TW202246391A - Polyimide, resin composition, polyimide film, and production method therefor - Google Patents

Abstract

Provided is a resin composition comprising: a poly(amic acid)/imide copolymer including a structural unit L represented by formula (1) and having a structure represented by general formula (A-1) as the X2 in general formula (1); an organic solvent; and at least one imidization catalyst selected from the group consisting of pyridine, triethylamine, 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, imidazole, benzimidazole, and N-tert-butoxycarbonylimidazole (N-Boc-imidazole). (In the formulae, X1 to X4, n, m, l, R1, R2, a, b, and * are as defined in the specification.).

Description

Polyimide, resin composition, polyimide film and manufacturing method thereof

The present invention relates to a polyamic acid-imide used for manufacturing substrates for flexible devices, a resin composition containing the same, a polyimide resin film, a resin film, and a manufacturing method thereof.

A film of polyimide resin is generally used as the resin film in applications requiring high heat resistance. Ordinary polyimide resins are produced by solution polymerization of aromatic carboxylic acid dianhydrides and aromatic diamines to produce polyimide precursors, which are then subjected to thermal imidization at high temperatures, or using catalysts High heat-resistant resin produced by chemical imidization.

Polyimide resin is an insoluble and infusible super heat-resistant resin with excellent properties such as thermal oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. Therefore, polyimide resins can be used in a wide range of fields including electronic materials. Examples of applications of polyimide resins in the field of electronic materials include insulating coating materials, insulating films, semiconductors, and electrode protection films for thin-film transistor liquid crystal displays (TFT-LCDs). Recently, polyimide resin is being studied as a flexible substrate utilizing its light weight and softness, instead of the glass substrate that has been used in the field of display materials.

In the case of using polyimide resin as a flexible substrate, the following steps are widely used: for example, coating a varnish containing polyimide resin or its precursor, and other components on a suitable support such as a glass substrate , dried to form a film, and after forming elements, circuits, and the like on the film, the film was peeled off from the glass substrate. However, when producing a laminate having a polyimide resin, heat treatment at a high temperature of 250° C. or higher is required in order to dry and imidize the polyimide precursor. Residual stress is generated in the above-mentioned laminate due to the heat treatment, and serious problems such as warpage and peeling occur. The reason for this is that polyimide has a larger coefficient of linear expansion than the materials constituting the above-mentioned support.

In order to reduce the residual stress of the above-mentioned laminates, the use of polyimide resins with a thermal expansion coefficient as small as that of glass is being studied. As a polyimide material with a small thermal expansion coefficient, the most well-known ones include 3,3',4 , 4'-biphenyltetracarboxylic dianhydride (hereinafter also referred to as BPDA) and polyimide of p-phenylenediamine. Although the thermal expansion coefficient of the polyimide material depends on the film thickness and fabrication conditions, it is reported that the polyimide exhibits a very low linear thermal expansion coefficient (Non-Patent Document 1).

However, ordinary polyimide resins including the polyimides described in the above documents will be colored into brown or yellow due to the high electron density, so the light transmittance in the visible light region is low, so it is difficult to achieve Sufficiently low yellowness (YI value) for applications requiring transparency. In addition, it is known that polyimide with a low coefficient of linear expansion usually has high molecular alignment, so the laminate is prone to turbidity and stains, resulting in poor transmittance (Patent Document 2).

In general, regarding yellowness (YI value), it is known that, for example, a solvent-soluble polyimide using a diamine having a trifluoromethyl group, or a polyimide using an alicyclic tetracarboxylic dianhydride or a diamine exhibits Very low yellowness (YI value) and residual stress (Patent Document 3 and Patent Document 4). [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2005/113647 [Patent Document 2] Japanese Patent No. 6443579 [Patent Document 3] International Publication No. 2019/211972 [Patent Document 4] International Publication No. 2020/138360 [Patent Document 5] Japanese Patent No. 4303623 [Patent Document 6] Japanese Patent No. 5595381 [Patent Document 7] Japanese Patent No. 6073528 [Patent Document 8] Japanese Patent Laid-Open No. 63-101424 [Patent Document 9] Japanese Patent Laid-Open No. 63-110219 [Non-patent literature]

[Non-Patent Document 1] "The Latest Polyimide-Basics and Applications-", edited by Japan Polyimide Research Society

[Problem to be solved by the invention]

As mentioned above, in order to use a polyimide resin as a colorless transparent flexible board|substrate, it is required to simultaneously realize two contradictory characteristics of excellent thermal characteristics and transparency. Especially recently, as the device type of TFT has changed to LTPS (Low Temperature Polysilicon), the development of a polyimide resin that is excellent in transparency even in a thermal history above the previous level is desired.

The polyimide resin described in Patent Document 1, which is a general polyimide, exhibits a low coefficient of linear thermal expansion, but has insufficient transparency when used in an LTPS step at 400° C. or higher. Also, although it is reported that the polyimide described in Patent Document 2 is excellent in coefficient of linear expansion (hereinafter also referred to as "CTE") and transparency by using specific tetracarboxylic dianhydride and diamine, but at 400 When heated above ℃, cloudiness and stains will occur in the laminate, and when used as a transparent substrate, the haze (hereinafter, also described as "HAZE value") is insufficient.

Furthermore, as a well-known technical idea, in order to achieve transparency, as described in Patent Document 3, it is known that by using an alicyclic acid dianhydride or a diamine that does not have an aromatic ring or using a molecule that causes a large volume Diamine (for example, 2,2'-bis(trifluoromethyl)benzidine, also referred to as TFMB hereinafter) with a twisted functional group inside to inhibit intramolecular charge transfer (CT) migration. However, these polyimides with excellent transparency have insufficient heat resistance and thermal characteristics in the state of polyamic acid. In order to obtain high transparency, it is necessary to make a solvent-soluble polyimide that has been imidized during solution polymerization. However, these polyimides have large linear expansion coefficients when formed into films, lack thermal stability in high temperature regions above 430°C, and have insufficient solubility in solvents.

In order to achieve these opposite properties, that is, thermal properties and transparency at the same time, the mixing or copolymerization of polyimide and polyamic acid is being studied, but it is known that even if these resins are simply mixed with each other, problems occur during molding. Phase separation is not suitable as a transparent substrate (Patent Document 5). The reason is that the heat-resistant polyimide has a high planarity and rigid skeleton, so it is not easy to dissolve with the soluble polyimide having a curved group during film formation, resulting in phase separation.

Patent Document 4 discloses that storage stability and molding processability can be improved by locally coexisting an amide structure and an amide structure in a molecule. However, the inventors of the present invention confirmed that the polyamic acid-imide resin composition described in Patent Document 4 lacks heat resistance, and the yellowness (YI value) and haze (HAZE) significantly deteriorated. The main reason is that the monomer skeletons of polyimide and polyamic acid are common. The more the ratio of monomer skeletons in polyimide and polyamic acid is, the more it can suppress the Haze caused by phase separation. On the other hand, it is more difficult to achieve the opposite characteristics of thermal characteristics and transparency at the same time.

In addition, Patent Document 6 discloses that the bending system and transparency can be improved by locally coexisting an imide structure and an amic acid structure in the molecule and using an alicyclic diamine. However, the inventors of the present invention confirmed that the yellowness (YI value) and haze (HAZE) of the block polyimide described in Patent Document 6 are lower than the heat history at 430° C. or higher in the LTPS step. Significantly worse. The main reason is that alicyclic diamine is used as the diamine. Alicyclic diamine has excellent bending resistance, but on the other hand, it will cause alicyclic decomposition in the heat history above 430°C, making it difficult to achieve heat resistance. Realize the combination of toughness and bending resistance at the same time.

Furthermore, the common polyimide resins containing polyimide described in the above-mentioned patent documents 7 to 9 will be colored into brown or yellow due to the higher electron density, so the light transmittance in the visible light region is low, so Difficult to use in fields requiring transparency. In addition, it was found that when a polyimide resin film was formed using a conventional resin composition, the fluidity of the resin composition was insufficient in the curing step (up to heating to about 400° C.), and the obtained polyimide The in-plane uniformity of the film thickness of the resin film was insufficient. Thus, in the conventional polyimide resin film, the characteristics required for the colorless transparent substrate for a display, such as the in-plane uniformity of a film thickness, and yellowness (YI value) are insufficient.

The present invention was made in view of the above circumstances to solve the above-mentioned problems, and an object of the present invention is to provide a polyamide acid having excellent thermal properties using aromatic ester diamine as a main component and a polyamide having excellent transparency. A polyamide-imide copolymer resin composition that achieves both transparency and heat resistance through amine block copolymerization, or a combination of polyimide with excellent bending resistance and transparency and excellent heat resistance Polyamic acid-imide copolymer resin composition that realizes transparency, heat resistance, and bending resistance at the same time by polyamide acid block copolymerization, and polyimide or polyimide containing the same Amine copolymers, or polyamic acid or polyamides using 4-aminobenzoic acid 4-amino-3-fluorophenyl ester (APAB) to reduce defects in polyimide films during infrared (IR) curing A resin composition of an amine acid-imide copolymer, or a resin composition or a polyimide resin capable of obtaining a polyimide resin film having excellent in-plane uniformity of film thickness and low yellowness (YI value) A film, and a method of manufacturing the same, a method of manufacturing a display, a method of manufacturing a laminate, and a method of manufacturing a flexible device. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention conducted diligent research and repeated experiments. As a result, they found that a polyimide film obtained by curing a resin composition containing a polyamic acid-imide copolymer having a specific structure It has excellent transparency, haze, heat resistance, and linear expansion coefficient, has low residual stress and bending resistance, or reduces the defects of polyimide film during infrared (IR) curing, and/or by making The resin composition contains an aprotic polar substance with a boiling point of 250°C to 350°C. The resin becomes soft and has fluidity. When it is made into a polyimide resin film, the in-plane uniformity of the film thickness is improved, and the YI can also be reduced. , and completed the present invention based on these findings. That is, the invention is as follows.

{式中，X ₁及X ₃表示四價有機基，X ₂及X ₄表示二價有機基，n、m、及l為正之整數，且 包含下述通式(A-1)： [化2]

(式中，R ₁及R ₂分別獨立地表示碳數1～20之一價有機基、或鹵素，a及b分別獨立地為0～4之整數，並且*表示鍵結部) 所表示之結構作為上述通式(1)中之X ₂}。 ＜2＞ 如項目1之樹脂組合物，其中上述咪唑化合物係選自由1-甲基咪唑、N-第三丁氧基羰基咪唑(N-Boc-咪唑)、2-甲基咪唑、2-苯基咪唑、苯并咪唑、2-乙基-4-甲基咪唑、4-乙基-2-甲基咪唑、4-甲基-2-苯基咪唑、2-十一烷基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1H-咪唑、及1,2-二甲基咪唑所組成之群中之至少一者， 上述吡啶化合物係選自由4-二甲基胺基吡啶、2,2'-聯吡啶、菸鹼酸、異喹啉、吡啶、及2-甲基吡啶所組成之群中之至少一者，且/或 上述三級胺化合物係選自由1,8-二氮雜雙環[5.4.0]-7-十一烯、1,4-二氮雜雙環[2.2.2]辛烷、N-甲基嗎啉、及三乙基胺所組成之群中之至少一者。 ＜3＞ 如項目1或2之樹脂組合物，其中上述(e)醯亞胺化觸媒係上述咪唑化合物。 ＜4＞ 如項目1至3中任一項之樹脂組合物，其中上述(e)醯亞胺化觸媒之含量相對於上述聚醯胺酸-醯亞胺共聚物100質量份為5質量份以上。 ＜5＞ 一種樹脂組合物，其包含聚醯胺酸-醯亞胺共聚物、及(d)有機溶劑， 上述聚醯胺酸-醯亞胺共聚物包含下述通式(1)所表示之結構單元： [化3]

{式中，X ₁及X ₃表示四價有機基，X ₂及X ₄表示二價有機基，n、m、及l為正之整數，且 包含下述通式(A-1)： [化4]

(式中，R ₁及R ₂分別獨立地表示碳數1～20之一價有機基、或鹵素，a及b分別獨立地為0～4之整數，並且*表示鍵結部) 所表示之結構作為上述通式(1)中之X ₂}，且 上述聚醯胺酸-醯亞胺共聚物之重量平均分子量為170,000以上。 ＜6＞ 如項目1至4中任一項之樹脂組合物，其中上述聚醯胺酸-醯亞胺共聚物之重量平均分子量為170,000以上。 ＜7＞ 一種樹脂組合物，其包含聚醯胺酸、(d)有機溶劑、及(e)醯亞胺化觸媒， 上述聚醯胺酸包含下述通式(3)所表示之結構單元： [化5]

{式中，X ₁表示四價有機基，X ₂表示二價有機基，並且n為正之整數，且 包含下述通式(A-1)： [化6]

(式中，R ₁及R ₂分別獨立地表示碳數1～20之一價有機基、或鹵素，a及b分別獨立地為0～4之整數，並且*表示鍵結部) 所表示之結構作為上述通式(3)中之X ₂}， 上述(e)醯亞胺化觸媒係選自由1-甲基咪唑、N-第三丁氧基羰基咪唑(N-Boc-咪唑)、2-甲基咪唑、2-苯基咪唑、苯并咪唑、2-乙基-4-甲基咪唑、4-乙基-2-甲基咪唑、4-甲基-2-苯基咪唑、2-十一烷基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1H-咪唑、4-二甲基胺基吡啶、2,2'-聯吡啶、菸鹼酸、異喹啉、吡啶、2-甲基吡啶、1,8-二氮雜雙環[5.4.0]-7-十一烯、1,4-二氮雜雙環[2.2.2]辛烷、N-甲基嗎啉、及三乙基胺所組成之群中之至少一者。 ＜8＞ 一種樹脂組合物，其包含聚醯胺酸、(d)有機溶劑、及(e)醯亞胺化觸媒， 上述聚醯胺酸包含下述通式(3)所表示之結構單元： [化7]

{式中，X ₁表示四價有機基，X ₂表示二價有機基，並且n為正之整數，且 包含下述通式(A-1)： [化8]

(式中，R ₁及R ₂分別獨立地表示碳數1～20之一價有機基、或鹵素，a及b分別獨立地為0～4之整數，並且*表示鍵結部) 所表示之結構作為上述通式(3)中之X ₂}， 上述(e)醯亞胺化觸媒係咪唑化合物，且上述(e)醯亞胺化觸媒之含量相對於上述聚醯胺酸100質量份為5質量份以上。 ＜9＞ 一種樹脂組合物，其包含聚醯胺酸、(d)有機溶劑、及(e)醯亞胺化觸媒， 上述聚醯胺酸包含下述通式(3)所表示之結構單元： [化9]

{式中，X ₁表示四價有機基，X ₂表示二價有機基，並且n為正之整數，且 包含下述通式(A-1)： [化10]

(式中，R ₁及R ₂分別獨立地表示碳數1～20之一價有機基、或鹵素，a及b分別獨立地為0～4之整數，並且*表示鍵結部) 所表示之結構作為上述通式(3)中之X ₂}， 上述(e)醯亞胺化觸媒係咪唑化合物，且 上述聚醯胺酸之重量平均分子量為170,000以上。 ＜10＞ 如項目7或8之樹脂組合物，其中上述聚醯胺酸之重量平均分子量為170,000以上。 ＜11＞ 如項目1至10中任一項之樹脂組合物，其中上述(e)醯亞胺化觸媒之含量相對於上述聚醯胺酸-醯亞胺共聚物100質量份或上述聚醯胺酸100質量份為10質量份以上。 ＜12＞ 如項目1至11中任一項之樹脂組合物，其中上述(e)醯亞胺化觸媒係包含N-第三丁氧基羰基咪唑(N-Boc-咪唑)及/或1-甲基咪唑之咪唑化合物。 ＜13＞ 如項目1至12中任一項之樹脂組合物，其中上述聚醯胺酸-醯亞胺共聚物或上述聚醯胺酸之重量平均分子量為220,000以上。 ＜14＞ 如項目1至13中任一項之樹脂組合物，其進而包含沸點250℃～350℃之非質子性極性物質。 ＜15＞ 如項目14之樹脂組合物，其中上述非質子性極性物質為環丁碸。 ＜16＞ 如項目1至15中任一項之樹脂組合物，其中上述通式(1)中之X ₄或(3)中之X ₂係選自由下述通式(A-4)、下述通式(A-5)及下述通式(A-6)： [化11]

{式中，R ₈～R ₁₁分別獨立地表示碳數1～20之一價有機基、或鹵素，並且h～k分別獨立地為0～4之整數，Z ₂表示鍵結基，並且*表示鍵結部} [化12]

{式中，R ₁₂及R ₁₃分別獨立地表示碳數1～20之一價有機基、或鹵素，l及m分別獨立地為0～4之整數，並且*表示鍵結部} [化13]

{式中，R ₁₄及R ₁₅分別獨立地表示碳數1～20之一價有機基、或鹵素，n及о分別獨立地為0～4之整數，並且*表示鍵結部} 所表示之結構所組成之群中之至少1種。 ＜17＞ 如項目1至6、11至16中任一項之樹脂組合物，其中上述通式(1)中之X ₃係選自由下述通式(A-3)： [化14]

{式中，R ₄～R ₇分別獨立地表示碳數1～20之一價有機基、或鹵素，d～g分別獨立地為0～4之整數，Z ₁表示鍵結基，並且*表示鍵結部} 所表示之結構、源自4,4'-氧二鄰苯二甲酸二酐(ODPA)之結構、源自4,4'-(六氟亞異丙基)二鄰苯二甲酸酐(6FDA)之結構、源自聯苯四羧酸二酐(BPDA)之結構、及源自4,4'-聯苯雙(偏苯三甲酸單酯酸酐)(TAHQ)之結構所組成之群中之至少1種。 ＜18＞ 如項目1至6、11至17中任一項之樹脂組合物，其中上述(e)醯亞胺化觸媒之含量相對於上述聚醯胺酸-醯亞胺共聚之重複單元1莫耳為0.02～0.15莫耳%之範圍。 ＜19＞ 一種聚醯胺酸-醯亞胺共聚物，其特徵在於包含下述通式(1)所表示之結構單元L： [化15]

{式中，X ₁及X ₃表示四價有機基，X ₂及X ₄表示二價有機基，n、m、及l為正之整數，將包含X ₁及X ₂之結構單元稱為結構單元N，並且將包含X ₃及X ₄之結構單元稱為結構單元M， 於X ₂係源自4-胺基苯甲酸4-胺基-3-氟苯酯之基之情形時，下述構成1、2除外： 1.於X ₃係源自9,9-雙(3,4-二羧基苯基)茀二酸酐(BPAF)之基之情形時，X ₂係源自4,4'-二胺基二苯基碸、及/或2,2'-雙(三氟甲基)聯苯胺之基；及 2.X ₃係源自降𦯉烷-2-螺-α-環戊酮-α'-螺-2''-降𦯉烷-5,5'',6,6''-四羧酸二酐之基；}，且 具有下述通式(A-1)： [化16]

{式中，R ₁及R ₂分別獨立地表示碳數1～20之一價有機基、或鹵素，a及b分別獨立地為0～4之整數，並且*表示鍵結部} 或下述通式(A-2)： [化17]

{式中，R ₃表示碳數1～20之一價有機基、或鹵素，並且c為0～4之整數。*表示鍵結部} 所表示之結構作為上述X ₂。 ＜20＞ 如項目19之聚醯胺酸-醯亞胺共聚物，其中上述通式(1)中之X ₃係選自由下述通式(A-3)： [化18]

