))， 　　將由聚醯亞胺所構成的薄膜之調製步驟的步驟(ii)中所採用之最終加熱溫度條件由燒成溫度350℃變更為300℃， 　　進一步地，將由聚醯亞胺所構成的薄膜之調製步驟的步驟(ii)中所採用之環境氣體由氮變更為空氣(將惰性氣體烘箱內所流通的氣體由氮變更為空氣，於空氣中實施加熱步驟)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 (實施例8) 　　作為芳香族二胺，使用上述通式(14)表示之化合物(TFMB)4.7074g(14.7mmol)與胺基改質聚矽氧油(信越化學工業股份有限公司製之商品名「X-22-9409」)0.4020g (0.3 mmol相當)之混合物，以取代單獨使用上述通式(14)表示之2,2’-雙(三氟甲基)聯苯胺(TFMB)4.8035g(15.00 mmol：Seika股份有限公司製)， 　　將四甲基脲(TMU)之使用量由33.8g變更為35.02g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 　　又，所得到的聚醯亞胺，由所用之單體之種類或其量比，其係含有相當於前述通式(1)表示之重複單位之重複單位(相當於重複單位(A)之重複單位)與相當於前述通式(2)表示之重複單位之重複單位(相當於重複單位(B)之重複單位)者，且該等重複單位之含有比率以莫耳比([相當於重複單位(A)之重複單位]：[相當於重複單位(B)之重複單位])計為15：85。 (比較例1) 　　作為四羧酸二酐，使用上述通式(13)表示之化合物(CpODA)2.3063g(6.00mmol)與上述通式(11)表示之苯均四酸酐(PMDA)1.9631g(9.00mmol)之混合物，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為36.3g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 　　又，所得到的聚醯亞胺，由所用之單體之種類或其量比，其係含有相當於前述通式(1)表示之重複單位之重複單位(相當於重複單位(A)之重複單位)與相當於前述通式(2)表示之重複單位之重複單位(相當於重複單位(B)之重複單位)者，且該等重複單位之含有比率以莫耳比([相當於重複單位(A)之重複單位]：[相當於重複單位(B)之重複單位])計為40：60。 (比較例2) 　　作為四羧酸二酐，單獨使用上述通式(11)表示之苯均四酸酐(PMDA)3.2718g(15.00mmol)，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為32.3g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。又，所得到的聚醯亞胺，由所用之單體之種類或其量比，其係相當於前述通式(2)表示之重複單位之重複單位(相當於重複單位(B)之重複單位)的含有比率為100莫耳%者。 (比較例3) 　　作為四羧酸二酐，單獨使用下述通式(16)：
Figure 02_image035
表示之化合物(4,4’-聯鄰苯二甲酸酐：BPDA：東京化成工業股份有限公司製)4.4133g(15.00mmol)，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g (12.75mmol)之混合物，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為36.9g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 (比較例4) 　　作為四羧酸二酐，使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(16)表示之化合物(4,4’-聯鄰苯二甲酸酐：BPDA：東京化成工業股份有限公司製)3.7513g(12.75mmol)之混合物(CpODA與BPDA之莫耳比(CpODA：BPDA)為15：85)，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物， 　　將四甲基脲(TMU)之使用量由33.8g變更為37.7g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 (比較例5) 　　作為四羧酸二酐，單獨使用上述通式(11)表示之苯均四酸酐(PMDA)3.2718g(15.00mmol)，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物，作為芳香族二胺，使用下述通式(17)：
Figure 02_image037
表示之化合物(m-聯甲苯胺：m-Tol：東京化成工業股份有限公司製)3.1844g(15.00mmol)，以取代使用上述通式(14)表示之2,2’-雙(三氟甲基)聯苯胺(TFMB)4.8035g (15.00 mmol：Seika股份有限公司製)，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為25.8g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 (比較例6) 　　作為四羧酸二酐，單獨使用上述通式(16)表示之化合物(4,4’-聯鄰苯二甲酸酐：BPDA：東京化成工業股份有限公司製)4.4133g(15.00mmol)，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物， 　　作為芳香族二胺，使用上述通式(17)表示之化合物(m-Tol)3.1844g(15.00mmol)，以取代使用上述通式(14)表示之2,2’-雙(三氟甲基)聯苯胺(TFMB)4.8035g(15.00mmol：Seika股份有限公司製)，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為30.4g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 (比較例7) 　　作為四羧酸二酐，使用下述通式(18)：
Figure 02_image039
表示之化合物(1,2,4,5-環己烷四羧酸二酐：CHDA) 0.5044g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為32.4g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 (比較例8) 　　作為四羧酸二酐，使用下述通式(19)：
Figure 02_image041
表示之化合物(1,2,3,4-環戊烷四羧酸二酐：CPDA) 0.4728g (2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA) 2.7810g(12.75mmol)之混合物，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為32.2g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 (比較例9) 　　作為四羧酸二酐，使用下述通式(20)：
Figure 02_image043
表示之化合物(1,2,3,4-環丁烷四羧酸二酐：CBDA) 0.4412 g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA) 2.7810g(12.75mmol)之混合物，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為32.1g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 (比較例10) 　　作為芳香族二胺，使用上述通式(17)表示之化合物(m-Tol)3.1844g(15.00mmol)，以取代使用上述通式(14)表示之2,2’-雙(三氟甲基)聯苯胺(TFMB)4.8035g(15.00mmol：Seika股份有限公司製)，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為27.3g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。 (比較例11) 　　作為四羧酸二酐，使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(16)表示之化合物(4,4’-聯鄰苯二甲酸酐：BPDA：東京化成工業股份有限公司製)3.7513g(12.75mmol)之混合物(CpODA與BPDA之莫耳比(CpODA：BPDA)為15：85)，以取代使用上述通式(13)表示之化合物(CpODA)0.8650g(2.25mmol)與上述通式(11)表示之苯均四酸酐(PMDA)2.7810g(12.75mmol)之混合物， 　　作為芳香族二胺，使用上述通式(17)表示之化合物(m-Tol)3.1844g(15.00mmol)，以取代使用上述通式(14)表示之2,2’-雙(三氟甲基)聯苯胺(TFMB)4.8035g(15.00mmol：Seika股份有限公司製)，且， 　　將四甲基脲(TMU)之使用量由33.8g變更為31.2g(使反應液中之聚醯胺酸濃度成為20mass%之量)以外，係與實施例1相同地得到由聚醯亞胺所構成的薄膜(聚醯亞胺薄膜)。再者，關於所得之薄膜測定IR光譜後，確認到該薄膜為由聚醯亞胺所構成者。又，關於所得到之聚醯亞胺評估特性之結果(藉由上述之特性評估方法所求得之Tg或軟化溫度等)示於表1。
Figure 02_image045
由表1所示之結果亦明顯可知，由本發明之聚醯亞胺(實施例1～8)所構成的薄膜，全光線透過率均為85%以上，為透明性充分高者。又，由本發明之聚醯亞胺(實施例1～8)所構成的薄膜，黃色度(YI)均為16以下(至於由於氮環境下加熱所得到之聚醯亞胺(實施例1～6及8)所構成的薄膜為11以下)，而且CTE為-20ppm/K～20ppm/K。如此地，由本發明之聚醯亞胺(實施例1～8)所構成的薄膜，均具有可於要求視覺辨認性之用途利用的程度之充分高度之全光線透過率與充分低之黃色度，而且確認到具有與玻璃或銅等之無機物同等程度之線膨脹係數。亦即，確認到由本發明之聚醯亞胺(實施例1～8)所構成的薄膜均為以更高度水準地且平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數者。再者，由表1所示之結果亦明顯可知，本發明之聚醯亞胺(實施例1～8)，具有300℃以上之Tg、300℃以上之軟化溫度(軟化點)、400℃以上(較佳為450℃以上)之Td5%，具有充分高水準之耐熱性。又，亦可知本發明之聚醯亞胺(實施例1～8)，霧度(濁度：HAZE)均為5以下之值(1.1以下之值)，霧度為充分低者。 　　相對於此，比較例1～2中得到之聚醯亞胺，線膨脹係數為超過20ppm/K之高值，不為具有充分低之線膨脹係數者。又，比較例2中得到之聚醯亞胺，全光線透過率亦為小於83.0之值，亦可知尚未具有如本發明之聚醯亞胺所達成的非常高度水準之光透過性(全光線透過率較佳為83.0以上、更佳為85.0以上之透過性)。 　　一併考量如此之結果，與實施例1～8及比較例1～2中得到之聚醯亞胺的構造(比較例1中得到之聚醯亞胺，前述重複單位(A)相對於前述重複單位(A)及(B)之總量的含量為40莫耳%，比較例2中得到之聚醯亞胺，前述重複單位(B)之含量為100莫耳%(前述重複單位(A)之含量為0莫耳%))時，可知藉由含有前述重複單位(A)及(B)，且相對於前述重複單位(A)及(B)之總量而言，前述重複單位(A)之比率為5～35莫耳%的聚醯亞胺，會成為以更高度水準地且平衡良好地具有充分高度之全光線透過率(較佳為83.0以上、更佳為85.0以上之全光線透過率)、充分低之黃色度(較佳為16以下之YI)與充分低之線膨脹係數(較佳為-20ppm/K～20ppm/K之範圍之CTE)者。 　　又，與實施例1對比，於四羧酸二酐之混合物中，使用了BPDA(芳香族系四羧酸二酐)以取代PMDA(芳香族系四羧酸二酐)時(比較例4)，不僅全光線透過率無法成為充分且高度者，且YI之值成為18.2，亦無法使黃色度為充分低之值。進一步地，使用BPDA(芳香族系四羧酸二酐)時(比較例4)，線膨脹係數亦為60.7ppm/K，亦無法使線膨脹係數為充分低之值。如此地，可知於四羧酸二酐之混合物，使用了BPDA(芳香族系四羧酸二酐)以取代PMDA(芳香族系四羧酸二酐)時(比較例4)，無法達成充分低之黃色度與充分低之線膨脹係數。再者，與四羧酸二酐僅為BPDA的情況(比較例3)對比，亦可知四羧酸二酐為BPDA與CpODA之混合物時(比較例4)，黃色度(YI)之值上昇，因此與CpODA組合的芳香族系四羧酸二酐之種類為PMDA以外時，不一定可為以更高度水準地且平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數者。 　　又，與實施例1對比，可知於四羧酸二酐之混合物，使用了CHDA、CPDA或CBDA(脂肪族系之四羧酸二酐)以取代CpODA(脂肪族系之四羧酸二酐)時(CHDA：比較例7、CPDA：比較例8、CBDA：比較例9)，全光線透過率未達83%，無法得到83%以上之充分高度水準的全光線透過率。 　　又，與實施例1對比，可知作為芳香族二胺，利用了不具有氟系之取代基的m-Tol以取代使用具有氟系之取代基的TFMB時(比較例10)，YI之值成為44.6，無法使黃色度成為充分低的值(16以下之YI)。進一步地可知全光線透過率之值成為75.4%，無法得到83%以上之充分高度水準的全光線透過率。同樣地，作為芳香族酸二酐，利用了BPDA以取代使用PMDA，且作為芳香族二胺，利用了不具有氟系之取代基的m-Tol以取代使用具有氟系之取代基的TFMB時(比較例11)，YI之值成為23.2，無法使黃色度成為充分低之值(16以下之YI)。進一步地可知全光線透過率之值成為79.6%，無法得到83%以上之充分高度水準的全光線透過率。 　　進一步地，將比較例2與比較例5予以對比時，雖聚醯亞胺之製造時所利用的芳香族二胺種類相異，但由其芳香族二胺之種類，可確認到於重複單位中導入具有含氟取代基(四氟甲基)的伸芳基時(比較例2)，聚醯亞胺之黃色度(YI)值成為更低值。同樣地，將比較例3與比較例6予以對比時，雖聚醯亞胺之製造時所利用的芳香族二胺種類相異，但由其芳香族二胺之種類，可確認到於重複單位中導入具有含氟取代基(四氟甲基)的伸芳基時(比較例3)，聚醯亞胺之黃色度(YI)值成為更低值。又，將比較例4與比較例11予以對比時，雖聚醯亞胺之製造時所利用的芳香族二胺種類相異，但由其芳香族二胺之種類，可確認到於重複單位中導入具有含氟取代基(四氟甲基)的伸芳基時(比較例4)，聚醯亞胺之黃色度(YI)值成為更低值。 　　一併考慮如此之芳香族二胺之種類所致的效果不同(傾向)，與實施例1～4之結果時，可知如本案般，藉由含有前述重複單位(A)及(B)，且相對於前述重複單位(A)及(B)之總量而言，前述重複單位(A)之比率為5～35莫耳%的聚醯亞胺，係成為以更高度水準地且平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數者。 　　再者，實施例7中得到之聚醯亞胺，除了加熱步驟中之環境氣體係利用空氣以外，係與實施例6相同方式所得者(利用本發明之聚醯胺酸所得者)。此處，一般而言，利用脂肪族系之酸二酐製造聚醯亞胺的情況，且必須於300℃左右的高溫下加熱(燒成)時，若於空氣中或含有至少500ppm以上(依情況為1000ppm以上)之氧的活性氣體環境下燒成聚醯胺酸來製造聚醯亞胺時，已知因氧氧化，會有聚醯亞胺變色為黃色，或伴隨氧氧化切斷聚合物主鏈而使分子量降低因而脆化的傾向。因此，通常，利用脂肪族系之酸二酐來製造透明性高之聚醯亞胺時，為了擔保更高度之視覺辨認性等，一般而言係於惰性氣體環境下(例如含有惰性氣體且氧濃度100ppm以下之環境下)燒成聚醯胺酸來得到聚醯亞胺。相對於此，實施例7中得到之本發明之聚醯亞胺，可知雖為於空氣中將聚醯胺酸加熱(燒成)而得到者，不僅全光線透過率為86%以上而具有非常高度之透明性，且聚醯亞胺之黃色度(YI)為16以下。由如此之結果，明顯可知本發明之聚醯胺酸(實施例1～8)，即使為製造在製造製程上空氣燒成為必要不可缺之領域，或者製造時或使用時必須採用高氧濃度條件(例如氧濃度成為500ppm以上之條件)及會產生氧之條件的領域等之產品所利用的聚醯亞胺的情況，於製造後或使用時亦可使聚醯亞胺具有充分的視覺辨認性，特別有用於調製如上述領域之產品所利用的聚醯亞胺。又，亦可知實施例7中得到之本發明之聚醯亞胺，線膨脹係數係與在氮中進行燒成之實施例6或實施例1同等程度(CTE：1.2ppm/K)，與於氮中進行燒成者同樣地為具有充分低之線膨脹係數者。再者，由表1所示結果，亦可知實施例7中得到之本發明之聚醯亞胺，雖為於空氣中將聚醯胺酸加熱(燒成)所得到者，如前所述，具有300℃以上之Tg、300℃以上之軟化溫度(軟化點)、400℃以上(較佳為450℃以上)之Td5%，為具有十分高水準之耐熱性者。 　　由如此之結果，亦可知本發明之聚醯胺酸(實施例1～8)，與加熱(燒成)時之環境無關地，例如，即使於氮環境下燒成時(實施例1～6及8)，或即使於空氣中燒成時(實施例7)，亦可充分抑制所得之聚醯亞胺之著色，可得到在充分抑制黃色度上昇的同時，透明性高，且線膨脹係數充分低的聚醯亞胺。 ＜關於實施例1～8中得到之聚醯亞胺薄膜之雷射剝離性＞ 　　由聚醯亞胺所構成的薄膜之調製步驟中，除了不實施步驟(iii)(薄膜之回收步驟：藉由將聚醯亞胺塗覆玻璃浸漬於90℃熱水中，由前述玻璃基板剝離聚醯亞胺薄膜，而得到聚醯亞胺薄膜之步驟)以外，係分別採用與實施例1～8記載之步驟相同的步驟，分別調製聚醯亞胺塗覆玻璃。接著，對各聚醯亞胺塗覆玻璃照射雷射，進行關於其剝離可否等之測定。亦即，使用Light Machinery公司製之商品「pm848(準分子雷射XeCl、308nm、最大脈衝能量320 mJ/cm2 )」作為雷射發射裝置，以將雷射之照射能量密度設為50～320mJ/cm2 (由低的能量密度(50mJ/cm2 )起，以每次10mJ/cm2 依次提高能量密度，至確認到剝離為止，利用確認到剝離之照射能量密度)，脈衝寬度設為20～30ns、重疊率(重複率)設為50%、雷射重複頻率(重複率)設為30Hz、雷射光之照射面形狀設為縱14mm、橫30mm之長方形的條件，對各聚醯亞胺塗覆玻璃自玻璃基板側照射雷射光，目視判斷由聚醯亞胺所構成的薄膜可否剝離(見到牛頓環時判斷為可剝離)，與有無著色、有無畫面(shot)不均。 　　其結果，可知採用與實施例1～8記載之步驟相同步驟而得到的聚醯亞胺塗覆玻璃，均以140mJ/cm2 之照射能量密度、重疊率(重複率)50%，於聚醯亞胺薄膜並無著色或畫面不均而可剝離(可確認到牛頓環)。由如此之結果，亦可知由本發明之聚醯亞胺所構成的薄膜，當於層合於玻璃上之狀態時(作為玻璃基板上之層合物時)，藉由照射雷射，可在充分抑制品質變化之下進行剝離。又，由該結果，明顯可知於玻璃基板(所謂的承載基板等)上層合由本發明之聚醯亞胺所構成的薄膜後，於該薄膜上直接構裝薄膜電晶體等，藉由進行所謂的雷射剝離(lift-off)加工，可由前述玻璃基板使由聚醯亞胺所構成的薄膜剝離，亦可知由本發明之聚醯亞胺所構成的薄膜，可適合地應用於製造構裝有薄膜電晶體等之顯示器等的方法等。 [產業上之可利用性] 　　如以上說明，依照本發明，可提供能夠以更高度水準地且平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數的聚醯亞胺；可效率良好地形成該聚醯亞胺之聚醯胺酸；該聚醯胺酸之溶液；以及由前述聚醯亞胺所構成的聚醯亞胺薄膜。 　　如此之本發明之聚醯亞胺，由於為以更高度水準地且平衡良好地具有充分高度之全光線透過率、充分低之黃色度與充分低之線膨脹係數者，故特別有用於作為例如可撓配線基板用薄膜、耐熱絕緣膠帶、電線漆包、半導體之保護塗覆劑、液晶配向膜、有機EL(有機電致發光)用透明導電性薄膜、有機EL照明用薄膜、可撓基板薄膜、可撓有機EL用基板薄膜、可撓透明導電性薄膜、有機薄膜型太陽電池用透明導電性薄膜、色素增感型太陽電池用透明導電性薄膜、可撓氣體障壁性薄膜、觸控式面板用薄膜、可撓顯示器用擋風玻璃保護膜、可撓顯示器用背膜、可撓顯示器用TFT基板、半導體用保護膜(緩衝塗層)、層間絕緣膜、光阻、影像感測器用微透鏡等之材料。Hereinafter, the present invention will be described in detail based on its suitable embodiments. [Polyimine] The polyimine of the present invention contains the following general formula (1):
Figure 02_image011
[In formula (1), R 1 , R 2 , and R 3 each independently represent one kind selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and R 10 represents a fluorine-containing The substituent is an arylene group having 6 to 40 carbon atoms, and n represents an integer of 0-12]. The repeating unit (A) represented by the following general formula (2):
Figure 02_image013
[In formula (2), R 10 represents an arylene group having 6 to 40 carbon atoms having a fluorine-containing substituent]. The repeating unit (B) indicated, and the content of the repeating unit (A) is 5 to 35 mol% relative to the total amount of the repeating units (A) and (B). Regarding the aforementioned repeating unit (A), the alkyl group selected for R 1 , R 2 , and R 3 in the general formula (1) is an alkyl group having 1 to 10 carbon atoms. If the carbon number exceeds 10, the glass transition temperature is lowered, and it is impossible to achieve a sufficiently high level of heat resistance necessary for use in various substrate materials. In addition, the number of carbon atoms in the alkyl group selected for R 1 , R 2 , and R 3 is preferably 1 to 6, more preferably 1 to 5, and still more preferably, from the viewpoint of easier purification 1～4, especially preferably 1～3. In addition, the alkyl group that can be selected as R 1 , R 2 , and R 3 in this way may be linear or branched. Furthermore, from the viewpoint of ease of purification, such an alkyl group is more preferably a methyl group or an ethyl group. In addition, from the viewpoint of obtaining a higher degree of heat resistance during the production of polyimide, R 1 , R 2 , and R 3 in the general formula (1) are more preferably independently hydrogen atoms or carbon numbers. The alkyl group of 1 to 10, among them, from the viewpoint of easy availability of raw materials or easier purification, it is particularly preferable that each independently is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group; particularly preferred It is a hydrogen atom or a methyl group. In addition, the plural R 1 , R 2 , and R 3 in this formula are particularly preferably the same in terms of ease of purification. In addition, R 10 in the aforementioned general formula (1) is an arylene group having 6 to 40 carbon atoms (fluorine-based arylene group) having a fluorine-containing substituent. The fluorine-containing substituent referred to herein is not particularly limited as long as it contains fluorine, and examples thereof include fluorine atoms themselves, or alkyl groups (fluoroalkyl groups) in which at least a part of them are substituted with fluorine atoms. Among such fluorine-containing substituents, from the viewpoint of obtaining higher heat resistance, particularly fluoroalkyl groups with 1 to 10 carbon atoms (such as fluoromethyl, difluoromethyl, trifluoromethyl, Trifluoroethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, nonafluoro-sec-butyl, nonafluoroisobutyl, nonafluoro-t -Butyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl and other fluorinated alkyl groups) are preferred; among them, the carbon number is 1 to 5 (More preferably, 1 to 3) The fluoroalkyl group is more preferable. Moreover, such a fluorine-containing substituent is more preferably a fluoroalkyl group having 1 to 5 (more preferably 1 to 3) carbon atoms from the viewpoint of availability of raw materials. In this way, regarding the aforementioned R 10 , the fluorine-containing substituent of the aforementioned arylene group is more preferably a fluoroalkyl group having 1 to 3 carbon atoms (more preferably 1 to 2) (particularly preferably a perfluoroalkyl group) . Furthermore, here, "fluoroalkyl" refers to a group in which part or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms (Furthermore, as long as such a group is at least part of the hydrogen atoms of the alkyl group replaced by fluorine atoms Substitution is sufficient, and part of the hydrogen atoms of the alkyl group may be further substituted with substituents other than fluorine atoms (for example, halogen atoms other than fluorine atoms, hydroxyl, alkoxy, phenoxy, deuterium, etc.), and, ""Perfluoroalkyl" refers to a group in which all hydrogen atoms of an alkyl group are replaced by fluorine atoms. Regarding the arylene group having a fluorine-containing substituent that can be selected as R 10 in the aforementioned general formula (1), the carbon number of the aforementioned arylene group (in addition, the carbon number refers to the carbon number of the aryl group itself, The carbon number in the aforementioned fluorine-containing substituent is 6-40 except for the carbon number. Moreover, the carbon number of such an aryl extension group is preferably 6-30, more preferably 12-20. If such a carbon number exceeds the aforementioned upper limit, the heat resistance tends to decrease. Such arylene groups include, for example, phenylene, biphenylene, bitriphenylene, naphthylene, anthrylene, phenylene, phenanthryl, phenanthryl, indenyl, and Pyrene or benzanthracenyl, etc., among them, from the viewpoint of availability, biphenylene, phenylene, and naphthylene are particularly preferred; more preferred are biphenylene and phenylene. Furthermore, the arylene group having a fluorine-containing substituent selected as R 10 in the aforementioned general formula (1) is preferably the following general formula (3) from the viewpoint of heat resistance or availability:
Figure 02_image015
[In the formula (3), R 5 represents a fluoroalkyl group having 1 to 10 carbon atoms (more preferably a perfluoroalkyl group)]. The base of expression, especially the following general formula (3-I)
Figure 02_image017
The base of expression is particularly good. Furthermore, in the polyimide of the present invention, as the aforementioned repeating unit (A), it can also be used in combination with a plurality of different repeating units (A) such as the type of R 10 . Furthermore, with regard to the aforementioned repeating unit (B), R 10 in the aforementioned general formula (2) has the same meaning as R 10 in the aforementioned general formula (1) (the suitable ones are also the same as those in the aforementioned general formula (1) Same for R 10 ). Furthermore, polyimide of the present invention, examples of the repeating unit (B), the kind of R 10 may also be a combination of a plurality of different types of repeating unit (B) be utilized. Furthermore, the polyimide of the present invention has a sufficient level of heat resistance, and at the same time exhibits a sufficiently high level of total light transmittance, a sufficiently low yellowness, and a sufficiently low From the viewpoint of the coefficient of linear expansion, it is preferable that all R 10 in the repeating units (A) and (B) are the same. In addition, in the polyimide of the present invention, with respect to the total amount of the repeating unit (A) represented by the general formula (1) and the repeating unit (B) represented by the general formula (2), the repeating unit ( The content of A) is 5 to 35 mol% based on the molar amount. If the content of the repeating unit (A) represented by the general formula (1) does not reach the aforementioned lower limit, it tends to be difficult to achieve a sufficiently high total light transmittance (more preferably, a total light transmittance of 83.0% or more). Furthermore, it is difficult to achieve a sufficiently low linear expansion coefficient (preferably a linear expansion coefficient of -20ppm/K to 20ppm/K), and it is impossible to achieve a sufficiently high total light transmittance and sufficient high-level balance at a high level. Low yellowness and sufficiently low linear expansion coefficient. On the other hand, when the content of the aforementioned repeating unit (A) exceeds the aforementioned upper limit, the linear expansion coefficient (preferably -20ppm/K to 20ppm/K) cannot be obtained at this time. Those with a sufficiently low yellowness and a sufficiently low linear expansion coefficient in a well-balanced manner at a high level. Furthermore, the polyimide of the present invention has a sufficiently high total light transmittance, and at the same time, it has a sufficiently low yellowness and a sufficiently low linear expansion coefficient at a higher level in a well-balanced perspective, compared to For the total amount of the repeating unit (A) represented by the general formula (1) and the repeating unit (B) represented by the general formula (2), the content ratio of the repeating unit (A) is more preferably 5-25 mol %, more preferably 10-20 mol%, particularly preferably 12.5-17.5 mol%. In addition, from the same viewpoint, the content of the repeating unit (B) must be 95 to 65 mol based on the molar amount relative to the total amount of the repeating unit (A) and the repeating unit (B) %, more preferably 95-75 mol%, still more preferably 90-80 mol%, particularly preferably 87.5-82.5 mol%. In addition, the polyimide of the present invention may contain other repeating units within a range that does not impair the effects of the present invention. Such other repeating units are not particularly limited, and well-known repeating units that can constitute polyimide can be appropriately used. In addition, when the polyimide of the present invention contains other repeating units, the total amount of the repeating unit (A) represented by the above general formula (1) and the repeating unit (B) represented by the above general formula (2) is preferably With respect to all the repeating units in the polyimide, the repeating units (A) and (B) are contained so as to become 50 mol% or more (more preferably 70 mol% or more). Furthermore, in this way, the content ratio of the total amount of the repeating unit (A) and the repeating unit (B) relative to all the repeating units in the polyimide is more preferably 80-100 mol%, and more Preferably, it is 90-100 mol%. If the content ratio of the total amount of repeating units (A) and (B) to all repeating units in the polyimide does not reach the aforementioned lower limit, it may be difficult to achieve a well-balanced and sufficiently low yellowness and The tendency of those with sufficiently low linear expansion coefficients. Furthermore, from the viewpoint of forming polyimide more efficiently, the polyimide of the present invention is substantially composed of repeating units (A) and (B) (substantially not containing other repeating units, More preferably, the total amount of the aforementioned repeating unit (A) and the aforementioned repeating unit (B) is 95 mol% or more, still more preferably 98 mol% or more, particularly preferably 99 mol% or more). Moreover, such a polyimide preferably has a linear expansion coefficient of -20 ppm/K to 20 ppm/K, more preferably -10 to 10 ppm/K, and still more preferably -5 to 5 ppm/K. When such a linear expansion coefficient exceeds the aforementioned upper limit, when it is combined with a metal or inorganic compound with a linear expansion coefficient in the range of 5-20 ppm/K, it tends to be easily peeled due to thermal history, and it is used as a substrate for microelectronics. When used, it is difficult to produce the final products of microelectronics with good yield (such as organic EL displays, touch panels, protective films (buffer coatings) for semiconductors, interlayer insulating films, photoresists, microlenses for image sensors, etc. ). On the other hand, when the linear expansion coefficient does not reach the lower limit, peeling or curling tends to occur easily when the inorganic substance is laminated. Furthermore, in the case of manufacturing devices for the upper or lower layers of the film made of polyimide, when the device is an inorganic compound, from the viewpoint of suppressing curling of the film or deformation during manufacturing, it is preferable to use an inorganic compound The same degree of polyimide with sufficiently low linear expansion coefficient. From this point of view, the polyimide of the present invention also preferably has a linear expansion coefficient within the above range. In addition, in the present invention, the following values are adopted for the value of the coefficient of linear expansion of polyimide. That is, first, with respect to the polyimide to be measured, a film composed of the polyimide with a size of 20 mm in length, 5 mm in width, and 13 μm in thickness is formed. After that, the film was vacuum dried (120°C for 1 hour), and heat-treated at 200°C for 1 hour in a nitrogen atmosphere to obtain a dried film. Then, using the dried film thus obtained as a sample, using a thermomechanical analyzer (trade name "TMA8310" manufactured by Rigaku) as a measuring device, in a nitrogen environment, using a tensile mode (49mN) and a heating rate of 5°C/min For the conditions, the length change in the longitudinal direction of the aforementioned sample was measured at 50°C to 200°C, and the average value of the length change per 1°C (1K) in the temperature range of 50°C to 200°C was obtained. Then, the aforementioned average value thus obtained is used as the value of the linear expansion coefficient of the polyimide film of the present invention (the value of the linear expansion coefficient of the polyimide film when the thickness is 13 μm is used as the value of the polyimide film of the present invention). The value of the linear expansion coefficient of imine). Furthermore, such a polyimide preferably has a 5% weight reduction temperature (Td5%) of 400°C or higher, more preferably 450-550°C. If the 5% weight reduction temperature does not reach the aforementioned lower limit, it will tend to be difficult to obtain sufficient heat resistance for use as a substrate for microelectronics products. On the other hand, if the aforementioned upper limit is exceeded, it may be difficult to manufacture The tendency of polyimide with such characteristics. Furthermore, such a 5% weight reduction temperature can be measured by setting the scanning temperature to 30°C to 550°C while circulating nitrogen in a nitrogen environment and heating at a temperature rise rate of 10°C/min. The temperature at which the weight of the sample is reduced by 5%. In addition, for such a measurement, for example, a thermogravimetric analyzer ("TG/DTA220" manufactured by SII Nanotechnology Co., Ltd.) can be used as a measurement device. In addition, such a polyimide preferably has a glass transition temperature (Tg) of 300°C or higher, more preferably 350 to 500°C. If such a glass transition temperature (Tg) does not reach the aforementioned lower limit, it will be difficult to obtain sufficient heat resistance for use as a substrate for microelectronics products (for example, when using polyimide as a solar cell, a liquid crystal display device) Or in the case of a transparent electrode substrate for an organic EL display device, in the heating step of the manufacturing process of the product, the tendency of deterioration (cracking, etc.) of the polyimide (substrate) is not sufficiently suppressed. On the other hand, When the upper limit is exceeded, it tends to be difficult to produce polyimide having such characteristics. Furthermore, such a glass transition temperature (Tg) can be measured at the same time by using a thermomechanical analyzer (trade name "TMA8311" manufactured by Rigaku) as a measuring device in the same way as the softening temperature measurement. In addition, when measuring the glass transition temperature, it is better to perform the measurement by scanning the range of 30°C to 550°C under the condition of a heating rate: 5°C/min in a nitrogen environment. Moreover, such a polyimide preferably has a softening temperature (softening point) of 300 to 550°C, more preferably 320 to 550°C, and still more preferably 340 to 510°C. If such a softening temperature does not reach the aforementioned lower limit, the heat resistance will decrease. For example, when a thin film composed of the polyimide is used as a substrate for the transparent electrode of a solar cell, a liquid crystal display device or an organic EL display device, the product During the manufacturing process, it tends to be difficult to sufficiently suppress the quality deterioration (cracking, etc.) of the film (substrate). On the other hand, when the above-mentioned upper limit is exceeded, the polyimide may be used in the production of polyimide. At the same time as the thermal ring-closing condensation reaction, the solid-phase polymerization reaction does not proceed sufficiently, and the film tends to become brittle when it is formed. Furthermore, the softening temperature of such polyimide can be measured as follows. That is, by preparing a film made of polyimide with a size of 5 mm in length, 5 mm in width, and 0.013 mm (13 μm) in thickness as a measurement sample, a thermomechanical analyzer (trade name "TMA8311" manufactured by Rigaku) ) As a measuring device, in a nitrogen environment, a temperature rise rate of 5°C/min is used, and a transparent quartz needle (tip diameter: 0.5mm) is inserted into the film under a pressure of 500mN at a temperature range of 30°C to 550°C. The needle is measured simultaneously with the glass transition temperature (Tg) (it can be measured by the so-called penetration (pin) method). In addition, in such a measurement, the softening temperature was calculated based on the measurement data in accordance with the method described in JIS K 7196 (1991). Furthermore, since such polyimine is difficult to dissolve in a solvent to determine its molecular weight, it is preferable to use the molecular weight (number average molecular weight or weight average molecular weight) or molecular weight distribution of the precursor polyamide acid (polyamide acid). As an indicator, to explore its suitability. The number average molecular weight (Mn) of the aforementioned polyamide acid (polyamide acid) of such a polyimide precursor is preferably 1,000 to 1,000,000, and more preferably 10,000 to 500,000 in terms of polystyrene. If such a number average molecular weight does not reach the aforementioned lower limit, it is not only difficult to achieve sufficient heat resistance, but also tends to be difficult to obtain polyimide efficiently. On the other hand, if the number average molecular weight exceeds the aforementioned upper limit, the viscosity increases and the filtration step It takes a long time or requires a large amount of diluting solvent for viscosity adjustment, so it tends to be difficult to process. In addition, the weight average molecular weight (Mw) of the aforementioned polyamide acid (polyamide acid) of such a polyimide precursor is preferably 1,000 