{式中，R ₄～R ₇分別獨立地表示碳數1～20之一價有機基、或鹵素，d～g分別獨立地為0～4之整數，Z ₁表示鍵結基，並且*表示鍵結部} 所表示之結構、源自4,4'-氧二鄰苯二甲酸二酐(ODPA)之結構、及源自4,4'-(六氟亞異丙基)二鄰苯二甲酸酐(6FDA)之結構所組成之群中之至少1種。 ＜21＞ 如項目19或20之聚醯胺酸-醯亞胺共聚物，其中上述通式(1)中之X ₄具有選自由下述通式(A-4)、下述通式(A-5)及下述通式(A-6)： [化19]

{式中，R ₈～R ₁₁分別獨立地表示碳數1～20之一價有機基、或鹵素，並且h～k分別獨立地為0～4之整數，Z ₂表示鍵結基，並且*表示鍵結部} [化20]

{式中，R ₁₂及R ₁₃分別獨立地表示碳數1～20之一價有機基、或鹵素，l及m分別獨立地為0～4之整數，並且*表示鍵結部，其中於上述X ₃係源自9,9-雙(3,4-二羧基苯基)茀二酸酐(BPAF)之基之情形時，上述通式(A-5)係源自4,4'-二胺基二苯基碸之基之情形除外} [化21]

{式中，R ₁₄及R ₁₅分別獨立地表示碳數1～20之一價有機基、或鹵素，n及о分別獨立地為0～4之整數，並且*表示鍵結部} 所表示之結構所組成之群中之至少1種。 ＜22＞ 一種聚醯胺酸-醯亞胺共聚物，其特徵在於包含下述通式(1)所表示之結構單元L： [化22]

{式中，X ₁及X ₃表示四價有機基，X ₂及X ₄表示二價有機基，n、m、及l為正之整數，將包含X ₁及X ₂之結構單元稱為結構單元N，將包含X ₃及X ₄之結構單元稱為結構單元M，且 X ₄係將源自4,4'-二胺基二苯基碸及/或2,2'-雙(三氟甲基)聯苯胺之基除外}，且 具有選自由下述通式(A-3)： [化23]

{式中，R ₄～R ₇分別獨立地表示碳數1～20之一價有機基、或鹵素，d～g分別獨立地為0～4之整數，Z ₁表示鍵結基，並且*表示鍵結部} 所表示之結構、源自4,4'-氧二鄰苯二甲酸二酐(ODPA)之結構、及源自4,4'-(六氟亞異丙基)二鄰苯二甲酸酐(6FDA)之結構所組成之群中之至少1種作為上述X ₃。 ＜23＞ 如項目22之聚醯胺酸-醯亞胺共聚物，其中上述通式(1)中之X ₄係選自由下述通式(A-4)、下述通式(A-5)及下述通式(A-6)： [化24]

{式中，R ₈～R ₁₁分別獨立地表示碳數1～20之一價有機基、或鹵素，並且h～k分別獨立地為0～4之整數，Z ₂表示鍵結基，並且*表示鍵結部} [化25]

{式中，R ₁₂及R ₁₃分別獨立地表示碳數1～20之一價有機基、或鹵素，i及j分別獨立地為0～4之整數，並且*表示鍵結部，其中於上述X ₃係源自9,9-雙(3,4-二羧基苯基)茀二酸酐(BPAF)之基之情形時，上述通式(A-5)係源自4,4'-二胺基二苯基碸之基之情形除外} [化26]

{式中，R ₁₄及R ₁₅分別獨立地表示碳數1～20之一價有機基、或鹵素，n及о分別獨立地為0～4之整數，並且*表示鍵結部} 所表示之結構所組成之群中之至少1種。 ＜24＞ 如項目19至23中任一項之聚醯胺酸-醯亞胺共聚物，其中構成上述通式(1)中之X ₂之二胺成分與構成X ₄之二胺成分之二胺組成或二胺種類之任一者不同。 ＜25＞ 如項目19至24中任一項之聚醯胺酸-醯亞胺共聚物，其中上述通式(1)中之X ₁係選自由源自聯苯四羧酸二酐(BPDA)之結構、源自4,4'-氧二鄰苯二甲酸二酐(ODPA)之結構、及源自4,4'-聯苯雙(偏苯三甲酸單酯酸酐)(TAHQ)之結構所組成之群中之至少1種。 ＜26＞ 如項目19至25中任一項之聚醯胺酸-醯亞胺共聚物，其中上述通式(1)中所包含之X ₁與X ₂之莫耳比(X ₂/X ₁)為0.84～1.00，且上述通式(1)中所包含之X ₃與X ₄(X ₄/X ₃)之莫耳比為1.01～2.00。 ＜27＞ 如項目19至26中任一項之聚醯胺酸-醯亞胺共聚物，其中包含上述通式(1)中之X ₁及X ₂之聚醯胺酸之結構單元N與包含X ₃及X ₄之聚醯亞胺之結構單元M之莫耳比(結構單元N之莫耳數：結構單元M之莫耳數)為60：40～95：5之範圍。 ＜28＞ 一種樹脂組合物，其含有如項目19至27中任一項之聚醯胺酸-醯亞胺共聚物、及(d)有機溶劑。 ＜29＞ 如項目28之樹脂組合物，其中上述樹脂組合物中所包含之全部聚合物中，包含X ₁及X ₂之聚醯胺酸之結構單元N之比率為60～95莫耳%。 ＜30＞ 如項目28或29之樹脂組合物，其進而包含(e)醯亞胺化觸媒。 ＜31＞ 一種聚醯亞胺共聚物，其特徵在於包含下述通式(2)所表示之結構單元： [化27]

{式中，X ₁及X ₃表示四價有機基，X ₂及X ₄表示二價有機基，並且n及m為正之整數，將包含X ₁及X ₂之結構單元稱為結構單元N，並且將包含X ₃及X ₄之結構單元稱為結構單元M，且 於X ₂係源自4-胺基苯甲酸4-胺基-3-氟苯酯之基之情形時，下述構成1、2除外： 1.於X ₃係源自9,9-雙(3,4-二羧基苯基)茀二酸酐(BPAF)之基之情形時，X ₂係源自4,4'-二胺基二苯基碸、及/或2,2'-雙(三氟甲基)聯苯胺之基；及 2.X ₃係源自降𦯉烷-2-螺-α-環戊酮a-α'-螺-2''-降𦯉烷-5,5'',6,6''-四羧酸二酐之基}，且 具有下述通式(A-1)： [化28]

{式中，R ₁及R ₂分別獨立地表示碳數1～20之一價有機基、或鹵素，a及b分別獨立地為0～4之整數，並且*表示鍵結部} 或下述通式(A-2)： [化29]

{式中，R ₃表示碳數1～20之一價有機基、或鹵素，c為0～4之整數，並且*表示鍵結部} 所表示之結構作為上述X ₂。 ＜32＞ 如項目31之聚醯亞胺共聚物，其中上述通式(2)中之X ₃係選自由下述通式(A-3)： [化30]

{式中，R ₄～R ₇分別獨立地表示碳數1～20之一價有機基、或鹵素，d～g分別獨立地為0～4之整數，Z ₁表示鍵結基，並且*表示鍵結部} 所表示之結構、源自4,4'-氧二鄰苯二甲酸二酐(ODPA)之結構、及源自4,4'-(六氟亞異丙基)二鄰苯二甲酸酐(6FDA)之結構所組成之群中之至少1種。 ＜33＞ 一種聚醯亞胺共聚物，其特徵在於具有下述通式(2)所表示之結構單元： [化31]

{式中，X ₁及X ₃表示四價有機基，X ₂及X ₄表示二價有機基，n及m為正之整數，將包含X ₁及X ₂之結構單元稱為結構單元N，將包含X ₃及X ₄之結構單元稱為結構單元M，且 X ₄係將源自4,4'-二胺基二苯基碸、2,2'-雙(三氟甲基)聯苯胺之基除外}，且 包含選自由下述通式(A-3)：

{式中，R ₄～R ₇分別獨立地表示碳數1～20之一價有機基、或鹵素，d～g分別獨立地為0～4之整數，Z ₁表示鍵結基，並且*表示鍵結部} 所表示之結構、源自4,4'-氧二鄰苯二甲酸二酐(ODPA)之結構、及源自4,4'-(六氟亞異丙基)二鄰苯二甲酸酐(6FDA)之結構所組成之群中之至少1種作為上述X ₃。 ＜34＞ 如項目33之聚醯亞胺共聚物，其中上述通式(2)中之X ₄係選自由下述通式(A-4)、下述通式(A-5)及下述通式(A-6)： [化32]

{式中，R ₈～R ₁₁分別獨立地表示碳數1～20之一價有機基、或鹵素，並且h～k分別獨立地為0～4之整數，Z ₂表示鍵結基，並且*表示鍵結部} [化33]

{式中，R ₁₂及R ₁₃分別獨立地表示碳數1～20之一價有機基、或鹵素，l及m分別獨立地為0～4之整數，並且*表示鍵結部，於上述X ₃係源自9,9-雙(3,4-二羧基苯基)茀二酸酐(BPAF)之基之情形時，上述通式(A-5)係源自4,4'-二胺基二苯基碸之基之情形除外} [化34]

{式中，R ₁₄及R ₁₅分別獨立地表示碳數1～20之一價有機基、或鹵素，n及о分別獨立地為0～4之整數，並且*表示鍵結部} 所表示之結構所組成之群中之至少1種。 ＜35＞ 如項目31至34中任一項之聚醯亞胺共聚物，其中上述通式(2)中之X ₁係選自由源自聯苯四羧酸二酐(BPDA)之結構、源自4,4'-氧二鄰苯二甲酸二酐(ODPA)之結構、及源自4,4'-聯苯雙(偏苯三甲酸單酯酸酐)(TAHQ)之結構所組成之群中之至少1種。 ＜36＞ 如項目31至35中任一項之聚醯亞胺共聚物，其中上述通式(2)中所包含之X ₁與X ₂之莫耳比(X ₂/X ₁)為0.84～1.00，且上述通式(2)中所包含之X ₃與X ₄(X ₄/X ₃)之莫耳比為1.01～2.00。 ＜37＞ 如項目31至36中任一項之聚醯亞胺共聚物，其中包含上述通式(2)中之X ₁及X ₂之聚醯亞胺之結構單元N與包含X ₃及X ₄之聚醯亞胺之結構單元M之莫耳比(結構單元N之莫耳數：結構單元M之莫耳數)為60：40～95：5之範圍。 ＜38＞ 一種樹脂組合物，其特徵在於：具有下述通式(I)所表示之聚醯亞胺前驅物、或者下述通式(I)所表示之聚醯亞胺前驅物骨架及下述通式(II)所表示之聚醯亞胺骨架，且 包含沸點250℃～350℃之非質子性極性物質， [化35]

{式中，P ₁表示二價有機基，P ₂表示四價有機基，且p表示正之整數} [化36]

{式中，P ₁表示二價有機基，P ₂表示四價有機基，且p表示正之整數}。 ＜39＞ 一種樹脂組合物，其包含下述通式(II)所表示之聚醯亞胺、溶劑、及沸點250℃～350℃之非質子性極性物質： [化37]

{式中，P ₁表示二價有機基，P ₂表示四價有機基，且p表示正之整數}。 [發明之效果] <1> A resin composition characterized by comprising a polyamic acid-imide copolymer, (d) an organic solvent, and (e) an imidization catalyst, and the above (e) imidization catalyst The medium is at least one selected from the group consisting of imidazole compounds, pyridine compounds, and tertiary amine compounds, and the above-mentioned polyamic acid-imide copolymer includes structural units represented by the following general formula (1): [chemical 1]

{In the formula, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, n, m, and l are positive integers, and include the following general formula (A-1): 2]

(wherein, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, a and b are independently an integer of 0 to 4, and * represents a bonding portion) The structure is X ₂ } in the above general formula (1). <2> The resin composition according to item 1, wherein the above-mentioned imidazole compound is selected from 1-methylimidazole, N-tert-butoxycarbonylimidazole (N-Boc-imidazole), 2-methylimidazole, 2-benzene imidazole, benzimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 4-methyl-2-phenylimidazole, 2-undecylimidazole, 1- At least one of the group consisting of benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1H-imidazole, and 1,2-dimethylimidazole, the above-mentioned pyridine compound is selected from 4 -At least one of the group consisting of dimethylaminopyridine, 2,2'-bipyridine, nicotinic acid, isoquinoline, pyridine, and 2-picoline, and/or the above-mentioned tertiary amine compound It is selected from 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane, N-methylmorpholine, and triethyl At least one member of the group consisting of amines. <3> The resin composition according to Item 1 or 2, wherein the above-mentioned (e) imidization catalyst is the above-mentioned imidazole compound. <4> The resin composition according to any one of items 1 to 3, wherein the content of the imidization catalyst (e) is 5 parts by mass relative to 100 parts by mass of the polyamic acid-imide copolymer above. <5> A resin composition comprising a polyamic acid-imide copolymer, and (d) an organic solvent, wherein the polyamic acid-imide copolymer comprises a compound represented by the following general formula (1): Structural unit: [Chem3]

{In the formula, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, n, m, and l are positive integers, and include the following general formula (A-1): 4]

(wherein, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, a and b are independently an integer of 0 to 4, and * represents a bonding portion) The structure is X ₂ } in the above-mentioned general formula (1), and the weight-average molecular weight of the above-mentioned polyamic acid-imide copolymer is 170,000 or more. <6> The resin composition according to any one of items 1 to 4, wherein the polyamide acid-imide copolymer has a weight average molecular weight of 170,000 or more. <7> A resin composition comprising a polyamic acid, (d) an organic solvent, and (e) an imidization catalyst, the polyamic acid comprising a structural unit represented by the following general formula (3) : [Chemical 5]

{In the _formula , X1 represents _a tetravalent organic group, X2 represents a divalent organic group, and n is a positive integer, and includes the following general formula (A-1): [Chemical 6]

(wherein, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, a and b are independently an integer of 0 to 4, and * represents a bonding portion) Structure As X ₂ } in the above-mentioned general formula (3), the above-mentioned (e) imidization catalyst is selected from 1-methylimidazole, N-tert-butoxycarbonylimidazole (N-Boc-imidazole), 2-methylimidazole, 2-phenylimidazole, benzimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 4-methyl-2-phenylimidazole, 2 -Undecylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1H-imidazole, 4-dimethylaminopyridine, 2,2'-bipyridine, Nicotinic acid, isoquinoline, pyridine, 2-picoline, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane At least one of the group consisting of alkanes, N-methylmorpholine, and triethylamine. <8> A resin composition comprising a polyamic acid, (d) an organic solvent, and (e) an imidization catalyst, the polyamic acid comprising a structural unit represented by the following general formula (3) : [chem 7]

{In the _formula , X1 represents _a tetravalent organic group, X2 represents a divalent organic group, and n is a positive integer, and includes the following general formula (A-1): [Chemical 8]

(wherein, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, a and b are independently an integer of 0 to 4, and * represents a bonding portion) Structure As X ₂ } in the above-mentioned general formula (3), the above-mentioned (e) imidization catalyst is an imidazole compound, and the content of the above-mentioned (e) imidization catalyst is relative to the above-mentioned polyamic acid 100 mass The part is 5 parts by mass or more. <9> A resin composition comprising a polyamic acid, (d) an organic solvent, and (e) an imidization catalyst, the polyamic acid comprising a structural unit represented by the following general formula (3) : [Chem 9]

{In the _formula , X1 represents _a tetravalent organic group, X2 represents a divalent organic group, and n is a positive integer, and includes the following general formula (A-1): [Chem. 10]

(wherein, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, a and b are independently an integer of 0 to 4, and * represents a bonding portion) Structure As X ₂ } in the above-mentioned general formula (3), the above-mentioned (e) imidization catalyst is an imidazole compound, and the weight-average molecular weight of the above-mentioned polyamic acid is 170,000 or more. <10> The resin composition according to Item 7 or 8, wherein the polyamic acid has a weight average molecular weight of 170,000 or more. <11> The resin composition according to any one of items 1 to 10, wherein the content of the imidization catalyst (e) is relative to 100 parts by mass of the above-mentioned polyamide acid-imide copolymer or the above-mentioned polyamide 100 mass parts of amine acids are 10 mass parts or more. <12> The resin composition according to any one of items 1 to 11, wherein the (e) imidization catalyst contains N-tert-butoxycarbonylimidazole (N-Boc-imidazole) and/or 1 - the imidazole compound of methylimidazole. <13> The resin composition according to any one of items 1 to 12, wherein the polyamic acid-imide copolymer or the polyamic acid has a weight average molecular weight of 220,000 or more. <14> The resin composition according to any one of items 1 to 13, further comprising an aprotic polar substance having a boiling point of 250°C to 350°C. <15> The resin composition according to item 14, wherein the above-mentioned aprotic polar substance is cyclobutene. <16> The resin composition according to any one of items 1 to 15, wherein X ₄ in the above general formula (1) or X ₂ in (3) is selected from the following general formula (A-4), the following Describe general formula (A-5) and following general formula (A-6): [Chemical 11]

{In the formula, R ₈ to R ₁₁ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, and h to k each independently represent an integer of 0 to 4, Z ₂ represents a bonding group, and * Indicates the bonding part} [Chem. 12]

{In the formula, R ₁₂ and R ₁₃ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, l and m each independently represent an integer of 0 to 4, and * represents a bonding portion} [Chem. 13 ]

{In the formula, R ₁₄ and R ₁₅ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, n and o are each independently an integer of 0 to 4, and * represents a bonding portion} At least one of the group of structures. <17> The resin composition according to any one of Items 1 to 6, 11 to 16, wherein X ₃ in the above general formula (1) is selected from the following general formula (A-3): [Chem. 14]

{In the formula, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents The structure represented by the bonding portion}, the structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), the structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride Anhydride (6FDA) structure, structure derived from biphenyl tetracarboxylic dianhydride (BPDA), and structure derived from 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ) At least 1 species in the group. <18> The resin composition according to any one of items 1 to 6, 11 to 17, wherein the content of the above-mentioned (e) imidization catalyst is relative to the repeating unit 1 of the above-mentioned polyamic acid-imide copolymerization The mole is in the range of 0.02 to 0.15 mole%. <19> A polyamic acid-imide copolymer characterized by comprising a structural unit L represented by the following general formula (1): [Chem. 15]

{In the formula, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, n, m, and l are positive integers, and the structural unit containing X ₁ and X ₂ is called a structural unit N, and the structural unit comprising X ₃ and X ₄ is called structural unit M, and when X ₂ is a base derived from 4-aminobenzoic acid 4-amino-3-fluorophenyl ester, the following constitution 1. Except for 2: 1. In the case where X ₃ is derived from the base of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), X ₂ is derived from 4,4'- Diaminodiphenylene, and/or 2,2'-bis(trifluoromethyl)benzidine; and 2.X ₃ is derived from nor-2-spiro-α-cyclopentanone- α'-spiro-2''-nor-alkane-5,5'',6,6''-tetracarboxylic dianhydride base; }, and has the following general formula (A-1): [Chemical 16 ]

{In the formula, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, a and b each independently represent an integer of 0 to 4, and * represents a bonding portion} or the following General formula (A-2): [Chem. 17]

{wherein, R ₃ represents a valent organic group with 1 to 20 carbons, or a halogen, and c is an integer of 0 to 4. The structure represented by * represents a bonding portion} is taken as the above-mentioned X ₂ . <20> The polyamic acid-imide copolymer as in item 19, wherein X in the above general formula ( ₁ ) is selected from the following general formula (A-3): [Chem. 18]

{In the formula, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents The structure represented by the bonding portion}, the structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), and the structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride (ODPA) At least one of the group consisting of the structure of formic anhydride (6FDA). <21> The polyamic acid-imide copolymer as in item 19 or 20, wherein X in the above-mentioned general formula ( ₁ ) has a formula selected from the following general formula (A-4), the following general formula (A -5) and the following general formula (A-6): [Chemical 19]

{In the formula, R ₈ to R ₁₁ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, and h to k each independently represent an integer of 0 to 4, Z ₂ represents a bonding group, and * Indicates the bonding part} [Chem. 20]

{In the formula, R ₁₂ and R ₁₃ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, l and m each independently represent an integer of 0 to 4, and * represents a bonding part, wherein in the above When _X3 is derived from the base of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), the above general formula (A-5) is derived from 4,4'-diamine Except for the case of the base of the diphenyl group} [Chem. 21]

{In the formula, R ₁₄ and R ₁₅ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, n and o are each independently an integer of 0 to 4, and * represents a bonding portion} At least one of the group of structures. <22> A polyamic acid-imide copolymer characterized by comprising a structural unit L represented by the following general formula (1): [Chem. 22]

{In the formula, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, n, m, and l are positive integers, and the structural unit containing X ₁ and X ₂ is called a structural unit N, the structural unit comprising X ₃ and X ₄ is called structural unit M, and X ₄ is derived from 4,4'-diaminodiphenylene and/or 2,2'-bis(trifluoroform base) except for the base of benzidine}, and has the general formula (A-3) selected from the following: [Chemical 23]

{In the formula, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents The structure represented by the bonding portion}, the structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), and the structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride (ODPA) At least one of the group consisting of the structure of formic anhydride (6FDA) is X ₃ . <23> The polyamic acid-imide copolymer as in item 22, wherein X in the above general formula ( ₁ ) is selected from the following general formula (A-4), the following general formula (A-5 ) and the following general formula (A-6): [Chemical 24]

{In the formula, R ₈ to R ₁₁ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, and h to k each independently represent an integer of 0 to 4, Z ₂ represents a bonding group, and * Indicates the bonding part} [Chem. 25]

{In the formula, R ₁₂ and R ₁₃ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, i and j are each independently an integer of 0 to 4, and * represents a bonding part, wherein in the above When _X3 is derived from the base of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), the above general formula (A-5) is derived from 4,4'-diamine Except for the case of the base of the diphenyl group} [Chem. 26]

{In the formula, R ₁₄ and R ₁₅ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, n and o are each independently an integer of 0 to 4, and * represents a bonding portion} At least one of the group of structures. <24> The polyamic acid-imide copolymer according to any one of items 19 to 23, wherein the diamine component constituting X2 in the above general formula (1) and the diamine component constituting _X4 are _two Either the amine composition or the type of diamine is different. <25> The polyamic acid-imide copolymer according to any one of items 19 to 24, wherein X in the above general formula ( ₁ ) is selected from biphenyltetracarboxylic dianhydride (BPDA) The structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), and the structure derived from 4,4'-biphenyl bis(trimellitic monoester anhydride) (TAHQ) At least one of the group formed. <26> The polyamic acid-imide copolymer according to any one of Items 19 to 25, wherein the molar ratio of X ₁ to X ₂ contained in the above general formula (1) (X ₂ /X ₁ ) is 0.84 to 1.00, and the molar ratio of X ₃ and X ₄ (X ₄ /X ₃ ) contained in the above general formula (1) is 1.01 to 2.00. <27> The polyamic acid-imide copolymer according to any one of items 19 to 26, wherein the polyamic acid structural unit N comprising X1 and X2 in the general _formula ( ₁ ) above and comprising The molar ratio of the structural unit M of the polyimides of _X3 and _X4 (the molar number of the structural unit N: the molar number of the structural unit M) is in the range of 60:40 to 95:5. <28> A resin composition comprising the polyamic acid-imide copolymer according to any one of items 19 to 27, and (d) an organic solvent. <29> The resin composition according to item 28, wherein in all the polymers contained in the above resin composition, the ratio of structural unit N of polyamic acid including X ₁ and X ₂ is 60-95 mol%. <30> The resin composition according to Item 28 or 29, further comprising (e) an imidization catalyst. <31> A polyimide copolymer characterized by comprising a structural unit represented by the following general formula (2): [Chem. 27]

{wherein, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, and n and m are positive integers, the structural unit comprising X ₁ and X ₂ is called a structural unit N, And the structural unit comprising X ₃ and X ₄ is called structural unit M, and when X ₂ is a group derived from 4-aminobenzoic acid 4-amino-3-fluorophenyl ester, the following constitution 1 , 2 except: 1. In the case where X ₃ is derived from the base of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), X ₂ is derived from 4,4'-bis Aminodiphenylamine, and/or 2,2'-bis(trifluoromethyl)benzidine; and 2.X ₃ is derived from nor-2-spiro-α-cyclopentanone a- α'-spiro-2''-nor-alane-5,5'',6,6''-tetracarboxylic dianhydride base}, and has the following general formula (A-1): [Chemical 28]

{In the formula, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, a and b each independently represent an integer of 0 to 4, and * represents a bonding portion} or the following General formula (A-2): [Chemical 29]

{wherein, R ₃ represents a valent organic group having 1 to 20 carbon atoms, or a halogen, c is an integer of 0 to 4, and * represents a bonding portion} The structure represented by the above-mentioned X ₂ . <32> The polyimide copolymer as in Item 31, wherein X in the above general formula ( ₂ ) is selected from the following general formula (A-3): [Chemical 30]

{In the formula, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents The structure represented by the bonding portion}, the structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), and the structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride (ODPA) At least one of the group consisting of the structure of formic anhydride (6FDA). <33> A polyimide copolymer characterized by having a structural unit represented by the following general formula (2): [Chemical 31]

{wherein, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, n and m are positive integers, the structural unit comprising X ₁ and X ₂ is called structural unit N, and The structural unit comprising X ₃ and X ₄ is called structural unit M, and X ₄ is derived from 4,4'-diaminodiphenylene, 2,2'-bis(trifluoromethyl)benzidine Except for the base}, and comprising the group selected from the following general formula (A-3):

{In the formula, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents The structure represented by the bonding portion}, the structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), and the structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride (ODPA) At least one of the group consisting of the structure of formic anhydride (6FDA) is X ₃ . <34> The polyimide copolymer according to item 33, wherein X in the above general formula ( ₂ ) is selected from the following general formula (A-4), the following general formula (A-5) and the following General formula (A-6): [Chemical 32]

{In the formula, R ₈ to R ₁₁ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, and h to k each independently represent an integer of 0 to 4, Z ₂ represents a bonding group, and * Indicates the bonding part} [Chem. 33]

{In the formula, R ₁₂ and R ₁₃ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, l and m each independently represent an integer of 0 to 4, and * represents a bonding portion, and in the above X When ₃ is derived from the base of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), the above general formula (A-5) is derived from 4,4'-diamine Except in the case of the base of diphenylphenylene} [Chem. 34]

{In the formula, R ₁₄ and R ₁₅ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, n and o are each independently an integer of 0 to 4, and * represents a bonding portion} At least one of the group of structures. <35> The polyimide copolymer according to any one of Items 31 to 34, wherein X in the above general formula ( ₂ ) is selected from a structure derived from biphenyltetracarboxylic dianhydride (BPDA), a source From the group consisting of structures derived from 4,4'-oxydiphthalic dianhydride (ODPA) and structures derived from 4,4'-biphenylbis(trimellitic monoester anhydride) (TAHQ) At least one of them. <36> The polyimide copolymer according to any one of items 31 to 35, wherein the molar ratio (X ₂ /X ₁ ) of X ₁ and X ₂ contained in the above-mentioned general formula (2) is 0.84～ 1.00, and the molar ratio of X ₃ and X ₄ (X ₄ /X ₃ ) contained in the above general formula (2) is 1.01-2.00. <37> The polyimide copolymer according to any one of items 31 to 36, wherein the structural unit N of polyimide comprising X1 and X2 in the above general _formula ( ₂ ) and comprising _X3 and X The molar ratio of the structural unit M of the polyimide ₄ (the molar number of the structural unit N: the molar number of the structural unit M) is in the range of 60:40 to 95:5. <38> A resin composition characterized by having a polyimide precursor represented by the following general formula (I), or a polyimide precursor skeleton represented by the following general formula (I) and the following The polyimide skeleton represented by the general formula (II), and contains an aprotic polar substance with a boiling point of 250°C to 350°C, [Chemical 35]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer} [化36]

{wherein, P1 represents _a divalent organic group, P2 represents a tetravalent organic group, and _p represents a positive integer}. <39> A resin composition comprising polyimide represented by the following general formula (II), a solvent, and an aprotic polar substance with a boiling point of 250°C to 350°C: [Chemical 37]

{wherein, P1 represents _a divalent organic group, P2 represents a tetravalent organic group, and _p represents a positive integer}. [Effect of Invention]

According to the present invention, it is possible to provide a polyamic acid-imide copolymer that realizes both transparency and heat resistance, and a resin composition containing it, and then provide a polyamide-imide copolymer having excellent transparency, haze, heat resistance and Polyimide film with coefficient of linear expansion, and method for producing same, and/or polyimide which uses aromatic acid dianhydride having skeletal skeleton as main component and has excellent bending resistance and transparency Block copolymerization with polyamic acid with excellent heat resistance can also provide a polyamic acid-imide copolymer resin composition that achieves both transparency and heat resistance, low residual stress and bending resistance , polyimide, or polyimide film, and methods for producing the same. Also, it is possible to provide a polyamic acid or polyimide containing 4-aminobenzoic acid 4-amino-3-fluorophenyl (APAB) which can reduce the defects of the polyimide film during infrared (IR) curing. The resin composition of amide acid-imide copolymer can further provide a polyimide film with reduced defects, and a manufacturing method thereof. Also, according to the present invention, it is possible to provide a resin composition capable of obtaining a polyimide resin film having excellent in-plane uniformity of film thickness and a low yellowness (YI value), a method for producing a polyimide resin film, A method for manufacturing a display, a method for manufacturing a laminate, and a method for manufacturing a flexible device.

Hereinafter, exemplary embodiments of the present invention (hereinafter, simply referred to as "embodiments") will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement after making various changes within the range of the summary. In addition, unless otherwise specified, the characteristic values described in the present invention mean values measured by the method described in the section of [Examples] or a method understood to be equivalent thereto.

＜Resin composition＞ The resin composition provided by one aspect of the present invention comprises (c) polyamide acid-imide copolymer, polyimide containing (a) polyamide acid and/or (b) polyimide Or polyamic acid, and (d) organic solvent, and other components, such as (e) imidization catalyst, may be contained as needed.

Hereinafter, each component will be demonstrated sequentially.

{式中，X ₁及X ₃表示四價有機基，X ₂及X ₄表示二價有機基，n、m、及l為正之整數，將包含X ₁及X ₂之結構單元稱為結構單元N，將包含X ₃及X ₄之結構單元稱為結構單元M} 且具有下述通式(A-1)： [化39]

{式中，R ₁及R ₂分別獨立地表示碳數1～20之一價有機基、或鹵素，a及b分別獨立地為0～4之整數，並且*表示鍵結部} 或下述通式(A-2)： [化40]

{式中，R ₃表示碳數1～20之一價有機基、或鹵素，c為0～4之整數，並且*表示鍵結部} 所表示之結構作為X ₂。 <First Embodiment> (A) Polyamic acid-imide copolymer The first embodiment of the present invention provides a polyamic acid-imide copolymer characterized by comprising the following general formula (1) The structural unit L represented by: [Chemical 38]

{In the formula, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, n, m, and l are positive integers, and the structural unit containing X ₁ and X ₂ is called a structural unit N, the structural unit comprising _X3 and _X4 is called structural unit M} and has the following general formula (A-1): [Chemical 39]

{In the _formula , R1 and R2 each independently represent a valent organic group with ₁ to 20 carbon atoms or a halogen, a and b each independently represent an integer of 0 to 4, and * represents a bonding part} or the following General formula (A-2): [Chemical 40]

{wherein, R ₃ represents a valent organic group having 1 to 20 carbon atoms, or a halogen, c is an integer of 0 to 4, and * represents a bonding portion} The structure represented is X ₂ .

{式中，R ₃、c及*如通式(A-2)中所定義}。 Also, as a specific example of the structure represented by the general formula (A-2), the following general formula (A-2a) can be exemplified: [Chem. 41]

{In the formula, R ₃ , c and * are as defined in the general formula (A-2)}.

The polyamic acid-imide copolymer of the first embodiment can be used as a polyimide precursor, and when using it to form a polyimide film, the coefficient of linear expansion is low, the residual stress is low, and the haze (Haze value) ) and yellowness (YI value) are small. Also, when the polyamic acid-imide copolymer of the first embodiment is used to form a polyimide film, the yellowness (YI value) in the high temperature range is small, and the haze (Haze value) is small. From this point of view, it is preferable that the weight average molecular weight of the polyamic acid-imide copolymer of the first embodiment is 170,000 or more, and/or it is preferable that X2 is derived from ₄ -aminobenzoic acid In the case of the base of 4-amino-3-fluorophenyl ester, the following constitutions 1 and 2 are excluded: Composition 1. In _X3 , it is derived from 9,9-bis(3,4-dicarboxyphenyl) fennel In the case of an acid anhydride (BPAF) group, X is derived from 4,4' _- diaminodiphenylsulfone and/or 2,2'-bis(trifluoromethyl)benzidine; and 2.X ₃ is derived from nor-2-spiro-α-cyclopentanone-α'-spiro-2''-nor-5,5'',6,6''-tetracarboxylic acid di Anhydride base.

{式中，R ₄～R ₇分別獨立地表示碳數1～20之一價有機基、或鹵素，d～g分別獨立地為0～4之整數，Z ₁表示鍵結基，並且*表示鍵結部} 所表示之結構、源自4,4'-氧二鄰苯二甲酸二酐(ODPA)之結構、源自4,4'-(六氟亞異丙基)二鄰苯二甲酸酐(6FDA)之結構、源自聯苯四羧酸二酐(BPDA)之結構、及源自4,4'-聯苯雙(偏苯三甲酸單酯酸酐)(TAHQ)之結構所組成之群中之至少1種作為X ₁及/或X ₃。 <Second Embodiment> The second embodiment of the present invention provides a polyamic acid-imide copolymer characterized in that it contains the structural unit L represented by the above general formula (1), and contains a polyamide selected from the following general formula: Formula (A-3): [Chemical 42]

{In the formula, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents The structure represented by the bonding part}, the structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), the structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride Anhydride (6FDA) structure, structure derived from biphenyl tetracarboxylic dianhydride (BPDA), and structure derived from 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ) At least one of the groups is X ₁ and/or X ₃ .

When the polyamide acid-imide precursor of the second embodiment is made into a polyimide film, the linear expansion coefficient is low, the residual stress is low, the bending resistance is excellent, the haze (Haze value) and the yellowness ( YI value) is smaller. In addition, when the polyamic acid-imide copolymer of the second embodiment is made into a polyimide film, the yellowness (YI value) and the haze (Haze value) in the high temperature range are small. In the second embodiment, from this point of view, it is preferable to include at least one selected from the group consisting of a structure represented by general formula (A-3), a structure derived from ODPA, and a structure derived from 6FDA 1 as X ₃ , and/or preferably when X ₃ is derived from 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), X ₄ is derived from Except for radicals derived from 4,4'-diaminodiphenylamine and/or 2,2'-bis(trifluoromethyl)benzidine.

{式中，P ₁表示二價有機基，P ₂表示四價有機基，且p表示正之整數}。 (聚醯亞胺樹脂) [化44]

{式中，P ₁表示二價有機基，P ₂表示四價有機基，且p表示正之整數}。 <Third Embodiment> In the third embodiment of the present invention, the resin composition is characterized by having a polyimide precursor represented by the following general formula (I), or a polyimide precursor represented by the following general formula (I). The polyimide precursor skeleton and the polyimide skeleton represented by the following general formula (II), and contain an aprotic polar substance with a boiling point of 250°C to 350°C, or the resin composition is characterized in that it contains the following Polyimide represented by the general formula (II), a solvent, and an aprotic polar substance with a boiling point of 250°C to 350°C. (polyimide precursor) [Chem. 43]

{wherein, P1 represents _a divalent organic group, P2 represents a tetravalent organic group, and _p represents a positive integer}. (polyimide resin) [Chem. 44]

{wherein, P1 represents _a divalent organic group, P2 represents a tetravalent organic group, and _p represents a positive integer}.

The polyimide of the third embodiment is obtained by thermally imidizing the polyimide precursor, and it can also be chemically imidized. From the viewpoint of the transparency of the obtained polyimide film, thermal imidization is preferable. In addition, the resin composition may contain an imidization accelerator.

The resin composition according to the third embodiment contains an aprotic polar substance with a boiling point of 250°C to 350°C, and in the curing step (heating step), the aprotic polar substance exhibits plasticization at a high temperature of, for example, 250°C or higher. The effect of the agent makes the resin soft and fluid, and when it is made into a polyimide resin film (hereinafter also referred to as a polyimide film), the in-plane uniformity of the film thickness can be improved, and the YI can also be reduced.

Furthermore, the resin composition of the third embodiment may further contain a solvent, such as an aprotic solvent. The aprotic solvent should be distinguished from the above-mentioned aprotic polar substance having a boiling point of 250°C to 350°C.

Here, the P2 groups in the general formulas (I) and ( _II ) are acid anhydride residues, which may be the same or different. Also, the P ₁ groups in the general formulas (I) and (II) are diamine residues, which may be the same or different.

{式中，X ₁表示四價有機基，X ₂表示二價有機基，並且n為正之整數，且 具有下述通式(A-1)： [化46]

(式中，R ₁及R ₂分別獨立地表示碳數1～20之一價有機基、或鹵素，a及b分別獨立地為0～4之整數，並且*表示鍵結部) 所表示之結構作為上述通式(3)中之X ₂}，且 係與特定之(e)醯亞胺化觸媒一起調配或聚醯胺酸之重量平均分子量為170,000以上。第四實施方式之聚醯胺酸或包含源自其之結構單元之聚醯胺酸-醯亞胺共聚物可減少紅外線(IR)固化時之聚醯亞胺膜之缺陷。 <Fourth embodiment> (B) Polyamic acid In the fourth embodiment of the present invention, there is provided a polyamic acid or a polyamic acid-imide copolymer containing a structural unit derived therefrom, The polyamic acid is characterized in that it comprises a structural unit represented by the following general formula (3): [Chemical 45]

{In the _formula , X1 represents _a tetravalent organic group, X2 represents a divalent organic group, and n is a positive integer, and has the following general formula (A-1): [Chemical 46]

(wherein, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, a and b are independently an integer of 0 to 4, and * represents a bonding portion) The structure is X ₂ } in the above general formula (3), and it is prepared together with a specific (e) imidization catalyst or the weight average molecular weight of polyamic acid is 170,000 or more. The polyamic acid of the fourth embodiment or the polyamic acid-imide copolymer including structural units derived therefrom can reduce defects of the polyimide film during infrared (IR) curing.

Features of the first, second, third and fourth embodiments may be combined or interchanged. The first, second, third, and fourth embodiments have common configurations, and preferred configurations and the like will be described below.

(a) <Embodiment of polyamide part> The polyamic acid moiety constituting the polyamic acid-imide copolymer of the present invention is a moiety represented by the structural unit N in the above general formula (1).

In the above general formula ( ₁ ), X1 is _a tetravalent organic group, and the multiple X1s present in the polyimide precursor may be the same as or different from each other. As X ₁ , a tetravalent organic group derived from the following tetracarboxylic dianhydride can be illustrated.