to 5,000,000 in terms of polystyrene. In addition, the lower limit of the numerical range of the weight average molecular weight (Mw) is more preferably 5,000, still more preferably 10,000, and particularly preferably 20,000. In addition, the upper limit of the numerical range of the weight average molecular weight (Mw) is more preferably 5,000,000, still more preferably 500,000, and particularly preferably 100,000. If such a weight average molecular weight does not reach the aforementioned lower limit, it is not only difficult to achieve sufficient heat resistance, but also tends to be difficult to obtain polyimide efficiently. On the other hand, if the aforementioned upper limit is exceeded, the viscosity increases and a filtration step is required. It takes a long time or requires a large amount of diluting solvent for viscosity adjustment, so it tends to be difficult to process. Further, the molecular weight distribution (Mw/Mn) of the aforementioned polyamide acid (polyamide acid) of such a polyimide precursor is preferably 1.1-5.0, more preferably 1.5-3.0. If such a molecular weight distribution does not reach the aforementioned lower limit, it tends to be difficult to manufacture. On the other hand, if it exceeds the aforementioned upper limit, it tends to be difficult to obtain a uniform film when forming a thin film. Furthermore, the molecular weight (Mw or Mn) or molecular weight distribution (Mw/Mn) of such polyimide can be measured using a gel permeation chromatography (GPC) measuring device (EcoSEC HLC-8320GPC manufactured by TOSOH, column: TOSOH GPC column TSKgel Super AW2500, 3000, 4000, column temperature: 40°C, developing solvent: dimethylacetamide solvent (flow rate 0.5mL/min.) added with 10mM LiBr for measurement as a measuring device The data is calculated in terms of polystyrene. In addition, such polyimide is in relation to the appropriate value of yellowness (YI) (below 16), and is guaranteed to be used in transparent displays, solar cells, touch panels, windshield protective films, and transparent FPCs. From the viewpoint of high visibility required when glass is used to replace flexible transparent materials, the total light transmittance is more preferably 83% or more (more preferably 85% or more, particularly preferably 87% or more). If such a total light transmittance does not reach the aforementioned lower limit, even if the yellowness is 16 or less, depending on the value of the yellowness, it is difficult to exhibit the required transparency (visibility) when used for various purposes. In addition, from the viewpoint of obtaining higher transparency of such polyimide, the haze (turbidity) is more preferably 5 or less (more preferably 4 or less, particularly preferably 3 or less). Furthermore, from the viewpoint of obtaining a higher degree of transparency of such a polyimide, the yellowness (YI) is more preferably 16.0 or less (more preferably 11.0 or less, particularly preferably 10.5 or less). Moreover, when such yellowness exceeds the aforementioned upper limit, it is difficult to ensure the high degree of hue, lightness, chroma, brightness, hue, contrast, chroma, and transparency (visual recognition) necessary for the purpose, so even if the full light is transmitted With a rate of 83% or more, it is difficult to achieve the performance required for various applications. In addition, such total light transmittance, haze (turbidity) and yellowness (YI) can be used with the product name "HAZE METER NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. or Nippon Denshoku Industries Co., Ltd. The company’s product name "Spectrophotometer SD6000" is used as the measuring device (the product name "HAZE METER NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. is used to measure total light transmittance and haze. The company’s trade name "Spectrophotometer SD6000" measures the degree of yellowness), and a film made of polyimide with a thickness of 10-15 μm (preferably 13 μm) is used as the value measured for the measurement sample. However, as for the yellowness (YI), as described below, the measured value of a film with a thickness of 13 μm or a conversion value of a film with a thickness of 13 μm is adopted. That is, as long as the total light transmittance and haze (turbidity) are a film made of polyimide with a thickness of 10 to 15 μm, the thickness is sufficiently thin and does not affect the measured value, so the same polyimide The imine can be measured to the same value. On the other hand, the yellowness (YI) tends to be affected by the thickness of the film. Therefore, in the present invention, a thin film having a thickness in the aforementioned range (10-15 μm) is used as a sample for measurement, and As the value of the yellowness (YI), a value converted to a film thickness of 13 μm is used (in addition, it is a measured value when measured with a film thickness of 13 μm). In this way, in the present invention, the value of the yellowness (YI) is a value measured using a film having a thickness of 13 μm or converted to a value of a film having a thickness of 13 μm. From this point of view (yellowness can be converted to a value of 13μm thick film), the total light transmittance, haze (turbidity) and yellowness (YI) can be measured using the aforementioned range (10～ A film with a thickness in the range of 15μm) (Furthermore, when measuring YI using a film with a thickness other than 13μm as a measurement sample, it must be converted to a thickness of 13μm as described above. Therefore, this is not necessary From the viewpoint of conversion, it is preferable to prepare and use a film made of polyimide with a thickness of 13 μm as a measurement sample). In addition, the vertical and horizontal dimensions of the measurement sample may be any size that can be placed in the measurement location of the aforementioned measuring device, and the vertical and horizontal dimensions can be changed as appropriate. Furthermore, such total light transmittance is obtained by measuring according to JIS K7361-1 (issued in 1997), and haze (turbidity) is obtained by measuring according to JIS K7136 (issued in 2000) The yellowness (YI) is obtained by measuring according to ASTM E313-05 (issued in 2005). In addition, the method which can be used suitably for manufacturing such a polyimide is as follows. [Polyamic acid] The polyamic acid of the present invention contains the following general formula (4):
Figure 02_image019
[In formula (4), R 1 , R 2 , and R 3 each independently represent one kind selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and R 10 represents a fluorine-containing The substituent is an arylene group having 6 to 40 carbon atoms, and n represents an integer of 0-12]. The repeating unit (C) represented by the following general formula (5):
Figure 02_image021
[In formula (5), R 10 represents an arylene group having 6 to 40 carbons having a fluorine-containing substituent]. The repeating unit (D) indicated, and the content of the repeating unit (C) is 5 to 35 mol% relative to the total amount of the repeating units (C) and (D). Such a polyamide acid can be suitably used in the production of the polyimide of the present invention (it can be obtained as a reaction intermediate (precursor) in the production of the polyimide of the present invention). So the general formula R (4) in the 1, R 2, R 3, R 10 and n lines in the general formula R (1) in the 1, R 2, R 3, R 10 and n are the same as those which Suitable ones are also the same as R 1 , R 2 , R 3 , R 10 and n in the above general formula (1). Yet, so the general formula (5) in the Department of R 10 in the general formula (2) is the same as those of R 10 (i.e., the general formula (1) is the same as those of R 10), adapted Zheyi Same as R 10 in the above general formula (2). In addition, in the polyamide acid of the present invention, with respect to the total amount of the repeating unit (C) represented by the general formula (4) and the repeating unit (D) represented by the general formula (5), the repeating unit ( The content of C) is based on the molar amount of 5 to 35 molar%. If the content of the repeating unit (C) represented by the general formula (4) does not reach the aforementioned lower limit, when the polyamide acid is used to produce polyimide, it is difficult to achieve a sufficiently high total light transmittance (preferably It tends to have a total light transmittance of 83.0% or more), and it is difficult to be a product with a sufficiently low linear expansion coefficient (preferably -20ppm/K～20ppm/K linear expansion coefficient), and cannot be balanced at a high level Polyimide with sufficiently high total light transmittance, sufficiently low yellowness and sufficiently low coefficient of linear expansion. On the other hand, when the content of the aforementioned repeating unit (C) exceeds the aforementioned upper limit, in this case, it is also impossible to obtain a sufficiently low linear expansion coefficient (preferably -20 ppm) when the polyamide acid is used to produce polyimide. /K～20ppm/K (linear expansion coefficient) of polyimide, can not be manufactured at a high level, well-balanced, with sufficient height of total light transmittance, sufficiently low yellowness and sufficiently low linear expansion coefficient. Polyimide. Furthermore, in the polyimide of the present invention, the polyimide is used to obtain a polyimide having a sufficiently low yellowness and a sufficiently low linear expansion coefficient at a higher level and in a good balance In terms of the total amount of the repeating unit (C) and the repeating unit (D), the content of the repeating unit (C) is more preferably 5-25 mol%, and still more preferably 10-20 Mole%, particularly preferably 12.5 to 17.5 mole%. In addition, the polyamide acid of the present invention may contain other repeating units in a range that does not impair the effect of the present invention. Such other repeating units are not particularly limited, and known repeating units that can constitute polyamide acid can be appropriately used. In addition, when other repeating units are contained in the polyamide acid of the present invention, the total amount of the repeating unit (C) represented by the general formula (4) and the repeating unit (D) represented by the general formula (5) is preferred , With respect to all the repeating units in the polyamide acid, the repeating units (C) and (D) are contained in a manner of 50 mol% or more (more preferably 70 mol% or more). Furthermore, with respect to all repeating units in such polyamide acid, the content ratio of the total amount of the repeating unit (C) and the repeating unit (D) is more preferably 80-100 mol%, and More preferably, it is 90-100 mol%. If the total content of such repeating units (C) and (D) does not reach the aforementioned lower limit, it will be difficult to produce a well-balanced total light transmittance, sufficiently low yellowness, and sufficiently low linear expansion. The coefficient of the tendency of polyimide. Furthermore, from the viewpoint of using the polyimide to form polyimide more efficiently, the polyimide of the present invention is preferably substantially composed of repeating units (C) and (D) (Substantially does not contain other repeating units, more preferably the total amount of the aforementioned repeating units (C) and (D) is 95 mol% or more, more preferably 98 mol% or more, particularly preferably 99 mol% or more ). In addition, the inherent viscosity [η] of such polyamide acid is preferably 0.05 to 3.0 dL/g, more preferably 0.1 to 2.0 dL/g. When the intrinsic viscosity [η] is less than 0.05 dL/g, when the film-like polyimide is used, the resulting film tends to become brittle. On the other hand, when it exceeds 3.0 dL/g, the viscosity is too high , The processability is reduced, for example, it is difficult to obtain a uniform film when manufacturing a film. In addition, such inherent viscosity [η] can be measured in the following manner. That is, first, tetramethylurea (TMU) is used as a solvent, and the aforementioned polyamide acid is dissolved in the tetramethylurea (TMU) to have a concentration of 0.5 g/dL to obtain a measurement sample (solution). Next, use the aforementioned measurement sample and use a dynamic viscometer at a temperature of 30°C to measure the viscosity of the aforementioned measurement sample, and use the obtained value as the intrinsic viscosity [η]. Furthermore, such a dynamic viscometer uses an automatic viscosity measuring device (trade name "VMC-252") manufactured by Clutch Corporation. Hereinafter, a method that can be used suitably in order to produce such a polyamide acid will be explained. (Method that can be suitably used to produce polyamide acid) There is no particular limitation on the method that can be suitably used to produce such polyamide acid. For example, it can be suitably used to contain the following general formula (10) :
Figure 02_image023
[In formula (10), R 1 , R 2 , and R 3 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and n represents 0 to 12 Integer]. The compound (A), and the following general formula (11):
Figure 02_image025
The compound (B) shown, and the content of the compound (A) is 5 to 35 mol% of the tetracarboxylic dianhydride (compound (I) relative to the total amount of the compound (A) and (B) ); and contains the following general formula (12):
Figure 02_image027
[In the formula (12), R 10 represents an arylene group having 6 to 40 carbon atoms having a fluorine-containing substituent]. The diamine compound (compound (II)) of the compound represented is reacted in the presence of an organic solvent to obtain the repeating unit (C) and the repeating unit (D), which are relative to the repeating unit (C) and ( D) In terms of the total amount, the content of the aforementioned repeating unit (C) is 5 to 35 mol% of polyamide acid. Furthermore, the repeating unit (C) is derived from the compound (A) and the compound represented by the general formula (12), and the repeating unit (D) is derived from the compound (B) and the general formula (12). ) Represents the compound. So polyamide compound of the general formula (10) The method for producing an acid used in the representation R (A) in the 1, R 2, R 3 and n, the Department of the general formula R (1) in the 1, R 2. R 3 and n have the same meaning (the suitable ones are also the same as R 1 , R 2 , R 3 and n in the above general formula (1)) and R 10 in the compound represented by the above general formula (12) is the general formula (1) and R (2) in the same sense (that is suitable Zheyi the general formula (1) and the same (R 2) of in 10) 10. The method for producing the compound (A) represented by the general formula (10) is not particularly limited, and a known method (for example, the method described in International Publication No. 2011/099518, etc.) can be suitably used. In addition, the method for producing the compound (B) represented by the general formula (11) is not particularly limited, and a known method can be suitably used. Moreover, such a compound (B) is pyromellitic anhydride (1,2,4,5-pyromellitic dianhydride, pyromellitic anhydride), and a commercially available one can also be suitably used for this compound. Further, the method for producing the compound represented by the aforementioned general formula (12) is not particularly limited, and a known method can be appropriately adopted. Moreover, the compound represented by such general formula (12) can also use a commercially available one suitably. In addition, for the aforementioned tetracarboxylic dianhydride (compound (I)), the content of the aforementioned compound (A) relative to the total amount of the aforementioned compounds (A) and (B) in the compound (I) must be 5～ 35 mol%. When the content of such compound (A) does not reach the aforementioned lower limit and exceeds the aforementioned upper limit, the content of the repeating unit (C) relative to the total amount of the repeating units (C) and (D) cannot be made the desired content Range (5～35 mol% range). In addition, from the same viewpoint, in the compound (I), the content ratio of the compound (A) is more preferably 5-25 mol% relative to the total amount of the compounds (A) and (B). More preferably, it is 10-20 mol%, and particularly preferably 12.5-17.5 mol%. In addition, as the aforementioned compound (I), in order to include other repeating units in the polyamide acid of the present invention, other tetracarboxylic dianhydrides other than the compounds (A) and (B) may be mixed and used. Furthermore, other tetracarboxylic dianhydrides other than such compounds (A) and (B) can be suitably used other well-known tetracarboxylic dianhydrides that can be used in the production of polyimides. At this time, the usage amount of other tetracarboxylic dianhydrides other than the compounds (A) and (B), as long as the content of the repeating units (C) and (D) in the obtained polyamide acid is in the desired range ( The above-mentioned suitable content range, etc.) may be appropriately adjusted. Furthermore, as the aforementioned tetracarboxylic dianhydride (compound (I)), it has a sufficient level of heat resistance, and at the same time exhibits a sufficiently high total light transmittance and a sufficiently low yellow color at a higher level in a well-balanced manner From the standpoint of the degree of thermal expansion and sufficiently low coefficient of linear expansion, the compound (I) is preferably one substantially composed of the aforementioned compounds (A) and (B) (the compound (I) substantially does not contain the compounds (A) and ( For other tetracarboxylic dianhydrides other than B), in compound (I), the total amount of the aforementioned compounds (A) and (B) is more preferably 95 mol% or more, and more preferably 98 mol% or more , The best is 99 mol% or more, and the best is 100 mol%). Furthermore, as the aforementioned compound (II), in order to make the polyamide acid of the present invention contain other repeating units, it may appropriately contain other diamine compounds (other aromatic diamines) other than the compound represented by the aforementioned general formula (12) And alicyclic diamines, etc.). For such other diamine compounds, other known diamine compounds that can be used in the production of polyimide can be suitably used. For such other diamine compounds, for example, siloxanes modified with amine groups at both ends can be suitably used. Specific examples of such two-terminal amino-modified silicones include 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and amino-modified silicones manufactured by Shin-Etsu Chemical Co., Ltd. Silicone oil (such as PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, X-22-9409, etc.), Gelest The company makes dimethylsiloxane diamines (such as DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A31, DMS-A32, DMS-A32R, DMS-A35, etc.). Furthermore, the usage amount of other diamine compounds other than the compound represented by the aforementioned general formula (12) in such compound (II) must be based on the ratio of the repeating units (C) and (D) in the obtained polyamide acid The content is adjusted appropriately so that the content becomes the desired range (the above-mentioned suitable content range, etc.). Furthermore, as a diamine compound (compound (II)), it has a sufficient level of heat resistance, and at the same time exhibits a sufficiently high total light transmittance, a sufficiently low yellowness, and a sufficient balance at a higher level. From the viewpoint of a low coefficient of linear expansion, the compound (II) is preferably a compound substantially composed of the compound represented by the aforementioned general formula (12) (compound (II) substantially does not contain other diamine compounds, and the compound (II) In II), it is more preferable that the total amount of the compound represented by the general formula (12) is 95 mol% or more, still more preferably 98 mol% or more, particularly preferably 99 mol% or more, and most preferably 100 mol% ear%). In addition, the aforementioned organic solvent is preferably an organic solvent that can dissolve both the aforementioned tetracarboxylic dianhydride (compound (I)) and the aforementioned diamine compound (compound (II)). Such organic solvents include, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfide, and γ-butyrolactone. Ester, propylene carbonate, ethylene carbonate, tetramethylurea (tetramethylurea (TMU)), 1,3-dimethyl-2-tetrahydroimidazolone, hexamethylphosphoramide, pyridine Aprotic polar solvents such as m-cresol, xylenol, phenol, and halogenated phenols; ether solvents such as tetrahydrofuran, dioxane, xerosol, glyme, etc.; cyclopentane Ketone solvents such as ketone, cyclohexanone or cycloheptanone; aromatic solvents such as benzene, toluene, xylene, etc. Such organic solvents can be used alone or in combination of two or more. In addition, the usage ratio of the above-mentioned tetracarboxylic dianhydride (compound (I)) and the above-mentioned diamine compound (compound (II)) is relative to 1 equivalent of the amine group of the above-mentioned diamine compound (compound (II)) The acid anhydride group in the above-mentioned tetracarboxylic dianhydride (compound (I)) is preferably 0.2 to 2 equivalents, more preferably 0.8 to 1.2 equivalents. If such a use ratio does not reach the aforementioned lower limit, the polymerization reaction does not proceed efficiently and a high molecular weight polyamide acid tends not to be obtained. On the other hand, if it exceeds the aforementioned upper limit, it may not be obtained like the aforementioned The tendency of high molecular weight polyamide acid. Further, the amount of the aforementioned organic solvent used is preferably such that the total amount of the aforementioned tetracarboxylic dianhydride (compound (I)) and the aforementioned diamine compound (compound (II)) is relative to the total amount of the reaction solution The amount is 1-50% by mass (more preferably 10-30% by mass). If the use amount of such an organic solvent does not reach the aforementioned lower limit, there is a tendency that polyamide acid cannot be efficiently obtained. On the other hand, if it exceeds the aforementioned upper limit, stirring tends to be difficult due to increased viscosity. In addition, when the tetracarboxylic dianhydride (compound (I)) is reacted with the diamine compound (compound (II)), from the viewpoint of increasing the reaction rate and obtaining polyamide acid with a high degree of polymerization, A basic compound is further added to the aforementioned organic solvent. There are no special restrictions on such basic compounds. Examples include triethylamine, tetrabutylamine, tetrahexylamine, 1,8-diazabicyclo[5.4.0]-undecene-7, pyridine, and isoquinoline. , Α-picoline and so on. In addition, the usage amount of such a basic compound is preferably 0.001 to 10 equivalents, more preferably 0.01 to 0.1 equivalents with respect to 1 equivalent of the above-mentioned tetracarboxylic dianhydride (compound (I)). If the use amount of such a base compound does not reach the aforementioned lower limit, the effect of the addition tends to decrease. On the other hand, if it exceeds the aforementioned upper limit, it tends to cause coloration or the like. In addition, the reaction temperature when the above-mentioned tetracarboxylic dianhydride (compound (I)) and the above-mentioned diamine compound (compound (II)) are reacted can be appropriately adjusted to a temperature at which these compounds can react. Limited, it is preferably -20°C to 200°C. In addition, as a method of reacting the above-mentioned tetracarboxylic dianhydride (compound (I)) with the above-mentioned diamine compound (compound (II)), a known method capable of performing a polymerization reaction of tetracarboxylic dianhydride and a diamine compound can be suitably used , There is no special limitation. For example, it can also be appropriately used in atmospheric pressure, nitrogen, helium, argon and other inactive environments, after dissolving the diamine compound in the solvent, adding the above-mentioned tetracarboxylic dianhydride (compound (I)), and then react for 10 to 48 hours. If such a reaction temperature or reaction time does not reach the aforementioned lower limit, it will tend to be difficult to react sufficiently. On the other hand, if the aforementioned upper limit is exceeded, the mixing rate of substances that degrade the polymer (oxygen, etc.) will increase and the molecular weight will tend to decrease. . In this way, by reacting the tetracarboxylic dianhydride (compound (I)) and the diamine compound (compound (II)) in the presence of an organic solvent, the polyamide acid of the present invention can be obtained. After the polyamide acid is prepared in this way, when the polyamide acid of the present invention is isolated from the aforementioned organic solvent, the isolation method is not particularly limited, and a known method capable of isolating polyamide acid can be appropriately used, such as , Can also be used as a re-precipitate and isolated method. [Polyamide acid solution] The polyamide acid solution of the present invention is one containing the above-mentioned polyamide acid of the present invention and an organic solvent. The organic solvent used for such a polyamide acid solution can be suitably used the same thing as the organic solvent used for the method which can be utilized suitably for manufacturing the said polyamic acid. Therefore, it is also possible to prepare the polyamide acid solution of the present invention by implementing a method that can be suitably used for the production of the polyamide acid described above, and using the reaction liquid obtained after the reaction as a polyamide acid solution as it is. That is, the polyamide acid solution of the present invention can also be prepared by reacting the tetracarboxylic dianhydride (compound (I)) and the diamine compound (compound (II)) in the presence of the aforementioned organic solvent. The polyamide is produced by obtaining a solution containing the polyamide and the organic solvent. The content of the aforementioned polyamic acid in such a polyamic acid solution is not particularly limited, and it is preferably 1-50% by mass, more preferably 10-30% by mass. If such a content does not reach the aforementioned lower limit, the molecular weight of the polyimide tends to decrease. On the other hand, if the content exceeds the aforementioned upper limit, the production of polyimide tends to become difficult. Moreover, such a polyimide solution can be suitably used for the production of the polyimide of the present invention. Furthermore, when such a polyimide solution is used in the production of polyimide, it can also be appropriately added and various additives (high molecular weight or imidization) that can be used to prepare polyimide The accelerators, deterioration preventives, antioxidants, light stabilizers, ultraviolet absorbers, modifiers, antistatic agents, flame retardants, plasticizers, nucleating agents, stabilizers, adhesion enhancers, lubricants, Molding agents, dyes, foaming agents, defoamers, surface modifiers, hard coat agents, leveling agents, surfactants, fillers (glass fibers, fillers, talc, mica, silica, etc.), etc.). In addition, when using such an additive, the content of the additive in the polyamide acid solution is not particularly limited, and it is preferably about 0.0001 to 80% by mass (more preferably 0.1 to 50% by mass). (Method that can be suitably used for the production of polyimide) The method that can be suitably used for the production