Examples of tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms, aliphatic tetracarboxylic dianhydrides having 6 to 50 carbon atoms, and alicyclic tetracarboxylic dianhydrides having 6 to 36 carbon atoms. Tetracarboxylic dianhydride. Among these, aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms are preferred from the viewpoint of yellowness in a high temperature range. The carbon number mentioned here also includes the number of carbons contained in a carboxyl group.

Examples of aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms include: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (hereinafter also referred to as 6FDA), 5 -(2,5-dioxotetrahydro-3-furyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride (hereinafter also referred to as PMDA), 1, 2,3,4-Benzene tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid Dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter also referred to as BPDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (hereinafter , also recorded as DSDA), 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4 diphthalic dianhydride, 1,1-ethylene-4, 4'-diphthalic dianhydride, 2,2-propylene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride , 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-penta Methyl-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride (hereinafter also referred to as ODPA), terephthalic bis(trimellitic anhydride) (hereinafter also referred to as TAHQ) Thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,-dicarboxyphenyl)benzene Dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2 -(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, bis [3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3 -(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4 -dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2, 3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,4,9,10 - Perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, etc.

As the aliphatic tetracarboxylic dianhydride having 6 to 50 carbon atoms, for example, ethylene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, etc. can be mentioned; Examples of alicyclic tetracarboxylic dianhydrides having 6 to 36 carbon atoms include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane Alkane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclopentanone bispiro-northane tetracarboxylic dianhydride (hereinafter, Also described as CPODA), 3,3',4,4'-dicyclohexyl tetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, Methyl-4,4'-bis(cyclohexane-12-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) Dianhydride, 1,1-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane alkane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane alkane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]octane- 7-ene-2,3,5,6-tetracarboxylic dianhydride, REL-[1S,5R,6R]-3-oxabicyclo[3,2]octane-2,4-dione-6 -Spiro-3'-(tetrahydrofuran-2',5'dione), 4-(2,5-dioxatetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2 -dicarboxylic anhydride, ethylene glycol-bis-3,4-dicarboxylic anhydride phenyl) ether, etc.

In _a preferred aspect, X is derived from the group selected from pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), 4,4'-biphenylbis(trimellitic acid Monoester anhydride) (TAHQ), 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), 3,3',4,4'-diphenylpyridine tetracarboxylic dianhydride ( DSDA), 4,4'-oxydiphthalic anhydride (ODPA), and cyclopentanone bisspironorthane tetracarboxylic dianhydride (CPODA).

From the viewpoint of the balance of coefficient of linear expansion (CTE), chemical resistance, glass transition temperature (Tg), and yellowness in high-temperature regions, PMDA, BPDA, DSDA, TAHQ, ODPA, and CPODA are preferable , more preferably BPDA, TAHQ, and ODPA.

The polyamic acid-imide copolymer may be obtained, for example, by using a dicarboxylic acid other than the above-mentioned tetracarboxylic dianhydride as a polyimide precursor as long as the performance is not impaired. By using such a precursor, various properties such as improvement of mechanical elongation, improvement of glass transition temperature, and reduction of yellowness can be adjusted in the obtained film. As such a dicarboxylic acid, a dicarboxylic acid and an alicyclic dicarboxylic acid having an aromatic ring may, for example, be mentioned. Particularly preferred is at least one compound selected from the group consisting of aromatic dicarboxylic acids having 8 to 36 carbon atoms and alicyclic dicarboxylic acids having 6 to 34 carbon atoms. The number of carbons mentioned here also includes the number of carbons contained in the carboxyl group. Among these, dicarboxylic acids having an aromatic ring are preferred.

Specifically as the dicarboxylic acid, for example, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3' -Biphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-sulfonyl dibenzoic acid , 3,4'-sulfonyl dibenzoic acid, 3,3'-sulfonyl dibenzoic acid, 4,4'-oxydibenzoic acid, 3,4'-oxydibenzoic acid, 3,3 '-Oxydibenzoic acid, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)propane, 2,2'-dimethyl-4,4'- Biphenyl dicarboxylic acid, 3,3'-dimethyl-4,4'-biphenyl dicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyl dicarboxylic acid, 9,9- Bis(4-(4-carboxyphenoxy)phenyl) fluorene, 9,9-bis(4-(3-carboxyphenoxy)phenyl) fluorene, 4,4'-bis(4-carboxyphenoxy base) biphenyl, 4,4'-bis(3-carboxyphenoxy)biphenyl, 3,4'-bis(4-carboxyphenoxy)biphenyl, 3,4'-bis(3-carboxyphenoxy)biphenyl Oxy)biphenyl, 3,3'-bis(4-carboxyphenoxy)biphenyl, 3,3'-bis(3-carboxyphenoxy)biphenyl, 4,4'-bis(4-carboxy Phenoxy)-terphenyl, 4,4'-bis(4-carboxyphenoxy)-terphenyl, 3,4'-bis(4-carboxyphenoxy)-terphenyl, 3, 3'-bis(4-carboxyphenoxy)-p-terphenyl, 3,4'-bis(4-carboxyphenoxy)-m-terphenyl, 3,3'-bis(4-carboxyphenoxy )-terphenyl, 4,4'-bis(3-carboxyphenoxy)-terphenyl, 4,4'-bis(3-carboxyphenoxy)-terphenyl, 3,4' -bis(3-carboxyphenoxy)-terphenyl, 3,3'-bis(3-carboxyphenoxy)-terphenyl, 3,4'-bis(3-carboxyphenoxy)-m Terphenyl, 3,3'-bis(3-carboxyphenoxy)-terphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2- Cyclohexanedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, etc.; and International Publication No. 2005/068535 The described 5-aminoisophthalic acid derivatives, etc. When these dicarboxylic acids are actually copolymerized with the polymer, they can also be used in the form of acyl chlorides derived from thionyl chloride or the like, active esters, and the like.

In the above general formula ( ₁ ), X is a divalent organic group, preferably the structure represented by the following general formula (A-1), the structure represented by the following general formula (A-4), the following general formula The structure represented by the formula (A-5), the structure represented by the following general formula (A-6), and the structure derived from the diamine represented by the following general formula (B-1), or derived from BAFL, Structures of BFAF, BAOFL, 44DAS, 33DAS, 44ODA, 34ODA, etc. As X ₂ , it is preferably a structure derived from 4-aminophenyl-4-aminobenzoate from the viewpoint of yellowness (YI value) in a high-temperature region, and in terms of haze (HAZE value) From this point of view, at least one structure derived from 4-aminobenzoic acid 4-amino-3-fluorophenyl (APAB), p-phenylenediamine (pPD), BAFL, and BFAF is preferable.

{式中，R ₁及R ₂分別獨立地表示碳數1～20之一價有機基、或鹵素，a及b分別獨立地為0～4之整數，並且*表示鍵結部}。 _The structure of X in the general formula (1) is represented by the following general formula (A-1) in one aspect: [Chemical 47]

{In the formula, R ₁ and R ₂ each independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, a and b each independently represent an integer of 0 to 4, and * represents a bonding portion}.

Here, R ₁ and R ₂ are not limited, and may be independently a valent organic group having 1 to 20 carbons, hydrogen (in the case of a and/or b=0), or halogen. As such organic groups, for example, alkyl groups such as methyl, ethyl, and propyl groups, halogen-containing groups such as trifluoromethyl groups, alkoxy groups such as methoxy groups and ethoxy groups; In the case of b=0, it may be hydrogen, or as halogen, fluorine or the like may be mentioned. Among them, hydrogen and/or phenyl are preferred from the viewpoint of yellowness (YI value) at a high temperature range, and hydrogen and/or phenyl are preferred from the viewpoint of haze (Haze value). , and at least one of the group consisting of fluorine.

Here, a and b are not limited, and may be an integer of 0-4, respectively. Among them, an integer of 0 to 2 is preferable from the viewpoint of yellowness (YI value) and residual stress, and 0 is particularly preferable from the viewpoint of yellowness (YI value) in a high-temperature region.

{式中，R ₁₄及R ₁₅分別獨立地表示碳數1～20之一價有機基、或鹵素，n及о分別獨立地為0～4之整數，並且*表示鍵結部}。 _The structure of X in the general formula (1) is represented by the following general formula (A-6) in one aspect: [Chemical 48]

{In the formula, R ₁₄ and R ₁₅ each independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, n and o are each independently an integer of 0 to 4, and * represents a bonding portion}.

Here, R ₁₄ and R ₁₅ are not limited, and may be independently a valent organic group having 1 to 20 carbons, hydrogen (when n and o=0) or halogen. Examples of such organic groups include alkyl groups such as methyl, ethyl, and propyl, halogen-containing groups such as trifluoromethyl, and alkoxy groups such as methoxy and ethoxy; In the case of =0, it may be hydrogen, or as halogen, fluorine, etc. may be mentioned. Among them, hydrogen and/or phenyl are preferred from the viewpoint of yellowness (YI value) in a high-temperature region, and hydrogen and/or phenyl groups are preferred from the viewpoint of haze (Haze value). , and at least one of the group consisting of fluorine.

Here, n and о are not limited, and may be integers of 0 to 4, respectively. Among them, an integer of 0 to 2 is preferable from the viewpoint of yellowness (YI value) and residual stress, and 0 is particularly preferable from the viewpoint of yellowness (YI value) in a high-temperature region.

{式中，R ₃表示碳數1～20之一價有機基、或鹵素，c為0～4之整數，並且*表示鍵結部}。 The structure of X in the general formula (1) is represented by the following general formula (A- ₂ ) in one aspect: [Chemical 49]

{In the formula, R ₃ represents a valent organic group having 1 to 20 carbon atoms, or a halogen, c is an integer of 0 to 4, and * represents a bonding portion}.

Here, R ₃ is not limited and may be independently a valent organic group having 1 to 20 carbons, hydrogen (in the case of c=0) or halogen. Examples of such organic groups include alkyl groups such as methyl, ethyl, and propyl groups, halogen-containing groups such as trifluoromethyl groups, and alkoxy groups such as methoxy and ethoxy groups; In this case, it may be hydrogen, or as halogen, fluorine or the like may be exemplified. Among them, hydrogen is preferable from the viewpoint of yellowness (YI value) in a high-temperature region, and methyl and/or fluorine are preferable from the viewpoint of haze (Haze value).

Here, c is not limited and may be an integer of 0 to 4, respectively. Among them, an integer of 0 to 2 is preferable from the viewpoint of yellowness (YI value) and residual stress, and 0 is particularly preferable from the viewpoint of yellowness (YI value) in a high-temperature region.

{式中，R ₁、R ₂、a及b係與通式(A-1)同樣地定義}。 In one aspect, the structural unit represented by the general formula (A-1) is derived from a diamine represented by the following general formula (B-1): [Chemical 50]

{In the formula, R ₁ , R ₂ , a, and b are defined in the same manner as in the general formula (A-1)}.

As the diamine represented by the general formula (B-1), more specifically, 4-aminophenyl-4-aminobenzoate (hereinafter also referred to as APAB), 2-methyl -4-Aminophenyl-4-aminobenzoate (hereinafter also referred to as 2Me-APAB), 3-methyl-4-aminophenyl-4-aminobenzoate (hereinafter, Also referred to as 3Me-APAB), 2-fluoro-4-aminophenyl-4-aminobenzoate (hereinafter also referred to as 2F-APAB), 3-fluoro-4-aminophenyl-4 -aminobenzoate (hereinafter also referred to as 3F-APAB), 3-methyl-4-aminophenyl-3-methyl-4-aminobenzoate (hereinafter also referred to as 3F-APAB), , 3Me-APAB), etc.; in terms of yellowness (YI value) in the high temperature region, APAB is preferred, and in terms of haze (Haze value) reduction, APAB and 3Me-APAB are preferred , and 3F-APAB.

{式中，R ₃、及c係與通式(A-2)同樣地定義}。 In one aspect, the structural unit represented by the general formula (A-2) is derived from a diamine represented by the following general formula (B-2): [Chemical 51]

{In the formula, R ₃ and c are defined in the same manner as in the general formula (A-2)}.

As the diamine represented by the general formula (B-2), more specifically, p-phenylenediamine (pPD), m-phenylenediamine, 3,5-diaminobenzoic acid, etc. can be exemplified. From the standpoint of sex, pPD is preferred.

Polyamic acid, polyimide, polyamic acid-imide copolymer, and polyimide copolymer can be in the range of non-destructive yellowness, haze, residual stress, etc., except for the above general formula ( B-1) and the diamine represented by general formula (B-2) other than the diamine represented by general formula (B-1) and general formula (B-2), other diamine is used.

As other diamines, for example, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4 ,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'- Diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'- Diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene Oxy)benzene, bis[4-(4-aminophenoxy)phenyl]pyridine, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-amino Phenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4 -aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl) ) propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4- (4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, etc.; preferably one or more selected from these . The content of the above-mentioned other diamines in the total diamines is preferably less than 20 mol%, especially preferably less than 10 mol%. On the other hand, from the viewpoint of heat resistance at high temperature, it is preferable that the diamine used does not contain polysiloxane-based diamine. For example, "X-22-9409" and "X-22-1660B-3" manufactured by Shin-Etsu Chemical Co., Ltd., which are commercially available as polysiloxane-based diamines, may be mentioned.

The molar ratio (X ₂ /X ₁ ) of X ₁ and X ₂ in the polyamide moiety contained in the above general formula (1) is preferably 0.84-1.00 or 0.85-1.2, more preferably 0.90-1.1 , and more preferably 0.92 to 1,00. When X ₁ /X ₂ is 0.84 or more or 0.85 or more, residual stress decreases and YI decreases. When X ₁ /X ₂ is 1.2 or less or 1.00 or less, mechanical properties such as elongation and breaking strength are excellent.

The weight average molecular weight (Mw) of polyamic acid and polyamic acid part is preferably 1,000 or more, more preferably 1,000-300,000 or 2,639-300,000, still more preferably 10,000-200,000 or 10,000-250,000, especially preferably 30,000 ~200,000. When the weight average molecular weight is 1,000 or more, mechanical properties such as elongation and breaking strength are excellent, residual stress decreases, and YI decreases. When the weight average molecular weight is 300,000 or less, it is easy to control the weight average molecular weight during the synthesis of polyamic acid, a resin composition with moderate viscosity can be obtained, and the coatability of the resin composition becomes better. Also, if the Mw of the polyamic acid and the polyamic acid part is 170,000 or more, it tends to be excellent in transparency, haze, heat resistance, and linear expansion coefficient, so it is preferable, and a Mw of 220,000 or more is more preferable. It tends to have the structure represented by the above-mentioned general formula (A-1) as X2 in the general formula ( ₁ ), which is remarkable. In the present invention, the weight average molecular weight is a value calculated using gel permeation chromatography (hereinafter also referred to as GPC) as a standard polystyrene conversion value.

(b) <Embodiment of polyimide part> The polyimide moiety constituting the polyamic acid-imide copolymer of the present invention is a moiety represented by the structural unit M in the above general formula (1).

In the above general formula (1), X ₃ is a tetravalent organic group, preferably derived from the structure represented by the following general formula (A-3), or 4,4'-oxydiphthalic acid The structure of at least one of dianhydride (ODPA) and 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) can be used from the implementation of the above <polyamic acid section Tetravalent organic groups of tetracarboxylic dianhydrides described in Method>. In addition, the plurality of X ₃ present in the polyamide acid-imide copolymer that can be used as a polyimide precursor may be the same as or different from each other, and may be the same as or different from X ₁ .

X ₃ is preferably a structure derived from 9,9-bis(3,4-dicarboxyphenyl) stilnic anhydride (BPAF) from the viewpoint of yellowness (YI value) in a high-temperature region. From the viewpoint of residual stress, a structure derived from ODPA is preferable.

Examples of tetracarboxylic dianhydrides that can be used in addition to or instead of the aforementioned BPAF, ODPA, and 6FDA include aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms, and aliphatic tetracarboxylic dianhydrides having 6 to 50 carbon atoms. Carboxylic acid dianhydride, and alicyclic tetracarboxylic dianhydride with 6 to 36 carbon atoms. Among these, aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms are preferred from the viewpoint of yellowness in a high temperature range. The carbon number mentioned here also includes the number of carbons contained in a carboxyl group.

Examples of the above-mentioned aromatic tetracarboxylic dianhydride having 8 to 36 carbon atoms include 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (hereinafter also referred to as 6FDA), 5- (2,5-dioxotetrahydro-3-furyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride (hereinafter also referred to as PMDA), 1,2 ,3,4-Benzene tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter also referred to as BPDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (hereinafter, Also described as DSDA), 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4 diphthalic dianhydride, 1,1-ethylene-4,4 '-Diphthalic dianhydride, 2,2-propylene-4,4'-diphthalic dianhydride, 1,2-ethylidene-4,4'-diphthalic acid di anhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-penta Methylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride (hereinafter also referred to as ODPA), terephthalic bis(trimellitic anhydride) (hereinafter also referred to as TAHQ) thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,-dicarboxyphenyl) Phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[ 2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, Bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[ 3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3, 4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2 ,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, etc.

Examples of the aliphatic tetracarboxylic dianhydride having 6 to 50 carbon atoms include ethylene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, and the like; Examples of alicyclic tetracarboxylic dianhydrides having 6 to 36 carbon atoms include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane Alkane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclopentanone bispiro-northane tetracarboxylic dianhydride (hereinafter, Also described as CPODA), 3,3',4,4'-dicyclohexyl tetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, Methyl-4,4'-bis(cyclohexane-12-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) Dianhydride, 1,1-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane alkane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane alkane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]octane- 7-ene-2,3,5,6-tetracarboxylic dianhydride, REL-[1S,5R,6R]-3-oxabicyclo[3,2]octane-2,4-dione-6 -Spiro-3'-(tetrahydrofuran-2',5'dione), 4-(2,5-dioxatetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2 -dicarboxylic anhydride, ethylene glycol-bis-3,4-dicarboxylic anhydride phenyl) ether, etc.

In a preferred aspect, X ₁ or X ₃ is derived from pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), 4,4'-biphenylbis(partial Tricarboxylic acid monoester anhydride) (TAHQ), 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), 3,3',4,4'-diphenylpyridine tetracarboxylic acid At least one of the group consisting of dianhydride (DSDA), 4,4'-oxydiphthalic anhydride (ODPA), and cyclopentanone bisspironorthane tetracarboxylic dianhydride (CPODA).

In terms of the balance of coefficient of linear expansion (CTE), chemical resistance, glass transition temperature (Tg), and yellowness in the high temperature region, PMDA, BPDA, DSDA, TAHQ, and CPODA are preferred, and more Best for BPDA, and TAHQ.

The polyamic acid-imide copolymer may be obtained, for example, by using a dicarboxylic acid as a polyimide precursor in addition to the above-mentioned tetracarboxylic dianhydride within a range that does not impair its performance. By using such a precursor, various properties such as improvement of mechanical elongation, improvement of glass transition temperature, and reduction of yellowness can be adjusted in the obtained film. As such a dicarboxylic acid, a dicarboxylic acid and an alicyclic dicarboxylic acid having an aromatic ring may, for example, be mentioned. Particularly preferred is at least one compound selected from the group consisting of aromatic dicarboxylic acids having 8 to 36 carbon atoms and alicyclic dicarboxylic acids having 6 to 34 carbon atoms. The carbon number here also includes the number of carbons contained in the carboxyl group. Among these, dicarboxylic acids having an aromatic ring are preferred.