of the polyimide of the present invention is not particularly limited, and can be suitably used by making the polyimide of the present invention The content of the repeating unit (A) relative to the total amount of the repeating unit (A) and (B) is 5 to 35 mole% of polyimide method. Furthermore, the repeating unit (A) is derived from the repeating unit (C) and the repeating unit (B) is derived from the repeating unit (D). Such a method for the imidization of polyamide is not particularly limited as long as it can be used for imidization of polyamide. A known method can be suitably used. For example, it is preferable to use The above-mentioned polyamide acid of the present invention is a method of applying heat treatment under a temperature condition of 60-450°C (more preferably 80-400°C) for imidization, or using a so-called "imidating agent" for imidation The method of amination. When the method of imidization by performing such a heat treatment is adopted, the reaction tends to proceed slowly when the heating temperature is less than 60°C. On the other hand, when the upper limit is exceeded, coloration or thermal decomposition occurs. Causes the tendency of molecular weight to decrease. In addition, the reaction time (heating time) in the case of adopting the method of imidization by applying heat treatment is preferably 0.5 to 5 hours. If such a reaction time does not reach the aforementioned lower limit, it tends to be difficult to achieve sufficient imidization. On the other hand, if it exceeds the aforementioned upper limit, it tends to be colored or thermally decomposed to reduce the molecular weight. Furthermore, the above-mentioned polyamide acid of the present invention can be produced in a well-balanced manner with a sufficiently low degree of yellowness and a sufficiently low coefficient of linear expansion even if it is heated under conditions containing oxygen as in the atmosphere to be imidized. Therefore, the environmental conditions during heating are not particularly limited, and it can be in inert gas or in the atmosphere. In addition, when heating and manufacturing in the atmosphere, not only can the polyimide be manufactured in simpler equipment, but also the polyimide can be manufactured without the need to control the ambient gas, so that the manufacturing efficiency of the final product can be further improved. In addition, in order to promote high molecular weight or imidization during heating and imidization, so-called accelerators (additives) can also be used. As such accelerators, known reaction accelerators (for example, tertiary amine compounds such as imidazole compounds, pyridine compounds, triethylamine, etc., amino acid compounds, etc.) can be suitably used. The amount of such an accelerator used is not particularly limited. For example, relative to 100 parts by mass of the solid content (polyamide acid) in the polyamide acid solution, it is 1-60 parts by mass, preferably 5~ 50 parts by mass. In addition, when a method of using a so-called "imidating agent" to imidize polyamides is used, it is preferable to make the above-mentioned polyamides of the present invention in a solvent in the presence of an imidizing agent. Acid imidization. Such a solvent can suitably use the same organic solvent as the organic solvent used in the above-mentioned polyimide production method of the present invention. As such an imidizing agent, well-known imidizing agents can be suitably used, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride; pyridine, colin base, lutidine, and triethylamine , N-methyl piperidine and other tertiary amines. In addition, the reaction temperature at the time of the imidization of the imidization by adding the imidization agent is preferably 0 to 200°C, more preferably 30 to 150°C. Furthermore, the reaction time is preferably 0.1 to 48 hours. If the reaction temperature or time does not reach the aforementioned lower limit, it tends to be difficult to fully imidize. On the other hand, if the aforementioned upper limit is exceeded, the mixing rate of substances (oxygen, etc.) that degrade the polymer increases and the molecular weight decreases. Or the tendency of hue to deteriorate. Moreover, the amount of such imidizing agent used is not particularly limited, as long as it is a few millimoles to several moles relative to 1 mole of the repeating unit represented by the general formula (5) in the polyamide acid. Ears (preferably about 0.01 to 4.0 moles). In addition, a method that can be suitably used for producing the polyimide of the present invention is preferably a method comprising the following steps: the above-mentioned tetracarboxylic dianhydride (compound (I)) and the above-mentioned diamine compound (compound (II) )) react in the presence of an organic solvent to obtain the repeating unit (C) and the repeating unit (D), and relative to the total amount of the repeating units (C) and (D), the repeating unit ( C) Step (I) of polyamide acid (the above-mentioned polyamide acid of the present invention) with a content of 5 to 35 mol%; and by imidizing the aforementioned polyamide acid, a polyamide containing the aforementioned repeat The unit (A) and the aforementioned repeating unit (B), and relative to the total amount of the aforementioned repeating units (A) and (B), the content of the aforementioned repeating unit (A) is 5 to 35 mol% of polyamide Step (II) of amine (polyimine of the present invention described above). In this way, when the method including step (I) and step (II) is adopted as the method for producing the polyimide of the present invention, the polyimide can be produced in a series of steps. Furthermore, when using a method including such steps (I) and (II), and in the aforementioned imidization, when the method of imidization by heat treatment is used, the following method may also be used: After performing the aforementioned step (I), without isolating the polyamide acid of the present invention, the aforementioned tetracarboxylic dianhydride (compound (I)) and the aforementioned diamine compound (compound (II) are combined in an organic solvent. ) The reaction solution obtained by the reaction (the reaction solution containing the polyamide acid of the present invention) is used as it is or the aforementioned accelerator is added, and the reaction solution is subjected to a treatment (solvent removal treatment) for evaporating and removing the solvent to remove the solvent , By performing the aforementioned heat treatment to imidize. By carrying out the treatment of evaporating and removing the solvent, the polyamide acid of the present invention can be isolated in the form of a film or the like, and then heat treatment or the like can be carried out. The temperature condition in the method of such a treatment for evaporating and removing the solvent is preferably 0 to 180°C, more preferably 30 to 150°C. If the temperature condition in the process of evaporating and removing the solvent does not reach the aforementioned lower limit, it tends to be difficult to evaporate and remove the solvent sufficiently. On the other hand, when the aforementioned upper limit is exceeded, the solvent may boil and become a thin film containing bubbles or pores. tendency. In this case, for example, when producing a film-like polyimide, it is only necessary to apply the obtained reaction solution directly on a substrate (for example, a glass plate), and perform the above-mentioned treatment for evaporating and removing the solvent and heating treatment. Method to produce film-like polyimide. In addition, there are no particular restrictions on the coating method of such a reaction liquid, and a known method (casting method, etc.) can be appropriately used. In addition, when the polyamide acid of the present invention is isolated from the aforementioned reaction solution for use, the isolation method is not particularly limited, and a known method capable of isolating polyamide acid can be suitably used. For example, it can also be used as reprecipitation. The method of detachment of things. In addition, when the method including step (I) and step (II) is used, and when the method of using "imination agent" is used for imidation, the film-like polyimide can be formed more efficiently. From a standpoint, the following method can be suitably used: the reaction liquid obtained by reacting the above-mentioned tetracarboxylic dianhydride (compound (I)) and the above-mentioned diamine compound (compound (II)) in an organic solvent (in the implementation After step (I), the polyamide acid of the present invention is not isolated from the reaction solution, that is, the reaction solution is used directly), the reaction solution is added with an imidizing agent, and when the imidization has not yet fully progressed, The aforementioned reaction liquid is applied to a substrate such as glass, and the substrate is imidized. [Polyimide film] The polyimide film of the present invention is composed of the above-mentioned polyimide film of the present invention. The form of such a polyimide film is not particularly limited as long as it is a film shape, and it can be appropriately designed in various shapes (disc shape, cylindrical shape (thin film processed into a cylindrical shape), etc.). Further, the thickness of the polyimide film of the present invention is not particularly limited, and is preferably 1 to 500 μm, more preferably 10 to 200 μm. If such a thickness does not reach the aforementioned lower limit, the strength will decrease and the handling will tend to be difficult. On the other hand, if the aforementioned upper limit is exceeded, there will be cases where multiple coatings must be performed or the processing will be complicated. . Such a polyimide film can be obtained by adopting the method described as a suitable method for producing the above-mentioned polyimide, while appropriately adjusting the coating method, etc., to make the obtained polyimide form the desired The shape (film shape) is manufactured. Above, the polyimide, polyimide, polyimide acid solution, and polyimide film of the present invention have been explained. Thus, the polyimide and polyimide film of the present invention are highly advanced It is well-balanced and has a sufficiently high total light transmittance, a sufficiently low yellowness, and a sufficiently low coefficient of linear expansion, so even when it is laminated on a metal substrate, etc., it can sufficiently suppress film peeling due to heat, and With sufficient visibility, it is particularly useful for various applications, such as films for flexible wiring boards, heat-resistant insulating tapes, wire enamels, protective coatings for semiconductors, liquid crystal alignment films, transparent conductive films for organic EL , Display substrate materials (TFT substrates, transparent electrode substrates (such as transparent electrode substrates for organic EL, transparent electrode substrates for electronic paper, etc.), transparent electrode substrates for solar cells, thin films for organic EL lighting, etc. Flexible substrate films, flexible organic EL substrate films, flexible transparent conductive films, transparent conductive films for organic thin film solar cells, transparent conductive films for dye-sensitized solar cells, flexible gas barrier films, touch panels Substrate materials for control panels (films for touch panels, etc.), windshield protective films for flexible displays, backing films for flexible displays, seamless polyimide tapes for copiers (so-called transfer belts) , Interlayer insulating film, sensor substrate and other materials. Furthermore, the polyimide of the present invention is derived from its linear expansion coefficient, and is used in the above-mentioned applications, especially as substrate materials for displays (display substrates such as TFT substrates, transparent electrode substrates, etc.) or touch type When used as substrate materials for panels (films for touch panels, etc.), it can further improve the yield of final products (such as organic EL devices, etc.). Moreover, due to the characteristics of the polyimide of the present invention, for example, in microelectronics (organic EL displays, liquid crystal displays, touch panels, flexible display panels, high-brightness LED wafers, ultra-thin silicon wafers, When the polyimide of the present invention is used on the substrate material used in products such as three-dimensional semiconductor packages, semiconductor protective films (buffer coatings), interlayer insulating films, photoresists, microlenses for image sensors, etc.) Corresponding to the enlargement of the device, it is derived from its linear expansion coefficient, and it can also fully prevent cracking or curling during the heating step during manufacturing, achieving high yield of the final product, and contributing to the improvement of production efficiency and processing capacity. , So products can be manufactured at low cost. [Examples] Hereinafter, the present invention will be explained more specifically based on examples and comparative examples, but the present invention is not limited to the following examples. First, the evaluation method of the characteristics of the polyimide film obtained in each example and each comparative example will be described. <Molecular structure identification> The molecular structure identification of the compound obtained in each example and each comparative example was measured by IR using an IR measuring machine (manufactured by JASCO Corporation, trade name: FT/IR-4100) get on. <Measurement of Intrinsic Viscosity [η]> The value (unit: dL/g) of the intrinsic viscosity [η] of the polyamide acid obtained as an intermediate in each example and each comparative example was made by the automatic Viscosity measuring device (trade name "VMC-252"), using