Specifically as the dicarboxylic acid, for example, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3' -Biphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-sulfonyl dibenzoic acid , 3,4'-sulfonyl dibenzoic acid, 3,3'-sulfonyl dibenzoic acid, 4,4'-oxydibenzoic acid, 3,4'-oxydibenzoic acid, 3,3 '-Oxydibenzoic acid, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)propane, 2,2'-dimethyl-4,4'- Biphenyl dicarboxylic acid, 3,3'-dimethyl-4,4'-biphenyl dicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyl dicarboxylic acid, 9,9- Bis(4-(4-carboxyphenoxy)phenyl) fluorene, 9,9-bis(4-(3-carboxyphenoxy)phenyl) fluorene, 4,4'-bis(4-carboxyphenoxy base) biphenyl, 4,4'-bis(3-carboxyphenoxy)biphenyl, 3,4'-bis(4-carboxyphenoxy)biphenyl, 3,4'-bis(3-carboxyphenoxy)biphenyl Oxy)biphenyl, 3,3'-bis(4-carboxyphenoxy)biphenyl, 3,3'-bis(3-carboxyphenoxy)biphenyl, 4,4'-bis(4-carboxy Phenoxy)-terphenyl, 4,4'-bis(4-carboxyphenoxy)-terphenyl, 3,4'-bis(4-carboxyphenoxy)-terphenyl, 3, 3'-bis(4-carboxyphenoxy)-p-terphenyl, 3,4'-bis(4-carboxyphenoxy)-m-terphenyl, 3,3'-bis(4-carboxyphenoxy )-terphenyl, 4,4'-bis(3-carboxyphenoxy)-terphenyl, 4,4'-bis(3-carboxyphenoxy)-terphenyl, 3,4' -bis(3-carboxyphenoxy)-terphenyl, 3,3'-bis(3-carboxyphenoxy)-terphenyl, 3,4'-bis(3-carboxyphenoxy)-m Terphenyl, 3,3'-bis(3-carboxyphenoxy)-terphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2- Cyclohexanedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, etc.; and International Publication No. 2005/068535 The described 5-aminoisophthalic acid derivatives, etc. When these dicarboxylic acids are actually copolymerized with the polymer, they can also be used in the form of acyl chlorides derived from thionyl chloride or the like, active esters, and the like.

{式中，R ₄～R ₇分別獨立地表示碳數1～20之一價有機基或鹵素，d～g分別獨立地為0～4之整數，Z ₁表示鍵結基，並且*表示鍵結部} 所表示、或係源自4,4'-氧二鄰苯二甲酸二酐(ODPA)、及4,4'-(六氟亞異丙基)二鄰苯二甲酸酐(6FDA)。 _The structure of X in the general formula (1) or the following general formula (2) in one aspect, is the following general formula (A-3): [Chemical 52]

{wherein, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbons or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents a bond knot} represented by, or derived from, 4,4'-oxydiphthalic anhydride (ODPA), and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) .

Here, R ₆ to R ₉ are not limited, and may be independently a valent organic group having 1 to 20 carbons, hydrogen (in the case of d to g=0), or halogen. Examples of such organic groups include alkyl groups such as methyl, ethyl, and propyl groups, halogen-containing groups such as trifluoromethyl groups, and alkoxy groups such as methoxy and ethoxy groups; when d to g=0 In this case, it may be hydrogen, or as halogen, fluorine or the like may be exemplified. Among these, hydrogen is preferable from the viewpoint of yellowness (YI value) in a high-temperature region, and fluorine is preferable from the viewpoint of haze (Haze value).

Here, as Z ₁ , a single bond, a methylene group, an ethylidene group, an ether, a ketone, and the like can be exemplified. Among them, a single bond is more preferable from the viewpoint of YI in a high-temperature region, and a single bond and ether are preferable from the viewpoint of residual stress.

Here, d to g are not limited, and may be integers of 0 to 4, respectively. Among them, an integer of 0 to 2 is preferable from the viewpoint of yellowness (YI value) and residual stress, and 0 is particularly preferable from the viewpoint of yellowness (YI value) in a high-temperature region.

{式中，R ₄～R ₇、d～g、及Z ₁係與通式(A-3)同樣地定義，d及e較佳為分別獨立地為0～3之整數，f及g較佳為分別獨立地為0～4之整數}。 In one aspect, the structural unit represented by the general formula (A-3) is derived from the acid dianhydride represented by the following general formula (B-3): [Chemical 53]

{In the formula, R ₄ to R ₇ , d to g, and Z ₁ are defined in the same manner as the general formula (A-3), d and e are preferably independently integers of 0 to 3, and f and g are preferably Preferably, they are each independently an integer of 0 to 4}.

As the acid dianhydride represented by the general formula (B-3), more specifically, 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), 9,9-bis[ 4-(3,4-dicarboxyphenoxy) phenyl] stilbenic anhydride (BPF-PA), etc., in terms of haze (Haze value) reduction and high temperature range, BPAF is preferred, in terms of residual From the viewpoint of stress, BPAF and BPF-PA are preferable.

In the general formula (1) or the following general formula (2), _X4 is a divalent organic group, preferably a structure represented by at least one of the following general formulas (A-4) to (A-6) , a divalent organic group derived from the diamine described in the above <Embodiment of the Polyamic Acid Section> can be used. In addition, the plurality of X ₄ present in the polyimide or in the polyimide part may be the same as or different from each other, and from the viewpoint of realizing the opposite performance at the same time when it is made into polyimide, it is preferably the same as _X2 is different, more preferably, the diamine component constituting _X2 is different from the diamine component constituting _X4 in either the diamine composition or the type of diamine.

{式中，R ₈～R ₁₁分別獨立地表示碳數1～20之一價有機基、或鹵素，h～k分別獨立地為0～4之整數，Z ₂表示鍵結基，並且*表示鍵結部}。 The structure of X ₄ in the general formula (1) or the following general formula (2) is in one aspect represented by the following general formula (A-4): [Chem. 54]

{In the formula, R ₈ to R ₁₁ each independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, h to k each independently represent an integer of 0 to 4, Z ₂ represents a bonding group, and * represents Bonding Department}.

Here, R ₈ to R ₁₁ are not limited, and may be independently a valent organic group having 1 to 20 carbons, hydrogen (in the case of h to k=0), or halogen. Examples of such organic groups include alkyl groups such as methyl, ethyl, and propyl groups, halogen-containing groups such as trifluoromethyl groups, and alkoxy groups such as methoxy and ethoxy groups; where h to k=0 In this case, it may be hydrogen, or as halogen, fluorine or the like may be exemplified. Among them, hydrogen is preferable from the viewpoint of yellowness (YI value) in a high temperature range, and fluorine is preferable from the viewpoint of haze (Haze value).

Here, h to k are not limited, and may be integers of 0 to 4, respectively. Among them, an integer of 0 to 2 is preferable from the viewpoint of yellowness (YI value) and residual stress, and 0 is particularly preferable from the viewpoint of yellowness (YI value) in a high-temperature region.

As Z ₂ , a single bond, a methylene group, a vinyl group, an ether, a ketone, and the like can be exemplified. Among them, a single bond is preferable from the viewpoint of YI in a high temperature range.

{式中，R ₁₂及R ₁₃分別獨立地表示碳數1～20之一價有機基或鹵素，l及m分別獨立地為0～4之整數，並且*表示鍵結部，其中於上述通式(1)之X ₂係源自4-胺基苯甲酸4-胺基-3-氟苯酯之基，且X ₃係源自9,9-雙(3,4-二羧基苯基)茀二酸酐(BPAF)之基之情形時，通式(A-5)係將4,4'-二胺基二苯基碸或源自其之基除外}。 The structure of X ₄ in the general formula (1) or the following general formula (2) is in one aspect represented by the following general formula (A-5): [Chem. 55]

{In the formula, R ₁₂ and R ₁₃ independently represent a valent organic group with 1 to 20 carbons or a halogen, l and m are independently an integer of 0 to 4, and * represents a bonding part, wherein in the above general X ₂ of formula (1) is derived from the base of 4-aminobenzoic acid 4-amino-3-fluorophenyl ester, and X ₃ is derived from 9,9-bis(3,4-dicarboxyphenyl) In the case of the group of stilbenic anhydride (BPAF), general formula (A-5) excludes 4,4'-diaminodiphenylphenone or a group derived therefrom}.

Here, R ₁₂ and R ₁₃ are not limited, and each independently may be a monovalent organic group having 1 to 20 carbon atoms or a halogen such as fluorine. Examples of such organic groups include alkyl groups such as methyl, ethyl, and propyl, halogen-containing groups such as trifluoromethyl, aryl groups such as phenyl and naphthyl, and alkyl groups such as methoxy and ethoxy. Oxygen etc. Among these, a methyl group is preferable from the viewpoint of YI in a high temperature range.

Here, l and m are not limited and may be an integer of 0-4. Among them, from the viewpoint of YI and residual stress, an integer of 0 to 2 is preferable, and 0 is particularly preferable from the viewpoint of YI in a high-temperature region.

{式中，R ₁₄及R ₁₅分別獨立地表示碳數1～20之一價有機基、或鹵素，n及о分別獨立地為0～4之整數，並且*表示鍵結部}。 此處，R ₁₄、及R ₁₅並無限定，分別獨立地為碳數1～20之一價有機基即可。作為此種有機基，可例舉：甲基、乙基、丙基等烷基；三氟甲基等含鹵素之基；苯基、萘基等芳基；甲氧基、乙氧基等烷氧基；等。其中，就高溫區域下之YI之觀點而言，較佳為甲基及苯基。此處，n及о並無限定，為0～4之整數即可。其中，就YI與殘留應力之觀點而言，較佳為0～2之整數，就高溫區域下之YI之觀點而言，尤佳為0。 The structure of X ₄ in the general formula (1) or the following general formula (2) is in one aspect represented by the following general formula (A-6): [Chemical 56]

{In the formula, R ₁₄ and R ₁₅ each independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, n and o are each independently an integer of 0 to 4, and * represents a bonding portion}. Here, R ₁₄ and R ₁₅ are not limited, as long as they are each independently a valent organic group having 1 to 20 carbon atoms. Examples of such organic groups include: alkyl groups such as methyl, ethyl, and propyl; halogen-containing groups such as trifluoromethyl; aryl groups such as phenyl and naphthyl; and alkyl groups such as methoxy and ethoxy. Oxygen; etc. Among these, methyl group and phenyl group are preferable from the viewpoint of YI in a high temperature range. Here, n and о are not limited, and may be an integer of 0-4. Among them, an integer of 0 to 2 is preferable from the viewpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in a high-temperature region.

{式中，R ₈～R ₁₁及h～k係與通式(A-4)同樣地定義}。 In one aspect, the structural unit represented by the general formula (A-4) is derived from a diamine represented by the following general formula (B-4): [Chemical 57]

{In the formula, R ₈ to R ₁₁ and h to k are defined in the same manner as in the general formula (A-4)}.

As the diamine represented by the general formula (B-4), more specifically, 9,9-bis(4-aminophenyl)fluorene (BAFL), 9,9-bis(3-fluoro-4 -Aminophenyl) fluorine (BFAF), 9,9-bis(4-(aminophenoxy) phenyl) fluorine (BAOFL), etc., from the viewpoint of yellowness (YI value) at high temperature, BFAF is preferred, and BAFL is preferred from the viewpoint of reducing haze (Haze value).

或者下述通式(B-5-2)： [化59]

{式中，R ₁₂及R ₁₃、l及m係與通式(A-5)同樣地定義} 所表示之二胺等。 Also, the structural unit represented by the general formula (A-5) is derived from the following general formula (B-5-1): [Chemical 58]

Or the following general formula (B-5-2): [Chemical 59]

{In the formula, R ₁₂ and R ₁₃ , l and m are defined in the same manner as in the general formula (A-5)}, such as diamine represented.

As diamines represented by general formulas (B-5-1) and (B-5-2), more specifically, 4,4'-diaminodiphenylsulfone (44DAS), 3,3 '-Diaminodiphenylsulfone (33DAS). As another diamine, more specifically, bis[4-(4-aminophenoxy)phenyl]pyrone, bis[4-(3-aminophenoxy)phenyl]pyrone, etc. can be illustrated. From the viewpoint of yellowness (YI value) at high temperature, 44DAS is preferable, and 33DAS is preferable from the viewpoint of residual stress reduction.

{式中，R ₁₄及R ₁₅、n及о係與通式(A-6)同樣地定義}。 In one aspect, the structural unit represented by the general formula (A-6) is derived from a diamine represented by the following general formula (B-6): [Chemical 60]

{In the formula, R ₁₄ and R ₁₅ , n and o are defined in the same manner as in the general formula (A-6)}.

As the diamine represented by the general formula (B-6), more specifically, 4,4'-diaminodiphenyl ether (44ODA), 3,4'-diaminodiphenyl ether ( 34ODA), 2,3'-diaminodiphenyl ether, etc. From the viewpoint of yellowness (YI value) at high temperature, 44ODA is preferable, and 34ODA is preferable from the viewpoint of residual stress reduction.

The weight average molecular weight (Mw) of the polyimide or the polyimide part is preferably 1,000-100,000, more preferably 2,000-80,000 or 2,639-80,000, especially preferably 5,000-60,000. When the weight average molecular weight is 1,000 or more, mechanical properties such as elongation and breaking strength are excellent, residual stress decreases, and YI decreases. When the weight average molecular weight is 100,000 or less, phase separation at the time of forming a polyamide-imide copolymer film is suppressed, and the haze (HAZE value) decreases. In the present invention, the weight average molecular weight is a value calculated using gel permeation chromatography (hereinafter also referred to as GPC) as a standard polystyrene conversion value.

Regarding polyimide or its structural units, the molar ratio (X ₄ /X ₃ ) of X ₃ and X ₄ contained in the above general formula (1) is preferably 0.85-2.0 or 1.01-2.00, more preferably 0.95 to 1.5, more preferably 1.01 to 1.25. When the molar ratio is 0.85 or more or 1.01 or more, the heat resistance in the high-temperature region is excellent, and the YI value decreases. When the molar ratio is 2.00 or less, the reactivity with the polyamide acid portion increases, and the strength when formed into a film increases, so that mechanical properties such as elongation and breaking strength are excellent.

The polyimide or polyimide part molecular weight content of less than 1,000 is preferably less than 5% by mass relative to the total amount of the polyimide precursor or polyamide acid-imide copolymer , more preferably less than 1% by mass, more preferably less than 0.1% by mass. The residual stress of the polyimide film formed from the resin composition obtained using such polyimide or the polyimide part is reduced, and the haze (Haze value) formed on the polyimide film is reduced. The content of molecules with a molecular weight of less than 1,000 relative to the total amount of polyimide or polyimide parts can be calculated from the peak area obtained by GPC measurement using a solution in which the polyimide is dissolved.

In the polyimide precursor in one aspect of the present invention, in the range of non-destructive elongation, strength, stress, and yellowness, etc., in addition to the above general formulas (B-1) to (B-2) And (B-4) ~ (B-6) in addition to or instead of the diamine represented by the general formula (B-1) ~ (B-2) and (B-4) ~ (B-6) represented by the diamine Instead other diamines can be used. As other diamines, for example, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4 ,4'-Diaminobiphenyl, 3,4'-Diaminobiphenyl, 3,3'-Diaminobiphenyl, 4,4'-Diaminobenzophenone, 3,4'- Diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'- Diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene Oxy)benzene, bis[4-(4-aminophenoxy)phenyl]pyridine, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-amino Phenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4 -aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl) ) propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4- (4-Aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, etc.; preferably one or more selected from these .

The content of the above-mentioned other diamines in the total diamines is preferably 20 mol % or less, especially preferably 10 mol % or less. From the viewpoint of heat resistance at high temperatures, X ₄ and the diamines constituting it are preferably free of polysiloxane diamines like X ₂ , and are more preferably aromatic diamines or compositions.

(c) <Embodiment of polyamic acid-imide copolymer> The polyamic acid-imide copolymer of the present invention comprises the structural unit L represented by the above general formula (1) comprising the structural unit M as the polyamic acid part and the structural unit N as the polyimide part, Specific embodiments thereof are shown below.

The diamine (X ₂ ) of the above-mentioned polyamide acid portion and the diamine (X ₄ ) of the above-mentioned polyimide portion may have the same composition or type of diamine, or may have different compositions or types of diamine. The "same composition" as used herein means that when the diamines used in the polyamide acid part contain one or more kinds, the diamines in the polyimide part have completely the same composition. On the other hand, the "different composition" mentioned here means that when the diamine used in the polyamide part contains more than one kind, the diamines of the polyimide part do not have exactly the same composition, Instead, different diamines are included, or even if the same diamine is used, the ratio is different.

As the role of the polyamide part in one aspect of the present invention, it has high thermal stability and excellent dimensional stability in the high temperature region, and is preferably made of polyamide with high molecular planarity. A skeleton with high heat resistance at high temperatures in the case of amines.

As the acid dianhydride (X ₁ ) of the above-mentioned polyamic acid part, as shown in (a) <Embodiment of the polyamic acid part>, it is derived from the group consisting of pyromellitic dianhydride (PMDA), Benzene tetracarboxylic dianhydride (BPDA), 4,4'-biphenylbis(trimellitic acid monoester anhydride) (TAHQ), 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride ( BPAF), 3,3',4,4'-diphenyl tetracarboxylic dianhydride (DSDA), 4,4'-oxydiphthalic anhydride (ODPA), and cyclopentanone bispiro At least one of the group consisting of alkanetetracarboxylic dianhydride (CPODA).

From the viewpoint of the balance of coefficient of linear expansion (CTE), chemical resistance, glass transition temperature (Tg), and yellowness in high-temperature regions, PMDA, BPDA, DSDA, TAHQ, ODPA, and CPODA are preferable , more preferably BPDA, TAHQ, and ODPA. As X ₁ , in addition to the above-mentioned acid dianhydrides, those obtained by using dicarboxylic acids other than the above-mentioned tetracarboxylic dianhydrides may be used within the range not impairing the performance thereof. Moreover, although other tetracarboxylic dianhydride can also be added, it is preferable that it originates in the skeleton of an aromatic tetracarboxylic dianhydride or an aromatic dicarboxylic acid. Also, the _ratio of other acid dianhydrides and dicarboxylic acids in X1 is preferably at most 20 mol%, more preferably at most 10 mol%.

As the diamine (X ₂ ) of the above-mentioned polyamide acid part, it is preferably selected from (4-aminophenyl-4-aminobenzoate (APAB), 2-methyl-4-aminophenyl Methyl-4-aminobenzoate, 3-methyl-4-aminophenyl-4-aminobenzoate, 2-fluoro-4-aminophenyl-4-aminobenzoic acid ester (2F-APAB), 3-fluoro-4-aminophenyl-4-aminobenzoate (3F-APAB), 3-methyl-4-aminophenyl-3-methyl-4 -At least one of the group consisting of aminobenzoate and (2-phenyl-4-aminophenyl)-4-aminobenzoate (ph-APAB), in terms of linear expansion coefficient From the standpoint of balance between (CTE), chemical resistance, glass transition temperature (Tg), and yellowness in a high-temperature region, APAB, 2F-APAB, 3F-APAB, and Ph-APAB are preferred, and more APAB is preferred. As X ₂ , in addition to the above-mentioned acid dianhydride, other diamines can also be added in the range without impairing its performance, but do not contain cyclohexane ring or cyclopentane ring, preferably aromatic diamine Amine. The ratio of other diamines in X ₂ is preferably 20 mol% or less, more preferably 10 mol% or less. That is, the diamine (X ₄ ) as the above-mentioned imide moiety preferably does not contain The structures shown above are not necessarily limited thereto, as long as they are not exactly the same composition.

As the role of the imide part in one aspect of the present invention, it has high thermal stability in a high-temperature region, excellent optical properties, and high solubility to solvents, and preferably has excellent Optical properties, a skeleton with high solubility in solvents, or a skeleton that can impart bending resistance when forming a film.