tetramethylurea (TMU) as a solvent with a concentration of 0.5g/dL for measurement at a temperature of 30°C. <Measurement of glass transition temperature (Tg) and softening temperature> The value of the glass transition temperature (Tg) and softening temperature (unit: °C) of the polyimide obtained in each example and each comparative example is obtained by using For the film made of polyimide produced in each example and each comparative example, a measurement sample with a length of 5 mm, a width of 5 mm, and a thickness of 0.013 mm (13 μm) was prepared, and a thermomechanical analyzer (trade name manufactured by Rigaku) was used. TMA8311" is used as a measuring device, in a nitrogen environment, a transparent quartz needle (tip diameter: 0.5mm) is applied to the film under a pressure of 500mN at a heating rate of 5°C/min and a temperature range of 30°C to 550°C (scanning temperature). It is measured by inserting a needle (measurement by the so-called penetration (needling) method). In addition, the softening temperature is measured according to the method described in JIS K7196 (1991), based on the measurement data, in addition to the above-mentioned measurement sample. Calculate the softening temperature (softening point). <Measurement of the 5% weight loss temperature (Td5%)> The value of the 5% weight loss temperature (Td5%) of the polyimide obtained in each example and each comparative example (unit: ℃), by using the polyimide film produced in each example and each comparative example, using a thermogravimetric analyzer ("TG/DTA220" manufactured by SII Nanotechnology Co., Ltd.), and setting the scanning temperature to 30°C ～550℃, in a nitrogen environment, while circulating nitrogen while heating at 10℃/min., it is determined by measuring the temperature at which the weight of the sample used is reduced by 5%. ＜Total light transmittance, haze (turbidity) Measurement of degree) and degree of yellowness (YI)> The value of total light transmittance (unit: %), haze (turbidity: HAZE) and degree of yellowness of the polyimide obtained in each example and each comparative example YI), by directly using the film obtained in each example as a sample for measurement, using the product name "HAZE METER NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. or Nippon Denshoku Industries Co., Ltd. The product name "Spectrocolorimeter SD6000" manufactured by the company was used as a measuring device, and the measurement was performed separately. Furthermore, the total light transmittance was measured with the product name "HAZE METER NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. And haze, the yellowness was measured with the brand name "Spectrophotometer SD6000" manufactured by Nippon Denshoku Industries Co., Ltd. In addition, the total light transmittance was measured according to JIS K7361-1 (issued in 1997) The haze (turbidity) is obtained by measuring according to JIS K7136 (issued in 2000), and the chromaticity (YI) is obtained by measuring according to ASTM E313-05 (issued in 2005) Obtained. <Measurement of Coefficient of Linear Expansion (CTE)> The coefficient of linear expansion is obtained from the polyimide (polyimide in the shape of a film) obtained from each example and each comparative example After forming a thin film of length: 20mm, width: 5mm, and thickness: 13μm, the film is vacuum dried (120°C, 1 hour (Hr)), and heat-treated at 200°C for 1 hour (Hr) in a nitrogen environment, and used separately The resulting sample (dry film) was measured using a thermomechanical analyzer (trade name "TMA8310" manufactured by Rigaku) as a measuring device, in a nitrogen environment, in a tensile mode (49mN), and a heating rate of 5°C/min. The length change of the aforementioned sample at 50°C to 200°C is measured, and the average value of the length change per 1°C in the temperature range of 100°C to 200°C is obtained and measured. (Example 1) <CpODA preparation steps> According to the methods described in Synthesis Example 1, Example 1 and Example 2 of International Publication No. 2011/099518, the following general formula (13) was prepared:
Figure 02_image029
The compound represented (norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride: CpODA). Preparation procedure of polyamide acid> First, heat a 30ml three-necked flask with a heat gun to fully dry it. Next, replace the atmosphere in the fully dried three-necked flask with nitrogen to make the inside of the three-necked flask Nitrogen environment. Next, in the aforementioned three-necked flask, add the following general formula (14) as an aromatic diamine (diamine compound):
Figure 02_image031
After the indicated 2,2'-bis(trifluoromethyl)benzidine (TFMB) 4.8035g (15.00 mmol: manufactured by Seika Co., Ltd.), 33.8g of tetramethylurea (TMU) was added (to make the reaction liquid The polyamide acid concentration becomes 20 mass% (mass%), and the aromatic diamine (TFMB) is dissolved in the aforementioned tetramethylurea by stirring to obtain a solution. Next, in a three-necked flask containing the aforementioned solution, 0.8650 g (2.25 mmol) of the compound represented by the above general formula (13) (CpODA) and the above general formula (11) as tetracarboxylic dianhydride were added under a nitrogen atmosphere A mixture of 2.7810 g (12.75 mmol) of pyromellitic anhydride (pyromellitic anhydride: PMDA: Tokyo Chemical Industry Co., Ltd.) was stirred at room temperature (25° C.) for 12 hours under a nitrogen environment to obtain a reaction solution. In this way, polyamide acid is formed in the reaction liquid. Furthermore, use a part of the reaction solution (polyamide acid tetramethylurea solution: polyamide acid solution) to prepare a polyamide acid concentration of 0.5g/dL tetramethylurea solution, as described above , After measuring the inherent viscosity [η] of the polyamide acid of the reaction intermediate, the inherent viscosity [η] of the polyamide acid is 0.76 dL/g. <Steps for preparing a film made of polyimide: Steps (i) to (iii)> (Step (i): Solvent removal treatment) Prepare alkali-free glass (trade name "Eagle XG" manufactured by Corning Incorporated, vertical : 100mm, width 100mm, thickness 0.7mm) As a glass substrate, the reaction solution (polyamide acid solution) obtained as described above is heated and cured on the surface of the glass substrate so that the thickness of the coating film becomes 13μm Spin coating to form a coating film on the aforementioned glass substrate. After that, the glass substrate on which the coating film was formed was placed on a hot plate at 60° C. and allowed to stand for 2 hours to evaporate and remove the solvent from the coating film (solvent removal treatment). (Step (ii): Heating step after solvent removal treatment) After the solvent removal treatment is performed as described above, the glass substrate on which the coating film is formed is placed in an inert gas oven in which nitrogen flows at a flow rate of 3 L/min. In an inert gas oven, in a nitrogen environment, stand for 0.5 hours at a temperature of 25°C, then heat at a temperature of 135°C for 0.5 hours, and further, finally at a temperature of 350°C (hereinafter referred to as "final heating" Temperature condition") heating for 1 hour to harden the coating film to obtain a polyimide-coated glass coated with a polyimide film (polyimide film) on the glass substrate. (Step (iii): Film recovery step) Next, the polyimide-coated glass obtained in this way is immersed in hot water at 90°C, and the polyimide film is peeled from the glass substrate to recover the polyimide film. An imine film (a film with a size of 100 mm in length, 100 mm in width, and a thickness of 13 μm), and a film made of polyimide was obtained. Furthermore, in order to identify the molecular structure of the compound forming the thin film obtained in this way, the IR spectrum was measured using an IR measuring machine (manufactured by JASCO Corporation, trade name: FT/IR-4100). The IR spectrum is shown in Fig. 1 as such a measurement result. It is also obvious from the results shown in Fig. 1 that in the compound constituting the thin film formed in Example 1, C=O stretching vibration of the imine carbonyl group was observed at 1715.3 cm -1 . From the molecular structure identified based on the results, etc., it was confirmed that the obtained film was composed of polyimide. The polyimide obtained in this way contains a repeating unit equivalent to the repeating unit represented by the general formula (1) (equivalent to repeating the repeating unit (A) Unit) and the repeating unit corresponding to the repeating unit represented by the general formula (2) (equivalent to repeating unit (B)), and the content ratio of these repeating units is in molar ratio ([equivalent to repeating unit (A) Repeating unit: [Equivalent to repeating unit (B) Repeating unit]) 15:85. In addition, regarding the obtained polyimide, the evaluation results of the properties (Tg or softening temperature obtained by the evaluation method of the above properties) are shown in Table 1. (Example 2) As the tetracarboxylic dianhydride, 1.1534 g (3.00 mmol) of the compound (CpODA) represented by the above general formula (13) and 2.6172 g of pyromellitic anhydride (PMDA) represented by the above general formula (11) were used ( 12.00mmol), to replace 0.8650g (2.25mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810g (12.75mmol) of pyromellitic anhydride (PMDA) represented by the general formula (11) The mixture was obtained in the same manner as in Example 1, except that the usage amount of tetramethylurea (TMU) was changed from 33.8g to 34.30g (the polyamide acid concentration in the reaction liquid was changed to 20 mass%). Polyimide film (polyimide film). Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. In addition, the obtained polyimide contains a repeating unit corresponding to the repeating unit represented by the general formula (1) (equivalent to the repeating of the repeating unit (A), depending on the type or the amount ratio of the monomers used). Unit) and the repeating unit corresponding to the repeating unit represented by the general formula (2) (equivalent to repeating unit (B)), and the content ratio of these repeating units is in molar ratio ([equivalent to repeating unit (A) Repeating unit: [Equivalent to repeating unit (B) Repeating unit]) is counted as 20:80. (Example 3) As the tetracarboxylic dianhydride, 0.5766 g (1.50 mmol) of the compound (CpODA) represented by the general formula (13) and 2.9446 g of pyromellitic anhydride (PMDA) represented by the general formula (11) were used ( 13.50mmol), instead of using 0.8650g (2.25mmol) of the compound (CpODA) represented by the above general formula (13) and 2.7810g (12.75mmol) of pyromellitic anhydride (PMDA) represented by the above general formula (11) The mixture was obtained in the same manner as in Example 1, except that the amount of tetramethylurea (TMU) used was changed from 33.8g to 33.30g (the polyamide acid concentration in the reaction solution was 20 mass%). Polyimide film (polyimide film). Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. In addition, the obtained polyimide contains a repeating unit corresponding to the repeating unit represented by the general formula (1) (equivalent to the repeating of the repeating unit (A), depending on the type or the amount ratio of the monomers used). Unit) and the repeating unit corresponding to the repeating unit represented by the general formula (2) (equivalent to repeating unit (B)), and the content ratio of these repeating units is in molar ratio ([equivalent to repeating unit (A) Repeating unit: [Equivalent to repeating unit (B) Repeating unit]) is counted as 10:90. (Example 4) As the tetracarboxylic dianhydride, 1.7297 g (4.50 mmol) of the compound (CpODA) represented by the general formula (13) and 2.2903 g of the pyromellitic anhydride (PMDA) represented by the general formula (11) were used ( 10.50mmol), instead of using 0.8650g (2.25mmol) of the compound (CpODA) represented by the above general formula (13) and 2.7810g (12.75mmol) of pyromellitic anhydride (PMDA) represented by the above general formula (11) A film made of polyimide (polyimide film) was obtained in the same manner as in Example 1, except that TMU in which the polyamide acid concentration in the reaction liquid was 20 mass% was used as a mixture. Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. In addition, the obtained polyimide contains a repeating unit corresponding to the repeating unit represented by the general formula (1) (equivalent to the repeating of the repeating unit (A), depending on the type or the amount ratio of the monomers used). Unit) and the repeating unit corresponding to the repeating unit represented by the general formula (2) (equivalent to repeating unit (B)), and the content ratio of these repeating units is in molar ratio ([equivalent to repeating unit (A) Repeating unit: [Equivalent to repeating unit (B) Repeating unit]) is counted as 30:70. (Example 5) Except that the final heating temperature condition used in the step (ii) of the step (ii) of the preparation step of a polyimide film was changed from 350°C to 300°C, the polyimide was obtained in the same manner as in Example 1. A film made of imine (polyimide film). Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. (Example 6) The reaction solution (polyamide acid solution) used in the step (i) of the preparation step of the polyimide film was changed to the reaction obtained by the polyimide preparation step Solution 42.25g (polyamide acid 20mass% solution) is dissolved by the following general formula (15):
Figure 02_image033
Shown is an accelerator composed of imidazole-based compounds (manufactured by Tokyo Ohka Kogyo Co., Ltd.) 0.8450 g (10 parts by mass relative to 100 parts by mass of the solid content (polyamide) in the polyamide acid solution) Amount) the obtained solution (reaction solution with the aforementioned accelerator added (polyamide acid solution)), and further, the final step used in the step (ii) of the preparation step of the polyimide film Except that the heating temperature condition was changed from 350°C to 300°C, a film (polyimide film) composed of polyimide was obtained in the same manner as in Example 1. Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. (Example 7) The reaction solution (polyamide acid solution) used in the step (i) of the preparation step of a polyimide film was changed to the reaction obtained by the polyimide preparation step An accelerator (manufactured by Tokyo Ohka Kogyo Co., Ltd.) composed of an imidazole compound represented by the above general formula (15) is dissolved in 42.25 g (polyamide acid 20 mass% solution) 0.8450 g (relative to polyamide acid 100 parts by mass of the solid component (polyamide acid) in the solution is 10 parts by mass). The resulting dissolving liquid (reaction liquid (polyamide acid solution) added with the aforementioned accelerator) will be made of polyamide The final heating temperature condition used in the step (ii) of the step of preparing a film made of amine was changed from a firing temperature of 350°C to 300°C, and further, the step of preparing a film made of polyimide ( ii) Except that the ambient gas used is changed from nitrogen to air (the gas circulating in the inert gas oven is changed from nitrogen to air, and the heating step is carried out in the air), it is obtained by the same method as in Example 1. A film made of amine (polyimide film). Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. (Example 8) As the aromatic diamine, 4.7074 g (14.7 mmol) of the compound (TFMB) represented by the above general formula (14) and amino modified silicone oil (trade name manufactured by Shin-Etsu Chemical Co., Ltd.) were used "X-22-9409") 0.4020g (0.3 mmol equivalent) of the mixture, instead of using the 2,2'-bis(trifluoromethyl)benzidine (TFMB) represented by the general formula (14) alone, 4.8035g( 15.00 mmol: manufactured by Seika Co., Ltd.), except that the amount of tetramethylurea (TMU) used is changed from 33.8g to 35.02g (the amount of polyamide acid in the reaction solution is 20mass%) In the same manner as in Example 1, a film composed of polyimide (polyimide film) was obtained. Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. In addition, the obtained polyimide contains a repeating unit corresponding to the repeating unit represented by the general formula (1) (equivalent to the repeating of the repeating unit (A), depending on the type or the amount ratio of the monomers used). Unit) and the repeating unit corresponding to the repeating unit represented by the general formula (2) (equivalent to repeating unit (B)), and the content ratio of these repeating units is in molar ratio ([equivalent to repeating unit (A) Repeating unit: [Equivalent to repeating unit (B) Repeating unit]) 15:85. (Comparative Example 1) As the tetracarboxylic dianhydride, 2.3063 g (6.00 mmol) of the compound (CpODA) represented by the above general formula (13) and 1.9631 g of pyromellitic anhydride (PMDA) represented by the above general formula (11) were used ( 9.00mmol), to replace 0.8650g (2.25mmol) of the compound (CpODA) represented by the above general formula (13) and 2.7810g (12.75mmol) of pyromellitic anhydride (PMDA) represented by the above general formula (11) The mixture was obtained in the same manner as in Example 1, except that the usage amount of tetramethylurea (TMU) was changed from 33.8g to 36.3g (the amount of polyamide acid concentration in the reaction liquid became 20 mass%) Polyimide film (polyimide film). Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. In addition, the obtained polyimide contains a repeating unit corresponding to the repeating unit represented by the general formula (1) (equivalent to the repeating of the repeating unit (A), depending on the type or the amount ratio of the monomers used). Unit) and the repeating unit corresponding to the repeating unit represented by the general formula (2) (equivalent to repeating unit (B)), and the content ratio of these repeating units is in molar ratio ([equivalent to repeating unit (A) Repeating unit: [Equivalent to repeating unit (B) Repeating unit]) is calculated as 40:60. (Comparative Example 2) As the tetracarboxylic dianhydride, 3.2718 g (15.00 mmol) of pyromellitic anhydride (PMDA) represented by the general formula (11) was used alone instead of using the compound represented by the general formula (13) (CpODA) ) 0.8650g (2.25mmol) and 2.7810g (12.75mmol) of pyromellitic anhydride (PMDA) represented by the above general formula (11), and the amount of tetramethylurea (TMU) used is changed from 33.8g to Except for 32.3 g (the amount of polyamide acid concentration in the reaction solution being 20 mass%), a film made of polyimide (polyimide film) was obtained in the same manner as in Example 1. Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. In addition, the obtained polyimide is a repeating unit corresponding to the repeating unit represented by the general formula (2) (equivalent to the repeating unit of the repeating unit (B) ) With a content ratio of 100 mol%. (Comparative Example 3) As the tetracarboxylic dianhydride, the following general formula (16) was used alone:
Figure 02_image035
The compound represented (4,4'-biphthalic anhydride: BPDA: manufactured by Tokyo Chemical Industry Co., Ltd.) 4.4133 g (15.00 mmol) instead of 0.8650 g of the compound represented by the above general formula (13) (CpODA) (2.25mmol) and a mixture of 2.7810g (12.75mmol) of pyromellitic anhydride (PMDA) represented by the above general formula (11), and the amount of tetramethylurea (TMU) used was changed from 33.8g to 36.9g ( Except that the concentration of polyimide in the reaction liquid was set to 20 mass%), a film (polyimide film) made of polyimide was obtained in the same manner as in Example 1. Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. (Comparative Example 4) As the tetracarboxylic dianhydride, 0.8650 g (2.25 mmol) of the compound (CpODA) represented by the general formula (13) and the compound (4,4'-biphthalene) represented by the general formula (16) were used Dicarboxylic anhydride: BPDA: manufactured by Tokyo Chemical Industry Co., Ltd.) 3.7513 g (12.75 mmol) of a mixture (the molar ratio of CpODA to BPDA (CpODA: BPDA) is 15:85), instead of using the above general formula (13) A mixture of 0.8650 g (2.25 mmol) of the compound (CpODA) and 2.7810 g (12.75 mmol) of pyromellitic anhydride (PMDA) represented by the general formula (11), and the usage amount of tetramethylurea (TMU) is 33.8 Except that g was changed to 37.7 g (the polyamide acid concentration in the reaction liquid was set to 20 mass%), a film (polyimide film) composed of polyimide was obtained in the same manner as in Example 1. Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. (Comparative Example 5) As the tetracarboxylic dianhydride, 3.2718 g (15.00 mmol) of pyromellitic anhydride (PMDA) represented by the general formula (11) was used alone instead of using the compound represented by the general formula (13) (CpODA) ) 0.8650 g (2.25 mmol) and 2.7810 g (12.75 mmol) of pyromellitic anhydride (PMDA) represented by the above general formula (11). As an aromatic diamine, the following general formula (17) is used:
Figure 02_image037
The compound represented (m-tolidine: m-Tol: manufactured by Tokyo Chemical Industry Co., Ltd.) 3.1844 g (15.00 mmol) instead of using the 2,2'-bis(trifluoromethyl) represented by the general formula (14) Benzidine (TFMB) 4.8035g (15.00 mmol: manufactured by Seika Co., Ltd.), and the usage amount of tetramethylurea (TMU) was changed from 33.8g to 25.8g (to make the polyamide in the reaction liquid Except that the concentration becomes 20 mass%), a film composed of polyimide (polyimide film) was obtained in the same manner as in Example 1. Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. (Comparative Example 6) As the tetracarboxylic dianhydride, the compound represented by the above general formula (16) (4,4'-biphthalic anhydride: BPDA: manufactured by Tokyo Chemical Industry Co., Ltd.) was used alone, 4.4133 g (15.00) mmol), instead of using a mixture of 0.8650 g (2.25 mmol) of the compound (CpODA) represented by the above general formula (13) and 2.7810 g (12.75 mmol) of pyromellitic anhydride (PMDA) represented by the above general formula (11), as Aromatic diamine, using 3.1844 g (15.00 mmol) of compound (m-Tol) represented by the above general formula (17) instead of 2,2'-bis(trifluoromethyl) represented by the above general formula (14) Benzidine (TFMB) 4.8035g (15.00mmol: manufactured by Seika Co., Ltd.), and the usage amount of tetramethylurea (TMU) was changed from 33.8g to 30.4g (the concentration of polyamide in the reaction liquid was changed to Except for the amount of 20 mass%), a film made of polyimide (polyimide film) was obtained in the same manner as in Example 1. Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. (Comparative Example 7) As the tetracarboxylic dianhydride, the following general formula (18) was used:
Figure 02_image039
The compound represented (1,2,4,5-cyclohexanetetracarboxylic dianhydride: CHDA) 0.5044g (2.25mmol) and pyromellitic anhydride (PMDA) represented by the general formula (11) 2.7810g (12.75mmol) ) Instead of using a mixture of 0.8650 g (2.25 mmol) of the compound (CpODA) represented by the above general formula (13) and 2.7810 g (12.75 mmol) of pyromellitic anhydride (PMDA) represented by the above general formula (11), And, except that the amount of tetramethylurea (TMU) used was changed from 33.8g to 32.4g (the amount of polyamide acid concentration in the reaction solution was 20 mass%), the polyamide was obtained in the same manner as in Example 1. A film made of imine (polyimide film). Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. (Comparative Example 8) As the tetracarboxylic dianhydride, the following general formula (19) was used:
Figure 02_image041
The compound represented (1,2,3,4-cyclopentanetetracarboxylic dianhydride: CPDA) 0.4728g (2.25mmol) and pyromellitic anhydride (PMDA) represented by the general formula (11) 2.7810g (12.75mmol) ) Instead of using a mixture of 0.8650 g (2.25 mmol) of the compound (CpODA) represented by the above general formula (13) and 2.7810 g (12.75 mmol) of pyromellitic anhydride (PMDA) represented by the above general formula (11), And, except that the amount of tetramethylurea (TMU) used was changed from 33.8g to 32.2g (the amount of polyamide acid concentration in the reaction solution was 20 mass%), the polyamide was obtained in the same manner as in Example 1. A film made of imine (polyimide film). Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. (Comparative Example 9) As the tetracarboxylic dianhydride, the following general formula (20) was used:
Figure 02_image043
The compound represented (1,2,3,4-cyclobutane tetracarboxylic dianhydride: CBDA) 0.4412 g (2.25 mmol) and pyromellitic anhydride (PMDA) represented by the general formula (11) 2.7810 g (12.75 mmol) ) Instead of using a mixture of 0.8650 g (2.25 mmol) of the compound (CpODA) represented by the above general formula (13) and 2.7810 g (12.75 mmol) of pyromellitic anhydride (PMDA) represented by the above general formula (11), And, except that the used amount of tetramethylurea (TMU) was changed from 33.8g to 32.1g (the amount of polyamide acid concentration in the reaction solution was 20 mass%), the polyamide was obtained in the same manner as in Example 1. A film made of imine (polyimide film). Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. (Comparative Example 10) As an aromatic diamine, 3.1844 g (15.00 mmol) of the compound (m-Tol) represented by the general formula (17) was used instead of 2,2'-bis represented by the general formula (14) (Trifluoromethyl)benzidine (TFMB) 4.8035g (15.00mmol: manufactured by Seika Co., Ltd.), and the amount of tetramethylurea (TMU) used was changed from 33.8g to 27.3g (to make the reaction liquid Except that the polyimide concentration was 20 mass%), a film (polyimide film) made of polyimide was obtained in the same manner as in Example 1. Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1. (Comparative Example 11) As the tetracarboxylic dianhydride, 0.8650 g (2.25 mmol) of the compound (CpODA) represented by the general formula (13) and the compound (4,4'-biphthalene) represented by the general formula (16) were used Dicarboxylic anhydride: BPDA: manufactured by Tokyo Chemical Industry Co., Ltd.) 3.7513 g (12.75 mmol) of a mixture (the molar ratio of CpODA to BPDA (CpODA: BPDA) is 15:85), instead of using the above general formula (13) A mixture of 0.8650 g (2.25 mmol) of the compound (CpODA) represented by the general formula (11) and 2.7810 g (12.75 mmol) of pyromellitic anhydride (PMDA) represented by the general formula (11). As an aromatic diamine, the general formula (17) is used The represented compound (m-Tol) 3.1844g (15.00mmol), instead of using the 2,2'-bis(trifluoromethyl)benzidine (TFMB) represented by the general formula (14), 4.8035g (15.00mmol: Seika) Co., Ltd.), and the usage amount of tetramethylurea (TMU) was changed from 33.8g to 31.2g (the polyamide acid concentration in the reaction solution was changed to 20 mass%), and the same as in Example 1 In the same way, a film composed of polyimide (polyimide film) was obtained. Furthermore, after measuring the IR spectrum of the obtained film, it was confirmed that the film was composed of polyimide. In addition, the results of the evaluation properties of the obtained polyimine (Tg or softening temperature obtained by the above-mentioned property evaluation method) are shown in Table 1.