As the acid dianhydride (X ₃ ) of the polyimide portion, a tetravalent organic group derived from tetracarboxylic dianhydride can be used as shown in (b) <Embodiment of the polyimide portion>. In addition, a plurality of X ₃ existing in the polyimide precursor or in the polyamic acid-imide copolymer may be the same as or different from each other, and may be the same as or different from X ₁ . As X ₃ , from the viewpoint of excellent yellowness (YI value) and haze (Haze value) in a high-temperature region, it is preferable to include a structure derived from BPAF, and it is preferable to be from the viewpoint of residual stress. Structure derived from ODPA. In the case of using a skeleton derived from BPAF, a skeleton selected from PMDA, BPDA, DSDA, TAHQ, ODPA, and CPODA may be used at the same time in order to improve thermal stability in a high-temperature region. Among them, it is more preferable to include a skeleton selected from BPDA, TAHQ, and ODPA. The ratio of BPAF in _X3 is preferably at least 40 mol%, more preferably at least 50 mol%, still more preferably at least 70 mol%, and may be 100 mol%. From the standpoint of excellent bending resistance when made into a polyimide film, the higher the ratio of BPAF, the better.

As the diamine of the above-mentioned imide part, as shown in (b) <Embodiment of the polyimide part>, a divalent organic group derived from a diamine can be used. In addition, the plurality of X ₄ present in the polyimide precursor or in the polyamide-imide copolymer may be the same as or different from each other, and may be the same as or different from X ₂ , but they cannot be completely same. X ₄ is preferably at least one selected from the group consisting of 44BAFL, 33BAFL, BFAF, BAOFL, BAHF, 33DAS, and 44DAS in terms of coefficient of linear expansion (CTE), chemical resistance, and glass transition temperature (Tg) , and the viewpoint of the balance of the yellowness in the high temperature region, 44BAFL, 33BAFL, BFAF, BAOFL, 33DAS, 44DAS, 44ODA, and 34ODA are more preferable.

The polyamic acid _- imide copolymer comprises polyamic _acid part including X1 and X2 and polyimide part including _X3 and _X4 , and the structural unit of polyamic acid and above-mentioned polyimide The upper limit of the molar ratio of the structural unit (the molar number of the structural unit N: the molar number of the structural unit M) can be 95:5, 90:10, 85:15, 80:20, From the viewpoint of residual stress and haze (Haze value), it is preferably 95:5, and from the viewpoint of yellowness (YI value), it is more preferably 80:20. The lower limit of the molar ratio of the structural unit of the above-mentioned polyamide acid to the structural unit of the above-mentioned polyimide (the molar number of the structural unit N: the molar number of the structural unit M) can be 30:70, and can be 40: 60, it can be 50:50, it can be 60:40, and it is preferably 40:60 or 60:40 from the viewpoint of simultaneously establishing residual stress and yellowness (YI value).

The weight average molecular weight (Mw) of polyamic acid-imide copolymer (structural unit L) is preferably 2,639 or more, more preferably 2,639-300,000 or 10,000-300,000, further preferably 20,000-250,000, especially 40,000～200,000. When the weight average molecular weight is 2,639 or more, mechanical properties such as elongation and breaking strength are excellent, residual stress decreases, and YI decreases. When the weight average molecular weight is 300,000 or less, the balance between viscosity and concentration of the polyamic acid-imide copolymer varnish will be better, the workability will be better, and the film unevenness at the time of coating will be reduced. Also, if the Mw of the polyamic acid-imide copolymer is 170,000 or more, it tends to be excellent in transparency, haze, heat resistance, and linear expansion coefficient, so it is preferred, and more preferably a Mw of 220,000 or more. It tends to have the structure represented by the above-mentioned general formula (A-1) as X2 in the general formula ( ₁ ), which is remarkable. In addition, the weight average molecular weight (Mw) of the polyamic acid-imide copolymer is preferably at least 170,000, more preferably at least 220,000, from the viewpoint of IR (infrared) curing defect evaluation and outgassing evaluation. In the present invention, the weight average molecular weight is a value calculated using gel permeation chromatography (hereinafter also referred to as GPC) as a standard polystyrene conversion value.

<Embodiment of (B) Polyamic Acid> Regarding the polyamide which includes the structural unit represented by the above-mentioned general formula (3) and has the structure represented by the above-mentioned general formula (A- ₁ ) as the fourth embodiment of X2 Amino acid, in the general formula (3), X1 is _a tetravalent organic group, and the multiple _X1s present in the polyimide precursor may be the same or different. As X ₁ , a tetravalent organic group derived from a tetracarboxylic dianhydride is exemplified, and the tetracarboxylic dianhydride is the same as the tetracarboxylic dianhydride exemplified for the above-mentioned (A) polyamic acid-imide copolymer. .

In one aspect of polyamic acid, in the above-mentioned general formula (3), X ₂ is a divalent organic group, and the plurality of X ₂ existing in the polyimide precursor may be the same or different. As X ₂ , a divalent organic group derived from a diamine that is the same as that exemplified for the above-mentioned (A) polyamic acid-imide copolymer can be exemplified.

Regarding the polyamic acid, the structural unit represented by the general formula (A-1) is the same as the general formula (A-1) exemplified for the above-mentioned (A) polyamic acid-imide copolymer.

The weight average molecular weight (Mw) of the polyamic acid of the fourth embodiment is preferably 3,000 or more, more preferably 10,000-300,000, still more preferably 20,000-250,000, especially preferably 40,000-200,000. When the weight average molecular weight is 3,000 or more, mechanical properties such as elongation and breaking strength are excellent, residual stress decreases, and YI decreases. When the weight-average molecular weight is 300,000 or less, the balance between viscosity and concentration of the polyamic acid-imide copolymer varnish will be better, processability will be better, and film unevenness at the time of coating will be reduced.

Also, from the viewpoint of IR (infrared) curing defect evaluation and outgassing evaluation, the weight average molecular weight (Mw) of the polyamic acid in the fourth embodiment is preferably 170,000 or more, more preferably 240,000 or more. In the present invention, the weight average molecular weight is a value calculated using gel permeation chromatography (hereinafter also referred to as GPC) as a standard polystyrene conversion value.

(Diamine) As the diamine containing the P group in the general formulas ( _I ) and (II), for example: 4,4'-diaminodiphenylsulfone (4,4'-DAS), 3 ,4'-Diaminodiphenylsulfone (3,4'-DAS), 3,3'-Diaminodiphenylsulfone (3,3'-DAS), p-phenylenediamine (PDA), m- Phenylenediamine, 3,5-diaminobenzoic acid (DABA), 2,2'-dimethylbenzidine (mTB), 4,4'-diaminodiphenyl ether, 3,4'-diamine Diphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, Aminobenzoylaniline (DABAN), 9,9-bis(4-aminophenoxy)(BAFL), 9,9-bis[4-(4-aminophenoxy)phenyl]fenflure, 4-aminobenzoic acid-4-aminophenyl ester (APAB), 2-(4-aminophenyl)-5-aminobenzoxazole, 4,4'-diaminobiphenyl, 3 ,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3 '-Diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4- Bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4 -aminophenoxy)phenyl]pyridine, 4,4-bis(4-aminophenoxy)biphenyl (BAPB), 4,4-bis(3-aminophenoxy)biphenyl, bis [4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis (4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy) )phenyl)hexafluoropropane, and 1,4-bis(3-aminopropyldimethylsilyl)benzene, 1,3-bis[1-(4-aminophenyl)-1-methyl Ethyl]benzene] (BiSAM), 1,4-cyclohexanediamine (CHDA), 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2'-bis(trifluoromethyl) base)-4,4'-diaminodiphenyl ether (TFOMB), 2,2''-bis(trifluoromethyl)[1,1':4',1''-terphenyl]- 4,4''-Diamine etc. These diamines may be used alone or in combination of two or more.

[化62] 4-胺基苯甲酸-4-胺基苯酯(APAB)

[化63] 2,2'-雙(三氟甲基)聯苯胺(TFMB)

[化64] 9,9-雙(4-胺基苯基茀)(BAFL)

[化65] 4,4'-二胺基苯甲醯苯胺(DABAN)

[化66] 1,4-環己烷二胺(CHDA)

[化67] 對伸苯基二胺(PDA)

[化68] 3,5-二胺基苯甲酸(DABA)

[化69] 4,4-雙(4-胺基苯氧基)聯苯(BAPB)

[化70] 2,2'-雙(三氟甲基)-4,4'-二胺基二苯醚(TFOMB)

In the general formulas (I) and (II), P ₁ is preferably a structural unit derived from at least one diamine represented by the following general formulas (3) to (12). [Chemical 61] Diaminodiphenylsulfone (DAS)

[Chemical 62] 4-Aminobenzoic acid-4-aminophenyl ester (APAB)

[Chemical 63] 2,2'-bis(trifluoromethyl)benzidine (TFMB)

[Chemical 64] 9,9-bis(4-aminophenyl fluorene) (BAFL)

[Chemical 65] 4,4'-Diaminobenzylaniline (DABAN)

[Chemical 66] 1,4-Cyclohexanediamine (CHDA)

[Chemical 67] p-Phenylenediamine (PDA)

[Chemical 68] 3,5-Diaminobenzoic acid (DABA)

[Chemical 69] 4,4-bis(4-aminophenoxy)biphenyl (BAPB)

[Chemical 70] 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (TFOMB)

The content of the structure derived from the above-mentioned diamine compound in the total diamine (excluding the compound in which L1 and L2 are amino groups in the following general formula (13)) can be 20 mol% or more, 40 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, or 95 mol% or more.

(Acid dianhydride) As the _acid dianhydride containing the P2 group in the general formulas (I) and (II), for example: pyromellitic dianhydride (PMDA), 3,3',4,4'- Biphenyltetracarboxylic dianhydride (BPDA), 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA ), 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, 1,2,3,4-benzenetetracarboxylic dianhydride , 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4' -Diphenylenetetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2 ,2-Propylene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4 ,4'-Diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic anhydride Phthalic dianhydride, 4,4'-oxydiphthalic dianhydride (ODPA), terephthalic bis(trimellitic anhydride), thio-4,4'-diphthalic dianhydride, sulfonyl- 4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzenedi anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methanedianhydride, Bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2, 2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3 ,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8- Naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dicarboxylic acid anhydride, and 1,2,7,8-phenanthrene tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), dicyclohexyl-3,3',4 ,4'-tetracarboxylic dianhydride (CpODA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and so on. These acid dianhydrides may be used alone or in combination of two or more.

{式中，於R ₁、及R ₂分別存在複數個之情形時，分別獨立地表示碳數1～5之一價脂肪族烴基或碳數6～10之一價芳香族基，並且m表示1～200之整數}。 <Silicon-containing compound> The polyamic acid, polyamic acid-imide copolymer, polyimide copolymer, polyimide precursor or polyimide resin described above may contain the following general formula The structure represented by (14): [Chemical 71]

{In the formula, when R ₁ and R ₂ exist in plural, each independently represents a valent aliphatic hydrocarbon group with 1 to 5 carbons or a valent aromatic group with 6 to 10 carbons, and m represents An integer from 1 to 200}.

When the structure of the general formula (14) is included, Rth and residual stress of the obtained polyimide film become favorable, which is preferable.

{式中，R ₁分別獨立地為單鍵或碳數1～10之二價有機基，R ₂及R ₃分別獨立地為碳數1～10之一價有機基，至少一者為碳數1～5之一價脂肪族烴基，R ₄及R ₅分別獨立地為碳數1～10之一價有機基，至少一者為碳數6～10之一價芳香族基，R ₆及R ₇分別獨立地為碳數1～10之一價有機基，L ₁及L ₂分別獨立地為胺基、酸酐基、異氰酸基、羧基、酸酯基、醯鹵基、羥基、環氧基或巰基，i為1～200之整數，j及k分別獨立地為0～200之整數，0≦j/(i＋j＋k)≦0.50，且官能基當量為800以上}。 In order to make the resin have the structure of general formula (14), X ₁ to X ₄ in the above general formulas (1) and (2), or P ₁ or P ₂ in the above general formulas (I) and (II) may contain source From the structural unit of the silicon-containing compound represented by the following general formula (13): [Chemical 72]

{In the formula, R ₁ are each independently a single bond or a divalent organic group with 1 to 10 carbons, R ₂ and R ₃ are each independently a valent organic group with 1 to 10 carbons, at least one of which is a carbon number 1-5 monovalent aliphatic hydrocarbon groups, R ₄ and R ₅ are each independently a valent organic group with 1-10 carbons, at least one of which is a valent aromatic group with 6-10 carbons, R ₆ and R ₇ are each independently a valent organic group with ₁ to ₁₀ carbon atoms, and L1 and L2 are each independently an amine group, an acid anhydride group, an isocyanate group, a carboxyl group, an ester group, an acyl halide group, a hydroxyl group, an epoxy group, etc. group or mercapto group, i is an integer of 1 to 200, j and k are each independently an integer of 0 to 200, 0≦j/(i+j+k)≦0.50, and the functional group equivalent is 800 or more}.

In the resin composition, the silicon-containing compound represented by the above general formula (13): 20 mol% or less when diamine is set to 100 mol%; or When the acid dianhydride is 100 mol%, it is 20 mol% or less. When the silicon-containing compound is within the above range, it is preferable from the viewpoint of the filterability of the obtained polyimide precursor or polyimide resin composition. From the viewpoint of further improving filterability, when the total diamines or total acid dianhydrides in the resin composition are set to 100 mol%, the silicon-containing compound is less than 20.0 mol% and less than 19.0 mol%. , 18.0 mol% or less, 17.0 mol% or less, 16.0 mol% or less, 15.0 mol% or less, or 14.0 mol% or less. When the total diamine or total acid dianhydride of the resin composition is set as 100 mol%, the silicon-containing compound may exceed 0 mol%.

R ₁ in formula (13) are each independently a single bond or a divalent organic group having 1 to 10 carbon atoms. The divalent organic group having 1 to 10 carbon atoms may be any of linear, cyclic, and branched, and may be saturated or unsaturated. Examples of divalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms include methylene, ethylidene, n-propyl, isopropyl, n-butyl, second-butyl, and third-butyl , n-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and other straight-chain or branched alkyl; cyclopropyl, cyclobutyl, ring Cycloalkylene groups such as pentyl, cyclohexylene, cycloheptylene, and cyclooctylene. The divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferably at least one selected from the group consisting of ethylidene, normal-propylidene, and isopropylidene.

R ₂ and R ₃ in formula (13) are each independently a valent organic group having 1 to 10 carbons, and at least one of them is a valent aliphatic hydrocarbon group having 1 to 5 carbons.

The valent organic group having 1 to 10 carbon atoms may be linear, cyclic, or branched, and may be saturated or unsaturated. For example, examples of the valent organic group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, n-pentyl, Neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and other linear or branched alkyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, Cycloalkyl groups such as cyclooctyl; aromatic groups such as phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, etc.

The one-valent aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear, cyclic, or branched, and may be saturated or unsaturated. For example, as a C1-C5 valent aliphatic hydrocarbon group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group, third butyl group, n-pentyl group are mentioned , Neopentyl and other linear or branched chain alkyl groups; cyclopropyl, cyclobutyl, cyclopentyl and other cycloalkyl groups, etc. As a C1-C5 valent aliphatic hydrocarbon group, it is preferable that it is at least 1 sort(s) chosen from the group which consists of a methyl group, an ethyl group, and a n-propyl group.

R ₄ and R ₅ in formula (13) are each independently a valent organic group having 1 to 10 carbons, and at least one of them is a valent aromatic group having 6 to 10 carbons. The valent organic group having 1 to 10 carbon atoms may be any of linear, cyclic, and branched, and may be saturated or unsaturated. For example, as a C1-C10 valent organic group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group, third butyl group, n-pentyl group, Neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and other linear or branched alkyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, Cycloalkyl groups such as cyclooctyl; aromatic groups such as phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, etc. The valent aromatic group having 6 to 10 carbon atoms includes, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, etc., preferably phenyl, tolyl or xylyl .

Preferably, R ₆ and R ₇ in formula (13) are each independently a valent organic group having 1 to 10 carbon atoms, and at least one of them is an organic group having an unsaturated aliphatic hydrocarbon group. The monovalent organic group having 1 to 10 carbon atoms may be linear, cyclic, or branched. Examples of the valent organic group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, n-pentyl, neo Pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and other linear or branched alkyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclo Cycloalkyl groups such as octyl; aromatic groups such as phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, etc. The C1-C10 valent organic group is preferably at least one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group. The organic group having an unsaturated aliphatic hydrocarbon group may be an unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, and may be any of straight-chain, cyclic, and branched-chain. Examples of unsaturated aliphatic hydrocarbon groups having 3 to 10 carbon atoms include vinyl, allyl, 1-propenyl, 3-butenyl, 2-butenyl, pentenyl, and cyclopentenyl. , hexenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, etc. The unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms is preferably at least one selected from the group consisting of vinyl, allyl, and 3-butenyl.

Part or all of the hydrogen atoms of R ₁ to R ₇ in formula (13) may be substituted with substituents such as F, Cl, Br or other halogen atoms, or may not be substituted.

{上述式中，「*」表示鍵結鍵}所表示之2,5-二氧雜四氫呋喃-3-基。 L1 and L2 in the _formula ( ₁₃ ) are independently a valent organic group (also known as an acid anhydride group) containing an acid anhydride structure, an amine group, an isocyanate group, a carboxyl group, an alkoxycarbonyl group, a halogenated carbonyl group, a hydroxyl group , epoxy or mercapto. As a valent organic group containing an acid anhydride structure, for example, the following formula can be exemplified: [Chem. 73]

{In the above formula, "*" represents a bonding bond} represented by 2,5-dioxatetrahydrofuran-3-yl.

Among them, an amine group and an acid anhydride group are preferable, and an amine group is more preferable from the viewpoint of the viscosity stability of the resin composition.

The alkoxy group in the alkoxycarbonyl group can be an alkoxy group with 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy group, the third butoxyl group, etc.

The halogen atom in the halogenated carbonyl group is preferably a halogen atom other than a fluorine atom, more preferably a chlorine atom or an iodine atom.

From the viewpoint of filterability of the resin composition, the functional group equivalent weight of the silicon-containing compound represented by formula (13) is preferably 800 or more, more preferably 1000 or more, and still more preferably 1500 or more. On the other hand, when the functional group equivalent is 500 or less, filterability may deteriorate. The so-called functional group equivalent here refers to the molecular weight of the silicon-containing compound per 1 mol of functional group (unit: g/mol). The functional group equivalent can be measured by a known method based on existing standards and the like. In addition, when the functional group equivalent weight of the silicon-containing compound is 800 or more, the residual stress of the polyimide film under nitrogen atmosphere is small, so it is preferable. The reason for this is considered to be that, when the functional group equivalent is equal to or greater than a specific value, the polysiloxane domain increases and the stress is relaxed.

i in the formula (13) is an integer of 1-200, preferably an integer of 2-100, more preferably an integer of 4-80, further preferably an integer of 8-40. j and k are independently an integer of 0 to 200, and j may also be an integer of 1 to 200, preferably j and k are an integer of 0 to 50, more preferably an integer of 0 to 20, and more preferably an integer of 0 to 200. An integer of 50.

If the resin in the resin composition has a structure derived from formula (13), the residual stress of the polyimide film measured under a nitrogen atmosphere is good (smaller), so it is preferable. The reason for measuring under nitrogen atmosphere is that in the manufacturing process of displays, when inorganic films such as SiO and SiN are formed on polyimide films, they are sometimes exposed to nitrogen atmosphere, and the residual stress under nitrogen atmosphere is relatively small.