Figure 02_image045
It is also obvious from the results shown in Table 1 that the films composed of the polyimide of the present invention (Examples 1 to 8) have a total light transmittance of 85% or more and are sufficiently transparent. In addition, the film composed of the polyimide of the present invention (Examples 1 to 8) has a yellowness (YI) of 16 or less (As for the polyimide obtained by heating in a nitrogen environment (Examples 1 to 6) And 8) The film constituted by 11), and the CTE is -20ppm/K to 20ppm/K. In this way, the films composed of the polyimide of the present invention (Examples 1 to 8) all have a sufficiently high total light transmittance and a sufficiently low yellowness to be usable in applications requiring visibility. It was also confirmed that it has a linear expansion coefficient equivalent to that of inorganic substances such as glass or copper. That is, it was confirmed that the films composed of the polyimide of the present invention (Examples 1 to 8) all have a higher level and a well-balanced total light transmittance, a sufficiently low yellowness, and sufficient Low linear expansion coefficient. Furthermore, it is also obvious from the results shown in Table 1 that the polyimide of the present invention (Examples 1 to 8) has a Tg of 300°C or higher, a softening temperature (softening point) of 300°C or higher, and 400°C or higher (Preferably 450°C or higher) Td5%, with sufficiently high level of heat resistance. In addition, it is also known that the haze (turbidity: HAZE) of the polyimide of the present invention (Examples 1 to 8) is 5 or less (1.1 or less), and the haze is sufficiently low. In contrast, the polyimide obtained in Comparative Examples 1 to 2 had a high linear expansion coefficient exceeding 20 ppm/K, and it was not one having a sufficiently low linear expansion coefficient. In addition, the polyimide obtained in Comparative Example 2 has a total light transmittance of less than 83.0. It can also be seen that it does not yet have a very high level of light transmittance (total light transmittance) as achieved by the polyimide of the present invention. The rate is preferably 83.0 or higher, more preferably 85.0 or higher permeability). Considering these results together, the structure of the polyimide obtained in Examples 1 to 8 and Comparative Examples 1 to 2 (the polyimide obtained in Comparative Example 1, the aforementioned repeating unit (A) is relative to the aforementioned repeating unit). The total content of the units (A) and (B) is 40 mol%. For the polyimide obtained in Comparative Example 2, the content of the aforementioned repeating unit (B) is 100 mol% (the aforementioned repeating unit (A) When the content is 0 mol%)), it can be seen that by containing the repeating units (A) and (B), and relative to the total amount of the repeating units (A) and (B), the repeating unit (A) ) Polyimide with a ratio of 5 to 35 mol% will have a higher level and a well-balanced total light transmittance (preferably 83.0 or more, more preferably 85.0 or more of the total light Transmittance), sufficiently low yellowness (preferably YI below 16) and sufficiently low linear expansion coefficient (preferably CTE in the range of -20ppm/K to 20ppm/K). In addition, compared with Example 1, when BPDA (aromatic tetracarboxylic dianhydride) is used in place of PMDA (aromatic tetracarboxylic dianhydride) in the mixture of tetracarboxylic dianhydride (Comparative Example 4) , Not only the total light transmittance cannot be sufficiently high, but the value of YI becomes 18.2, and the yellowness cannot be made sufficiently low. Furthermore, when BPDA (aromatic tetracarboxylic dianhydride) is used (Comparative Example 4), the coefficient of linear expansion is also 60.7 ppm/K, and the coefficient of linear expansion cannot be made sufficiently low. In this way, it can be seen that when BPDA (aromatic tetracarboxylic dianhydride) is used in place of PMDA (aromatic tetracarboxylic dianhydride) in a mixture of tetracarboxylic dianhydrides (Comparative Example 4), a sufficiently low Its yellowness and sufficiently low linear expansion coefficient. Furthermore, compared with the case where tetracarboxylic dianhydride is only BPDA (Comparative Example 3), it can also be seen that when tetracarboxylic dianhydride is a mixture of BPDA and CpODA (Comparative Example 4), the value of yellowness (YI) increases. Therefore, when the type of aromatic tetracarboxylic dianhydride combined with CpODA is other than PMDA, it may not necessarily have a higher level and a well-balanced total light transmittance, a sufficiently low yellowness, and a sufficiently low level. The coefficient of linear expansion. In addition, compared with Example 1, it can be seen that the mixture of tetracarboxylic dianhydrides uses CHDA, CPDA or CBDA (aliphatic tetracarboxylic dianhydride) instead of CpODA (aliphatic tetracarboxylic dianhydride) When (CHDA: Comparative Example 7, CPDA: Comparative Example 8, CBDA: Comparative Example 9), the total light transmittance is less than 83%, and a sufficient high level of total light transmittance of 83% or more cannot be obtained. Also, compared with Example 1, it can be seen that when m-Tol without a fluorine-based substituent is used as an aromatic diamine in place of TFMB with a fluorine-based substituent (Comparative Example 10), the value of YI becomes 44.6, the yellowness cannot be made a sufficiently low value (YI below 16). Furthermore, it can be seen that the value of the total light transmittance is 75.4%, and a sufficiently high level of total light transmittance of 83% or more cannot be obtained. Similarly, when using BPDA instead of PMDA as an aromatic acid dianhydride, and using m-Tol without a fluorine-based substituent as an aromatic diamine instead of TFMB with a fluorine-based substituent (Comparative Example 11) The value of YI was 23.2, and the yellowness could not be sufficiently low (YI of 16 or less). Furthermore, it can be seen that the value of the total light transmittance is 79.6%, and a sufficiently high level of total light transmittance of 83% or more cannot be obtained. Furthermore, when comparing Comparative Example 2 with Comparative Example 5, although the types of aromatic diamines used in the production of polyimide are different, the type of aromatic diamine can be confirmed in the repeating unit When an arylene group having a fluorine-containing substituent (tetrafluoromethyl) was introduced in the fluorine-containing substituent (Comparative Example 2), the yellowness (YI) value of the polyimide became lower. Similarly, when comparing Comparative Example 3 and Comparative Example 6, although the type of aromatic diamine used in the production of polyimide is different, the type of aromatic diamine can be confirmed in the repeating unit When an arylene group having a fluorine-containing substituent (tetrafluoromethyl) was introduced in the fluorine-containing substituent (Comparative Example 3), the yellowness (YI) value of the polyimide became lower. In addition, when comparing Comparative Example 4 with Comparative Example 11, although the types of aromatic diamines used in the production of polyimide are different, the type of aromatic diamine can be confirmed in the repeating unit When an arylene group having a fluorine-containing substituent (tetrafluoromethyl) was introduced (Comparative Example 4), the yellowness (YI) value of the polyimide became lower. Considering the different effects (tendencies) caused by the types of such aromatic diamines together, when compared with the results of Examples 1 to 4, it can be seen that, as in this case, by containing the aforementioned repeating units (A) and (B), and With respect to the total amount of the repeating units (A) and (B), the polyimide with a ratio of the repeating unit (A) of 5 to 35 mol% is a higher level and well-balanced Those with sufficiently high total light transmittance, sufficiently low yellowness and sufficiently low linear expansion coefficient. Furthermore, the polyimide obtained in Example 7 was obtained in the same manner as in Example 6, except that the ambient air system in the heating step used air (obtained by using the polyimide acid of the present invention). Here, generally speaking, when the aliphatic acid dianhydride is used to produce polyimide, and it must be heated (calcined) at a high temperature of about 300°C, if it is contained in the air or at least 500ppm or more (according to When polyimide is made by firing polyimide in an oxygen active gas atmosphere of 1000ppm or more, it is known that due to oxygen oxidation, polyimide will change color to yellow, or the polymer will be cut off by oxygen oxidation. The main chain has a tendency to become brittle due to a decrease in molecular weight. Therefore, generally, when aliphatic acid dianhydrides are used to produce high-transparency polyimide, in order to ensure a higher degree of visibility, etc., it is generally under an inert gas environment (for example, containing inert gas and oxygen). (Under an environment with a concentration of 100 ppm or less) fire polyamide acid to obtain polyimide. In contrast, the polyimide of the present invention obtained in Example 7 is obtained by heating (calcining) polyamide acid in the air, and not only has a total light transmittance of 86% or more, but also has extraordinary High degree of transparency, and the yellowness (YI) of polyimide is 16 or less. From this result, it is obvious that the polyamide acid of the present invention (Examples 1 to 8), even if it is to be manufactured, air firing is an indispensable field in the manufacturing process, or high oxygen concentration conditions must be used during manufacture or use. (For example, when the oxygen concentration is 500 ppm or more) and the areas where oxygen is generated, the polyimide is used in products, and the polyimide has sufficient visibility after manufacture or during use. , Especially useful for preparing polyimide used in products in the above-mentioned fields. In addition, it can also be seen that the polyimide of the present invention obtained in Example 7 has a linear expansion coefficient equivalent to that of Example 6 or Example 1 (CTE: 1.2ppm/K) when fired in nitrogen. The one that is fired in nitrogen is similarly one having a sufficiently low coefficient of linear expansion. Furthermore, from the results shown in Table 1, it can be seen that the polyimide of the present invention obtained in Example 7 is obtained by heating (calcining) polyimide in air, as described above, It has a Tg of 300°C or higher, a softening temperature (softening point) of 300°C or higher, and a Td5% of 400°C or higher (preferably 450°C or higher), which is a very high level of heat resistance. From this result, it can be seen that the polyamide acid of the present invention (Examples 1 to 8) is independent of the environment during heating (sintering), for example, even when firing in a nitrogen environment (Examples 1 to 6) And 8), or even when fired in the air (Example 7), the coloration of the obtained polyimide can be sufficiently suppressed, and the increase in yellowness can be sufficiently suppressed, while the transparency is high, and the coefficient of linear expansion Fully low polyimide. <Regarding the laser releasability of the polyimide film obtained in Examples 1 to 8> In the preparation step of the polyimide film, except for the step (iii) (film recovery step: by The polyimide-coated glass is immersed in hot water at 90°C, and the polyimide film is peeled from the glass substrate to obtain the polyimide film) except for the steps described in Examples 1-8. The same steps are used to prepare polyimide coated glass. Next, each polyimide-coated glass was irradiated with a laser, and the peelability of the glass was measured. That is, the product "pm848 (excimer laser XeCl, 308nm, maximum pulse energy 320 mJ/cm 2 )" manufactured by Light Machinery is used as the laser emitting device to set the irradiation energy density of the laser to 50～320mJ /cm 2 (Starting from the low energy density (50mJ/cm 2 ), increasing the energy density by 10mJ/cm 2 each time, until peeling is confirmed, using the irradiation energy density at which peeling is confirmed), the pulse width is set to 20 ～30ns, the overlap rate (repetition rate) is set to 50%, the laser repetition frequency (repetition rate) is set to 30Hz, and the shape of the irradiation surface of the laser light is set to a rectangle with a length of 14mm and a width of 30mm. For each polyimide The coated glass was irradiated with laser light from the glass substrate side, and it was visually judged whether the film made of polyimide was peelable (when Newton's rings were seen, it was judged to be peelable), and whether it was colored or had unevenness in the shot. As a result, it can be seen that the polyimide-coated glass obtained by using the same steps as those described in Examples 1 to 8 has an irradiation energy density of 140 mJ/cm 2 and an overlap rate (repetition rate) of 50%. The imine film is peelable without coloring or unevenness (Newton's ring can be confirmed). From this result, it can also be known that the film composed of the polyimide of the present invention, when it is laminated on glass (as a laminate on a glass substrate), can be sufficiently Peeling is performed while suppressing quality changes. Also, from this result, it is clear that after laminating a thin film composed of the polyimide of the present invention on a glass substrate (so-called carrier substrate, etc.), a thin film transistor or the like is directly constructed on the thin film, and the so-called Laser lift-off processing can peel off the film made of polyimide from the aforementioned glass substrate. It is also known that the film made of polyimide of the present invention can be suitably applied to the manufacture of structured films Transistor and other display methods, etc. [Industrial Applicability] As explained above, according to the present invention, it is possible to provide a high-level, well-balanced, high-level total light transmittance, a sufficiently low yellowness, and a sufficiently low linear expansion coefficient. Polyimide; polyimide that can efficiently form the polyimide; the solution of the polyimide; and the polyimide film composed of the aforementioned polyimide. Such polyimide of the present invention has a high level and a well-balanced total light transmittance, a sufficiently low yellowness, and a sufficiently low coefficient of linear expansion, so it is particularly useful as, for example, Films for flexible wiring boards, heat-resistant insulating tapes, wire enamels, protective coatings for semiconductors, liquid crystal alignment films, transparent conductive films for organic EL (organic electroluminescence), organic EL lighting films, flexible substrate films , Flexible organic EL substrate film, flexible transparent conductive film, transparent conductive film for organic thin film solar cell, transparent conductive film for dye-sensitized solar cell, flexible gas barrier film, touch panel Thin film, windshield protective film for flexible display, back film for flexible display, TFT substrate for flexible display, protective film for semiconductor (buffer coating), interlayer insulating film, photoresist, microlens for image sensor And other materials.

[圖1]顯示實施例1中得到之聚醯亞胺的IR光譜之圖。[Figure 1] A graph showing the IR spectrum of the polyimide obtained in Example 1.

Claims (6)

一種聚醯亞胺，其含有 　　下述通式(1)：
Figure 03_image047
[式(1)中，R1 、R2 、R3 係分別獨立地表示選自由氫原子、碳數1～10之烷基及氟原子所成之群的1種，R10 表示具有含氟取代基之碳數6～40之伸芳基，n表示0～12之整數]， 表示之重複單位(A)，與 　　下述通式(2)：
Figure 03_image049
[式(2)中，R10 表示具有含氟取代基之碳數6～40之伸芳基]， 表示之重複單位(B)，且相對於前述重複單位(A)及(B)之總量而言，前述重複單位(A)之含量為5～35莫耳%。A polyimide containing the following general formula (1):
Figure 03_image047
[In formula (1), R 1 , R 2 , and R 3 each independently represent one kind selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and R 10 represents a fluorine-containing The substituent is an arylene group with 6-40 carbon atoms, n represents an integer of 0-12], the repeating unit (A) represented by the following general formula (2):
Figure 03_image049
[In formula (2), R 10 represents an arylene group having 6 to 40 carbon atoms with a fluorine-containing substituent], which represents the repeating unit (B), and is relative to the total of the foregoing repeating units (A) and (B) In terms of quantity, the content of the aforementioned repeating unit (A) is 5 to 35 mol%. 如請求項1之聚醯亞胺，其中前述通式(1)及(2)中之R10 ，均為下述通式(3)：
Figure 03_image051
[式(3)中，R5 表示碳數1～10之氟烷基]， 表示之基。Such as the polyimide of claim 1, wherein R 10 in the aforementioned general formulas (1) and (2) are all of the following general formula (3):
Figure 03_image051
[In the formula (3), R 5 represents a fluoroalkyl group having 1 to 10 carbon atoms], which represents the group. 如請求項1或2之聚醯亞胺，其中相對於前述重複單位(A)及(B)之總量而言，前述重複單位(A)之含量為5～25莫耳%。The polyimide of claim 1 or 2, wherein the content of the repeating unit (A) is 5-25 mol% relative to the total amount of the repeating unit (A) and (B). 一種聚醯胺酸，其含有下述通式(4)：
Figure 03_image053
[式(4)中，R1 、R2 、R3 係分別獨立地表示選自由氫原子、碳數1～10之烷基及氟原子所成之群的1種，R10 表示具有含氟取代基之碳數6～40之伸芳基，n表示0～12之整數]， 表示之重複單位(C)，與 　　下述通式(5)：
Figure 03_image055
[式(5)中，R10 表示具有含氟取代基之碳數6～40之伸芳基]， 表示之重複單位(D)，且相對於前述重複單位(C)及(D)之總量而言，前述重複單位(C)之含量為5～35莫耳%。A polyamide acid containing the following general formula (4):
Figure 03_image053
[In formula (4), R 1 , R 2 , and R 3 each independently represent one kind selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and R 10 represents a fluorine-containing The substituent is an arylene group having 6-40 carbon atoms, n represents an integer of 0-12], the repeating unit (C) represented by the following general formula (5):
Figure 03_image055
[In formula (5), R 10 represents an arylene group having 6 to 40 carbon atoms with a fluorine-containing substituent], which represents the repeating unit (D), and is relative to the total of the foregoing repeating units (C) and (D) In terms of quantity, the content of the aforementioned repeating unit (C) is 5 to 35 mol%. 一種聚醯胺酸溶液，其含有如請求項4之聚醯胺酸，與有機溶劑。A polyamic acid solution containing the polyamic acid of claim 4 and an organic solvent. 一種聚醯亞胺薄膜，其係由如請求項1～3中任一項之聚醯亞胺所構成。A polyimide film, which is composed of the polyimide according to any one of claims 1 to 3.
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