{式中，P ₅分別獨立地表示二價烴基，可相同，亦可不同，P ₃及P ₄與通式(13)中所定義之R ₂、R ₃相同，l表示1～200之整數} 所表示之二胺基(聚)矽氧烷。 From the perspective of the type of monomer, cost, and the molecular weight of the obtained polyimide precursor, L ₁ and L ₂ in the general formula (13) are preferably each independently an amine group. That is, the silicon-containing compound of the general formula (13) is preferably a silicon-containing diamine. As the silicon-containing diamine, for example, the following general formula (15) is preferred: [Chemical 74]

{In the formula, P ₅ independently represents a divalent hydrocarbon group, which may be the same or different, P ₃ and P ₄ are the same as R ₂ and R ₃ defined in the general formula (13), and l represents an integer of 1 to 200 } Represented diamino (poly) siloxane.

Preferred structures of _P3 and P4 in the above general _formula (15) include methyl, ethyl, propyl, butyl, and phenyl groups. Preferred among these is methyl.

l in the above general formula (15) is an integer of 1 to 200, preferably 3 to 200 from the viewpoint of the heat resistance of the polyimide obtained by using the silicon-containing diamine represented by the formula (15). Integer of .

The preferred range of the functional group equivalent of the compound represented by the general formula (15) is the same as that of the silicon-containing compound represented by the above general formula (13).

When the total monomer mass (the total mass of polyimide precursor/polyimide) is set as 100% by mass, the content (copolymerization ratio) of the silicon-containing compound represented by the general formula (13) is preferably 0.5 mass % or more and 20 mass % or less. When the silicon-containing compound is at least 0.5% by mass, the residual stress generated between the supports can be effectively reduced. When the silicon-containing compound is less than 20% by mass, the obtained polyimide film has good transparency (especially low haze value), and achieves higher total light transmittance and higher glass transition It is preferable from the viewpoint of temperature.

The silicon-containing compound used as a polyimide precursor/monomer used in polyimide can be synthesized using common technical knowledge at the time of filing as described above, or a commercially available product can be used. Examples of commercially available products include: two-block amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (functional group equivalent weight: 2200), X22-9409 (functional group equivalent weight: 670) ), two-block anhydride-modified methylphenyl polysiloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-168-P5-B (functional group equivalent: 2100)), two-block epoxy-modified methylphenyl polysiloxane oil Silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-2000 (functional group equivalent weight 620)), two-terminated amine-modified dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.: PAM-E (functional group equivalent weight 130), X22 -161A (functional group equivalent 800), X22-161B (functional group equivalent 1500), KF8012 (functional group equivalent 2200), Toray Dow Corning: BY16-853U (functional group equivalent 450), JNC: Silaplane FM3311 (quantity Average molecular weight 1000)), two-terminated epoxy-modified dimethyl polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-163A (functional group equivalent 1750), two-terminated alicyclic epoxy-modified dimethicone Methylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-169B (functional group equivalent weight: 1700)), two-end-blocked hydroxy-modified dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.: KF-6000), two-end-blocked Mercapto-modified dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-167B (functional group equivalent weight: 1700)), two-block anhydride-modified dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22- 168A (functional group equivalent weight 1000)), etc. Among them, from the viewpoint of price, improvement of chemical resistance, and improvement of Tg, dimethicone oil modified with two blocked amines is preferable.

(d) Organic solvents (d) The organic solvent is not particularly limited, as long as it can dissolve the above-mentioned (a) polyamic acid, (b) polyimide, (c) polyamic acid-imide copolymer and other components used arbitrarily. Can. Specific examples of such (d) organic solvents include, for example, aprotic solvents, phenol-based solvents, ether and glycol-based solvents, and the like.

From the viewpoint of improving the in-plane uniformity of the film thickness and reducing the YI value, the aprotic solvent is preferably polar, and/or preferably has a boiling point of 250°C to 350°C, for example, the following boiling point Aprotic polar substance at 250℃～350℃.

{式中，R ₁₂＝甲基所表示之3-甲氧基-N,N-二甲基丙醯胺(KJ Chemicals公司製造，商品名：Equamide M100)、及R ₁₂＝正丁基所表示之3-丁氧基-N,N-二甲基丙醯胺(KJ Chemicals公司製造，商品名：Equamide B100)}；γ-丁內酯、γ-戊內酯等內酯系溶劑；六甲基磷醯三胺、六甲基膦三醯胺等含磷系醯胺系溶劑；二甲基碸、二甲基亞碸、環丁碸等含硫系溶劑或含碸結構之化合物；環己酮、甲基環己酮等酮系溶劑；甲基吡啶、吡啶等三級胺系溶劑；乙酸(2-甲氧基-1-甲基乙基)酯等酯系溶劑等。 Examples of the aprotic solvent include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea, and amide solvents of the following general formula: [Chem. 75 ]

{In the formula, 3-methoxy-N,N-dimethylacrylamide represented by R ₁₂ = methyl (manufactured by KJ Chemicals, trade name: Equamide M100), and R ₁₂ = represented by n-butyl 3-butoxy-N,N-dimethylpropionamide (manufactured by KJ Chemicals, trade name: Equamide B100)}; lactone solvents such as γ-butyrolactone and γ-valerolactone; Phosphorus-based amide-based solvents such as phosphotriamine and hexamethylphosphine-triamide; sulfur-containing solvents such as dimethylsulfide, dimethylsulfoxide, and cyclobutylene, or compounds containing sulfur-containing structures; cyclohexyl Ketone-based solvents such as ketone and methylcyclohexanone; tertiary amine-based solvents such as picoline and pyridine; ester-based solvents such as (2-methoxy-1-methylethyl) acetate, etc.

Among them, the aprotic polar solvent preferably contains N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide At least one of amine, 3-methoxy-N,N-dimethylacrylamide, γ-butyrolactone, γ-valerolactone, and cyclobutane, more preferably cyclobutane.

As the phenolic solvent, for example, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, 6-xylenol, 3,4-xylenol, 3,5-xylenol, etc.; as ether and glycol solvents, for example: 1,2-dimethoxyethane, bis(2 -methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1, 4-Dioxane, etc.

From the viewpoint of the solubility of polyamic acid, polyimide, and polyamic acid-imide copolymer, (d) the organic solvent preferably contains At least one of them.

[other ingredients] The resin composition may further contain (e) an imidization catalyst, an aprotic polar substance, a surfactant, and an alkoxylate in addition to the above-mentioned (a), (b), (c) and (d) components. silane compounds, etc.

((e) imidization catalyst) In the step of obtaining a polyimide resin film from the resin composition by imidization, an imidization catalyst may be added to the resin composition.

The resin composition may contain an imidization catalyst in an amount of 0.01 to 0.5 mol% relative to 1 mol of the repeating unit of the (c) polyamide-imide copolymer. Yellowness (YI value) of the film can be suppressed by setting the content of the imidization catalyst to 0.01 mol% or more relative to 1 mol of the repeating unit of the polyamic acid-imide copolymer. Moreover, from the viewpoint of the storage stability of the resin composition, the content of the imidization catalyst is preferably 0.5 mol % or less. The content of the imidization catalyst is more preferably 0.015-0.5 mol%, further preferably 0.02-0.5 mol%, with respect to 1 mol of the repeating unit of the polyamic acid-imide copolymer, especially It is 0.02 to 0.15 mole%.

(e) The content of the imidization catalyst is preferable from the viewpoint of the effect of the present invention with respect to 100 parts by mass of the above-described polyamic acid-imide copolymer or polyamic acid It is at least 5 parts by mass, more preferably at least 10 parts by mass.

The imidization catalyst is not particularly limited, and examples thereof include pyridine, triethylamine, 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenyl Imidazole, imidazole, benzimidazole, N-tert-butoxycarbonylimidazole (N-Boc-imidazole) and the like. Also, as the imidization catalyst, from the viewpoint of the effect of the present invention, 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole , imidazole, benzimidazole, or N-tertiary butoxycarbonylimidazole (N-Boc-imidazole) and other imidazole compounds, more preferably 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole imidazole, imidazole, etc., and more preferably 1,2-dimethylimidazole, N-tert-butoxycarbonylimidazole (N-Boc-imidazole), 1-methylimidazole, etc., and more preferably include N-th The imidazole compound of tributoxycarbonylimidazole (N-Boc-imidazole) and/or 1-methylimidazole is particularly preferably N-Boc-imidazole from the standpoint of storage stability, and the yellowness at high temperature ( From the viewpoint of YI value), 1-methylimidazole is particularly preferable.

Moreover, it does not specifically limit as an imidization catalyst, A nitrogen-containing compound is mentioned, Specifically, an imidazole compound, a pyridine compound, a tertiary amine compound, etc. are mentioned.

Examples of imidazole compounds include: 1-methylimidazole, N-tert-butoxycarbonylimidazole (N-Boc-imidazole), 2-methylimidazole, 2-phenylimidazole, benzimidazole, 2-ethylimidazole, Base-4-methylimidazole, 4-ethyl-2-methylimidazole, 4-methyl-2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 1 - benzyl-2-phenylimidazole, 1H-imidazole, and 1,2-dimethylimidazole.

The pyridine compound may, for example, be 4-dimethylaminopyridine, 2,2'-bipyridine, nicotinic acid, isoquinoline, pyridine or 2-picoline.

Examples of tertiary amine compounds include: 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane, N-methyl Morpholine, and triethylamine.

These compounds can also be used in mixture of 2 or more types.

Among these, 1-methylimidazole, N-tert-butoxycarbonylimidazole (N-Boc-imidazole), 2-methylimidazole, 2-phenylimidazole, benzimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 4-methyl-2-phenylimidazole, 2 -undecylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, as pyridine compounds, preferably 4-dimethylaminopyridine, 2,2'- Bipyridine, niacin, isoquinoline, 2-picoline, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2] Octane, and N-methylmorpholine, more preferably 1-methylimidazole, and N-tert-butoxycarbonylimidazole (N-Boc-imidazole).

From the standpoint of IR (infrared) curing defect evaluation and outgassing evaluation, the content of the imidization catalyst is preferably 1 It is at least 5 parts by mass, more preferably at least 5 parts by mass, and especially preferably at least 10 parts by mass.

The following IR (infrared) curing defect evaluation can be improved by adopting any one or more of the following a.~c.; a. Using imidization catalyst as an additive b. Use aprotic polar substances with a boiling point of 250-350 as additives c. Making the molecular weight of polyamic acid-imide copolymer/polyamic acid high.

The mechanism for the good evaluation of IR (infrared) curing defects is not certain, but it is considered to be related to the acceleration of imidization. That is, it is considered that the cause of defects in IR curing is related to the formation of oligomers and the decomposition of oligomers by infrared rays, and it is considered that the reason for the good evaluation of defects in IR (infrared rays) curing is that imidization is promoted by using a.b. , thereby inhibiting the formation of oligomers. Also, regarding c., it is considered that as long as the molecular weight is increased, the formation of oligomers can also be suppressed as a result.

Also, the following outgassing evaluation can be improved by adopting any one or more of the following a. to c.; a. Using imidization catalyst as an additive b. Use aprotic polar substances with a boiling point of 250-350 as additives c. Making the molecular weight of polyamic acid-imide copolymer/polyamic acid high.

Although the mechanism of the good degassing evaluation is uncertain, it is considered to be related to the promotion of imidization. That is, it is considered that the cause of degassing is related to the low molecular weight components and oligomers remaining in the polyimide film after curing, and the reason for the good evaluation of outgassing is that the reduction of low molecular weight components and oligomers is suppressed by using a.b. Molecular weight components and formation of oligomers. Also, regarding c., it is considered that as long as the molecular weight is increased, the residue of low molecular weight components and oligomers can also be suppressed as a result.

(f) Aprotic polar substance having a boiling point of 250°C to 350°C The resin composition according to one aspect of the present invention contains an aprotic polar substance having a boiling point of 250°C to 350°C. Aprotic polar substances with a boiling point of 250°C to 350°C that can be preferably used do not contain OH groups, _NH2 groups, NH groups, and SH groups at boiling points of 250°C to 350°C, and have properties selected from ketones, esters, A compound having at least one chemical structure (functional group) of carbonate, amide, nitrile, oxene, and oxene.

If specific examples of compounds that can be preferably used are given, for example, compounds having a ketone structure with a boiling point of 250°C to 350°C include: benzophenone, methylbenzophenone, and dimethylbenzophenone , dodecanedione, etc.; Examples of compounds having an ester structure with a boiling point of 250°C to 350°C include: dibutyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, acetic acid 2-phenoxyethyl ester, butyl benzoate, isoamyl benzoate, dibutyl maleate, ethyl cinnamate, diethylene glycol diacetate, diethyl adipate, etc.; Examples of compounds having a carbonate structure having a boiling point of 250°C to 350°C include diphenyl carbonate, etc.; Examples of compounds having an amide structure with a boiling point of 250°C to 350°C include: benzamide, N,N-dimethylbenzamide, adipamide, etc.; Examples of compounds having a nitrile structure having a boiling point of 250°C to 350°C include adiponitrile, etc.; Examples of compounds having an azole structure having a boiling point of 250°C to 350°C include dibutyl azole, diphenyl phenylene, etc.; Examples of the compound having a sulfide structure having a boiling point of 250° C. to 350° C. include cyclobutane, 3-methylcyclobutane, dibutylsulfone, and benzenesulfonamide. Among these compounds, cyclobutane and 3-methylcyclobutane are more preferably used.

When an aprotic polar substance with a boiling point of 250°C to 350°C is added alone or in combination with a solvent to a polyamide-imide copolymer or a polyamide precursor for coating and curing (heating), it can The IR curing defect evaluation and outgassing evaluation were made favorable. The effect is particularly remarkable when 5 wt% or more is added when (the mass of the solvent + the mass of the aprotic polar substance) is set to 100 wt%. As the upper limit of the addition amount of the aprotic polar substance, when (the mass of the solvent + the mass of the aprotic polar substance) is set to 100 wt%, it is 100 wt%, and the more preferable addition amount is 30 wt% or less.

(Aprotic polar substance with a boiling point of 250°C to 350°C) The resin composition preferably contains an aprotic polar substance with a boiling point of 250°C to 350°C. Aprotic polar substances with a boiling point of 250°C to 350°C that can be preferably used do not contain OH groups, _NH2 groups, NH groups, and SH groups at boiling points of 250°C to 350°C, and have properties selected from ketones, esters, and carbonic acid. A compound having at least one chemical structure (functional group) among ester, amide, nitrile, oxene, and oxon. As long as the aprotic polar substance has a boiling point of 250° C. to 350° C., it can be repeated with the aprotic solvents described above.

If specific examples of compounds that can be preferably used are given, for example, compounds having a ketone structure with a boiling point of 250°C to 350°C include: benzophenone, methylbenzophenone, and dimethylbenzophenone , dodecanedione, etc.; Examples of compounds having an ester structure with a boiling point of 250°C to 350°C include: dibutyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, acetic acid 2-phenoxyethyl ester, butyl benzoate, isoamyl benzoate, dibutyl maleate, ethyl cinnamate, diethylene glycol diacetate, diethyl adipate, etc.; Examples of compounds having a carbonate structure having a boiling point of 250°C to 350°C include diphenyl carbonate, etc.; Examples of compounds having an amide structure with a boiling point of 250°C to 350°C include: benzamide, N,N-dimethylbenzamide, adipamide, etc.; Examples of compounds having a nitrile structure having a boiling point of 250°C to 350°C include adiponitrile, etc.; Examples of compounds having an azole structure having a boiling point of 250°C to 350°C include dibutyl azole, diphenyl phenylene, etc.; Examples of the compound having a sulfide structure having a boiling point of 250° C. to 350° C. include cyclobutane, 3-methylcyclobutane, dibutylsulfone, and benzenesulfonamide. Among these compounds, cyclobutane and 3-methylcyclobutane are more preferably used.

Aprotic polar substances with a boiling point of 250°C to 350°C are added alone or combined with a solvent to a polyamide precursor, or a resin with a polyamide precursor and a polyimide structure, or a solvent-soluble polyimide In addition, when coating and curing (heating) are carried out, compared with the case of no addition, the in-plane film thickness uniformity of the cured film can be improved, and the YI can be reduced. The effect is particularly remarkable when 5 wt% or more is added when (the mass of the solvent + the mass of the aprotic polar substance) is set to 100 wt%.

Aprotic polar substances with a boiling point of 250°C to 350°C will remain in the film even if the temperature is higher than 250°C in the curing step of polyimide (up to about 400°C) and will function at high temperatures The role of plasticizers. Therefore, it is considered that in the temperature range of 250° C. or higher in the curing step, the resin becomes soft and fluid, the in-plane uniformity of the film thickness is improved, and YI is also reduced. On the other hand, if the amount of the aprotic polar substance with a boiling point of 250° C. to 350° C. is large, all of it cannot be volatilized during curing, and a small amount remains in the cured film. In the manufacturing steps of flexible displays, CVD (Chemical Vapor Deposition, chemical vapor deposition) is sometimes used to form an inorganic film such as silicon nitride on the cured film, and form amorphous silicon or low-temperature polysilicon on it. layer, and again apply the same temperature as the curing temperature (re-annealing step). If the aprotic polar substance with a boiling point of 250°C to 350°C remains in the cured film, it will volatilize during re-annealing, causing the inorganic film formed on the film to bulge. In order to prevent this, it is necessary to suppress the remaining amount of the substance in the film to 1000 ppm or less.

Therefore, as the upper limit of the addition amount of the aprotic polar substance, in the case of a polyimide precursor, or a resin having a polyimide precursor skeleton and a polyimide skeleton, the (mass of solvent + non- When the mass of protic polar substance) is set to 100 wt%, it is 100 wt%. In the case of a solvent-soluble polyimide that further contains a solvent in addition to the polyimide precursor, or a resin having a polyimide precursor skeleton and a polyimide skeleton, the (mass of solvent + aprotic When the mass of polar substances) is set to 100 wt%, it is 50 wt%. In the case of a polyimide precursor, or a resin having a polyimide precursor skeleton and a polyimide skeleton, or a solvent-soluble polyimide, the addition amount is preferably 30 wt% or less

Among the aprotic polar substances, cyclobutane and 3-methylcyclobutane are excellent in improving the in-plane uniformity of the cured film and reducing YI. Although other substances also showed the same effect, the effect was remarkable when cyclobutane and 3-methylcyclobutane were used. When the boiling point of the aprotic polar substance is less than 250°C, the effect of improving the in-plane uniformity of the cured film and reducing the YI will not be exhibited. When the boiling point exceeds 350°C, the effect is exhibited, but more than 1000 ppm remains in the cured film, which is unfavorable from the viewpoint of degassing.

(surfactant) The coatability of the resin composition can be improved by adding a surfactant to the resin composition. Specifically, the occurrence of streaks in the coating film can be prevented.

Such a surfactant may, for example, be a silicone-based surfactant, a fluorine-based surfactant, or nonionic surfactants other than these. Examples of polysiloxane-based surfactants include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, and X-70-093 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd. ); SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (trade name, manufactured by Toray Dow Corning Silicone); SILWET L-77, L-7001 , FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nippon Unicar); DBE-814, DBE-224, DBE-621, CMS-626, CMS-222, KF-352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (trade name, BYK-Chemie Japan); Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.); and the like. As the fluorine-based surfactant, for example, MEGAFAC F171, F173, R-08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd., trade name); Fluorad FC4430, FC4432 (Sumitomo 3M Co., Ltd., trade name), etc. . As nonionic surfactants other than these, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, etc. are mentioned, for example.

Among these surfactants, silicone-based surfactants and fluorine-based surfactants are preferable from the viewpoint of coatability (streak suppression) of the resin composition. From the viewpoint of the YI value of the oxygen concentration and the influence on the total light transmittance, polysiloxane-based surfactants are preferred. When a surfactant is used, the compounding amount is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass relative to 100 parts by mass of the polyimide precursor in the resin composition.

(alkoxysilane compound) When the polyimide film obtained from the resin composition is used for flexible substrates, etc., from the viewpoint of obtaining good adhesion between the support and the polyimide film during the manufacturing process, the resin composition 0.01-20 mass parts of alkoxysilane compounds can be contained with respect to 100 mass parts of polyimide precursors. When content of an alkoxysilane compound is 0.01 mass parts or more with respect to 100 mass parts of polyimide precursors, favorable adhesiveness can be acquired between a support body and a polyimide film. Moreover, it is preferable that content of an alkoxysilane compound is 20 mass parts or less from a viewpoint of the storage stability of a resin composition. The content of the alkoxysilane compound is preferably 0.02 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 0.1 to 8 parts by mass relative to 100 parts by mass of the polyimide precursor. By using an alkoxysilane compound, in addition to the improvement of the above-mentioned adhesion, it is also possible to improve the coatability of the resin composition (suppression of streaks), and reduce the impact on the polyimide film based on the oxygen concentration during curing. The influence of the YI value.

之各者所表示之烷氧基矽烷化合物等。烷氧基矽烷化合物可單獨使用一種，亦可將兩種以上組合使用。 Examples of alkoxysilane compounds include: 3-ureidopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, 3-glycidyloxysilane Aminopropyltrimethoxysilane, γ-Aminopropyltrimethoxysilane, γ-Aminopropyltrimethoxysilane, γ-Aminopropyltributoxysilane, γ-Aminoethyltrimethoxysilane Ethoxysilane, γ-Aminoethyltripropoxysilane, γ-Aminoethyltributoxysilane, γ-Aminobutyltriethoxysilane, γ-Aminobutyltrimethoxy Silane, γ-aminobutyltripropoxysilane, γ-aminobutyltributoxysilane, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, di Phenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxybis-p-tolylsilane, triphenylsilanol, and the following structures: [Chem. 76]

The alkoxysilane compounds represented by each of them, etc. An alkoxysilane compound may be used individually by 1 type, and may use it in combination of 2 or more types.

[Method for producing polyamic acid-imide copolymer] The polyamic acid, polyimide, and polyamic acid-imide copolymer of the present invention can be synthesized by a production method comprising the following steps . For example, the manufacture method of polyamic acid-imide copolymer has following step 1～step 3: Step 1: make the tetracarboxylic dianhydride component (X ₃ ) The step of reacting with the diamine component (X ₄ ) to obtain a solvent-soluble polyimide solution; Step 2: dissolving the diamine (X ₂ ) of the polyamide acid part in the above general formula (1) in Steps in the polyimide obtained in step 1; and step 3: making the tetracarboxylic dianhydride component (X ₁ ) constituting the polyamide acid part of the above general formula (1) and the polyimide obtained in step 2 Solution reaction, the step of obtaining polyamic acid-imide copolymer.

First, specific implementations will be described sequentially from Step 1. Step 1 is the step of synthesizing the polyimide part in the above general formula (1). It can be synthesized by polycondensing the diamine of the polyimide part in the above-mentioned general formula (1) (for example, 44BAFL) and tetracarboxylic dianhydride (for example, BPAF). This reaction is preferably carried out in a solvent capable of dissolving the monomer and the polyimide to be purified using a reaction vessel in which water generated during imidization is removed. Specifically, for example, the method of adding a specific amount of BAFL and NMP to a separable flask equipped with a reflux tube and a Dean-Stark tube to completely dissolve BAFL, then adding a specific amount of BPAF, as Toluene, the azeotropic solvent of water, was heated to 180°C and stirred. It is preferable to properly discharge the water generated during heating at 180° C. and toluene as an azeotropic solvent to the outside of the container.

From the point of view of controlling the thermal linear expansion coefficient, residual stress, elongation, and yellowness (hereinafter, also referred to as YI) of the obtained resin film to the desired range, the fourth step in synthesizing the above-mentioned polyimide precursor is The ratio (molar ratio) of the carboxylic dianhydride component to the diamine component is preferably tetracarboxylic dianhydride:diamine=100:85 to 100:200 (relative to 1 mole part of tetracarboxylic dianhydride Diamine is in the range of 0.85 to 2.00 mole parts), more preferably in the range of 100:101 to 100:125 (1.01 to 1.25 mole parts of diamine relative to 1 mole part of acid dianhydride). By setting it as the said range, it becomes easy to react with a polyamic acid, and haze (Haze value) falls, and it is preferable in this point.

The reaction temperature is preferably 140°C or higher, more preferably 160°C, from the viewpoint of achieving imidization and water removal simultaneously. Also, from the standpoint of suppressing coloration due to the decomposition of the solvent and the reaction with the monomer, the reaction temperature is preferably 200°C or lower, more preferably 190°C or lower, and it is preferable to lower the temperature rapidly after the reaction is completed. below 100°C.

The reaction time is preferably at least 2 hours, more preferably at least 3 hours, from the viewpoint of increasing the molecular weight. On the other hand, the reaction time is preferably 12 hours or less, more preferably 6 hours or less, from the viewpoint of suppressing coloration due to decomposition of the solvent and reaction with the monomer.

Next, step 2 will be described. Step 2 is a step of dissolving the diamine (X ₂ ) of the polyamide acid part in the above general formula (1) in the polyimide obtained in the above step 1. After synthesizing the polyimide in step 1, add a certain amount of diamine (such as APAB) and NMP and stir well to dissolve the diamine. From the point of view of controlling the coefficient of thermal expansion, residual stress, elongation, and yellowness (hereinafter, also referred to as YI) of the polyimide copolymer film finally obtained within the desired range, it is preferable to set it as the source Component of tetracarboxylic dianhydride derived from polyimide part (X ₃ ): Component derived from diamine component of polyimide part and polyamic acid part (X ₂ and X ₄ ) = 100: 150～ 100:3000 (1.50-30 mole parts of diamine with respect to 1 mole part of tetracarboxylic dianhydride), more preferably 100:225-100:2000 (1 mole part with respect to tetracarboxylic dianhydride 1 Mole parts and diamine are in the range of 2.25-20 mole parts), and the mole ratio (diamine/tetracarboxylic dianhydride) is more preferably 2.25-20. By setting the above range, the uniformity of the reaction when tetracarboxylic dianhydride is reacted in step 3 is improved, the molecular weight distribution is close to 2.00, and the ratio of oligomers with a molecular weight of 1,000 or less is obtained. The amine copolymer has improved thermal stability in the high temperature range when it is formed into a film.

The temperature for dissolving diamine is preferably 40°C or higher, more preferably 60°C or higher, from the viewpoint of improving the solubility of diamine and improving uniformity. On the other hand, it is preferably 120°C or lower, more preferably 100°C or lower, from the viewpoint of suppressing coloration due to a side reaction with a solvent.

Next, step 3 will be described. In step 3, polyamide can be synthesized by adding tetracarboxylic dianhydride of the polyamic acid part in the above general formula (1) to the solution of polyimide and diamine dissolved in the above step 2, and performing polycondensation reaction Amino acid-imide copolymer.

As a method for producing a polyamic acid-imide copolymer including steps different from the steps 1 to 3 above, the method described in International Publication No. 2020/138360 is known. Specifically, in the imidization step of the above-mentioned step 1, the step of imidizing the diamine _compounds corresponding to X2 and _X4 can be included simultaneously, and the _two common to X2 and _X4 can be used. Amine compounds.

However, according to the results confirmed by the inventors of the present invention, when using the same production method as the International Publication No. 2020/138360 manual, that is, when the imide is synthesized in step 1, it will be equivalent to the general formula ( When the diamine of B-1) or (B-2) is used as a raw material, the molecular weight does not fully increase, and the polyamic acid-imide copolymer which can be evaluated cannot be obtained. It is believed that the reason is that the diamines represented by the general formulas (B-1) and (B-2) have high reactivity, lack of thermal stability in high-temperature solvents, and if the amine is in a state of excess relative to the acid If the diamine is heated at high temperature (about 180°C), the diamine will react with solvent or oxygen to cause deactivation, and the molecular weight will not be sufficiently increased when the polyamic acid-imide copolymer is synthesized in the subsequent steps.

Specifically, the NMP solution (hereinafter, also referred to as varnish) of polyimide-polyamic acid copolymer was obtained by performing a reproducibility test under the same conditions as the examples in the International Publication No. 2020/138360 manual, and the results It was confirmed that the weight average molecular weight (Mw) of the obtained polyamic acid-imide copolymer was 2,638, and the number average molecular weight (Mn) was 1,326. Therefore, from the viewpoint of the molecular weight of the copolymer, the production method including the above steps 1 to 3 is better than the production method described in WO 2020/138360 pamphlet.

From the viewpoint of controlling the coefficient of thermal expansion, residual stress, elongation, and YI of the obtained resin film within desired ranges, the polyamic acid part when synthesizing the above-mentioned polyamic acid-imide copolymer The molar ratio (X ₂ /X ₁ ) of the tetracarboxylic dianhydride component (X ₁ ) to the diamine component (X ₂ ) is preferably 0.85-1.2, more preferably 0.90-1.1, further preferably 0.92-1.00 . By setting it as the said range, it becomes easy to react with polyimide, and haze (Haze value) falls, and it is preferable in this point.

Also, from the viewpoint of controlling the coefficient of thermal expansion, residual stress, elongation, and YI of the obtained resin film within desired ranges, the polyimide used when synthesizing the above-mentioned polyamic acid-imide copolymer The molar ratio (X ₄ /X ₃ ) of the tetracarboxylic dianhydride component (X ₃ ) to the diamine component (X ₄ ) in the part is preferably in the range of 0.85 to 2.0, more preferably in the range of 0.95 to 1.5, and further Preferably it is in the range of 1.01 to 1.25. By setting it as the said range, heat resistance at high temperature improves, the decomposition reaction at the time of heating is suppressed, and yellowness (YI value) and haze (Haze value) are reduced, and it is preferable in this point.

Also, from the viewpoint of controlling the coefficient of thermal expansion, residual stress, elongation, and YI of the obtained resin film within desired ranges, the polyamic acid used in the synthesis of the above-mentioned polyamic acid-imide copolymer And the molar ratio of the tetracarboxylic dianhydride component (X ₁ and X ₃ ) and the diamine component (X ₂ and X ₄ ) of the polyimide part ((the number of moles of X ₂ + the number of moles of X ₄ ) /(the number of moles of X1 ₊ the number of moles of _X3 )) is preferably in the range of 0.92 to 1.05, more preferably in the range of 0.94 to 1.00. By setting it in the above range, the molecular weight of the polyamic acid-imide copolymer is easily increased, and the workability as a resin composition is improved, and the coating unevenness at the time of film production can be suppressed, and the haze (Haze value) is reduced. Better from this point of view. Also, within the above range, the number of blocked amines in the polyamic acid-imide copolymer decreases, the decomposition reaction during heating is suppressed, the thermal stability in the high temperature region is improved, and the yellowness (YI value) is reduced.

When synthesizing polyamic acid-imide copolymer, the molecular weight can be controlled by adjusting the ratio of the tetracarboxylic dianhydride component to the diamine component and adding an end-capping agent. The closer the ratio of the acid dianhydride component to the diamine component is 1:1 and the less the amount of end-capping agent used, the more the molecular weight of the polyimide can be increased.

High-purity products are recommended as tetracarboxylic dianhydride components and diamine components. The purity is preferably at least 98% by mass, more preferably at least 99% by mass, and still more preferably at least 99.5% by mass. When using multiple acid dianhydride components or diamine components in combination, it is sufficient that the acid dianhydride components or diamine components as a whole have the above-mentioned purity, but all types of acid dianhydride components and diamine components used are preferred. Each has the above-mentioned purity.

As the solvent for the reaction, the solvents shown in the above (d) organic solvent can be used without limitation.

As other components, the compounds described in the above (e) imidization catalyst can be used without limitation.

The solvent used in the synthesis of polyimide preferably has a boiling point of 60°C to 300°C under normal pressure, more preferably 140°C to 280°C, and especially preferably 170°C to 270°C. If the boiling point of the solvent is higher than 300°C, a long time is required for the drying step. On the other hand, if the boiling point of the solvent is lower than 60° C., the unevenness of the surface of the resin film and the mixing of air bubbles in the resin film may occur in the drying step, and a uniform film may not be obtained.

As mentioned above, it is preferable that the boiling point of the solvent under normal pressure is 170°C to 270°C, and it is more preferable to use a solvent with a vapor pressure of 250 Pa or less at 20°C from the viewpoint of solubility and edge shrinkage during coating. solvent. More specifically, it is preferable to use a compound selected from N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), N,N-dimethylacetamide (DMAc), and N , One or more solvents from the group consisting of N-dimethylformamide (DMF), and solvents described in the above item "(d) Organic solvents" can be used appropriately. The moisture content in the solvent is preferably 3000 mass ppm or less. These solvents can be used individually or in mixture of 2 or more types.

[Manufacturing method of polyamide acid] The polyamic acid of the fourth embodiment of the present invention is not limited, and can be produced, for example, by the method described in International Publication No. 2017/051827.

{式中，X ₁及X ₃表示四價有機基，X ₂及X ₄表示二價有機基，並且n、及m為正之整數} 所表示之結構單元，且具有上述通式(A-1)或上述通式(A-2)所表示之結構作為X ₂。 <Polyimide Copolymer> As another aspect of the present invention, there is provided a polyimidized polyamide-imide copolymer comprising (c) a polyamide-imide copolymer contained in the above-mentioned resin composition. Films of imide copolymers. In more detail, a kind of polyimide copolymer can be provided, it is characterized in that comprising following general formula (2): [Chemical 77]

{wherein, X ₁ and X ₃ represent tetravalent organic groups, X ₂ and X ₄ represent divalent organic groups, and n and m are positive integers} The structural unit represented by the above general formula (A-1 ) or the structure represented by the above general formula (A-2) as X ₂ .

The polyimide copolymer preferably satisfies any of the following from the viewpoint of excellent transparency, haze, heat resistance, and linear expansion coefficient of the polyimide film containing it: General formula (2) _The diamine component of X2 in the above-mentioned general formula (A-1) or the structure represented by the above-mentioned general formula (A-2) is a compound in which ₂ * are substituted by -NH2; General formula ( _X3 in 2) is at least one selected from the group consisting of the structure represented by the above general formula (A-3), the structure derived from ODPA, and the structure derived from 6FDA; General formula (2) X ₁ is at least one selected from the group consisting of a structure derived from BPDA, a structure derived from ODPA, and a structure derived from TAHQ; X ₁ and X ₂ included in the general formula (2) The molar ratio (X ₂ /X ₁ ) is 0.84 to 1.00; The molar ratio of X ₃ and X ₄ (X ₄ /X ₃ ) included in the general formula (2) is 1.01 to 2.00; and The molar ratio of the structural unit of the polyimide of X1 and X2 in general _formula ( ₂ ) and the structural unit of the polyimide comprising _X3 and _X4 (the molar number of structural unit N: structural unit The molar number of M) is in the range of 60:40 to 95:5; X ₁ or X ₃ is selected from the structure represented by the above general formula (A-3), derived from 4,4'-oxodi At least one of the group consisting of the structure of phthalic dianhydride (ODPA) and the structure derived from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA); X ₄ is at least one selected from the group consisting of structures represented by the above general formula (A-4), general formula (A-5) and general formula (A-6).

From the viewpoint of excellent transparency, haze, heat resistance and linear expansion coefficient of the polyimide film containing the polyimide copolymer, it is preferable that X in the general formula ( ₂ ) is derived from In the case of the base of 4-aminobenzoic acid 4-amino-3-fluorophenyl ester, the following constitutions 1 and 2 are excluded: Composition 1. _X3 is derived from 9,9-bis(3,4-di In the case of the base of carboxyphenyl) stilbenic anhydride (BPAF), X is derived from 4,4' _- diaminodiphenylene, and/or 2,2'-bis(trifluoromethyl)bis The base of aniline; and the composition 2.X ₃ is derived from nor-alkane-2-spiro-α-cyclopentanone a-α'-spiro-2''-nor-alkane-5,5'',6,6 ''-tetracarboxylic dianhydride base.

In terms of transparency, heat resistance, low residual stress and bending resistance, the polyimide copolymer is preferably derived from 9,9 _- bis(3,4-dicarboxyphenyl) In the case of the base of stilbenic anhydride (BPAF), X in the general formula ( ₂ ) will be derived from 4,4'-diaminodiphenylene, 2,2'-bis(trifluoromethyl) The base of benzidine is excluded.

{式中，X ₁表示四價有機基，X ₂表示二價有機基，並且n為正之整數} 且(e)醯亞胺化觸媒係包含N-第三丁氧基羰基咪唑(N-Boc-咪唑)及/或1-甲基咪唑之咪唑化合物，或其特徵在於(e)醯亞胺化觸媒係咪唑化合物，且(e)醯亞胺化觸媒之含量相對於聚醯胺酸100質量份為5質量份以上。 <Resin Composition Containing Polyamic Acid> As another aspect of the present invention, there is provided a resin composition characterized by comprising polyamic acid, (d) organic solvent and (e) imide as described above. As an amination catalyst, the above-mentioned polyamic acid comprises a structural unit represented by the following general formula (3): [Chemical 78]

_{ wherein, X1 represents _a tetravalent organic group, X2 represents a divalent organic group, and n is a positive integer} and (e) the imidization catalyst system includes N-tertiary butoxycarbonylimidazole (N- Boc-imidazole) and/or the imidazole compound of 1-methylimidazole, or it is characterized in that (e) the imidization catalyst is an imidazole compound, and (e) the content of the imidization catalyst is relative to the polyamide 100 mass parts of acids are 5 mass parts or more.

The resin composition comprising the structural unit represented by the general formula (3) preferably comprises N-tertiary butoxycarbonylimidazole (N-Boc-imidazole) and 1-methylimidazole as (e) imidization catalyst media. Also, the content of the (e) imidization catalyst is preferably in the range of 0.02 to 0.15 moles per 1 mole of the repeating unit of polyamic acid having the structural unit represented by the general formula (3).

X ₁ , X ₂ and n in the general formula (3) can be as defined in the above-mentioned general formula (1) or (2), and as X ₁ , it is preferably selected from the structure represented by the above-mentioned general formula (A-3) , Structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), source At least one selected from the group consisting of a structure derived from biphenyltetracarboxylic dianhydride (BPDA) and a structure derived from 4,4'-biphenylbis(trimellitic monoester anhydride) (TAHQ), and As X ₂ , it is preferably selected from the above general formula (A-1), the above general formula (A-2), the above general formula (A-4), the general formula (A-5), and the general formula (A- 6) At least one of the group consisting of the structures represented, more preferably the structure represented by the above general formula (A-1).

The weight average molecular weight (Mw) of polyamic acid is preferably 2,639 or more, more preferably 2,639-300,000 or 10,000-300,000, still more preferably 20,000-250,000, especially preferably 40,000-200,000. When the weight average molecular weight is 2,639 or more, mechanical properties such as elongation and breaking strength are excellent, residual stress decreases, and YI decreases. When the weight-average molecular weight is 300,000 or less, the polyamic acid-containing varnish has a good balance between viscosity and concentration, good processability, and reduced film unevenness during coating. Also, if the Mw of polyamic acid is 170,000 or more, it tends to be excellent in transparency, haze, heat resistance, and linear expansion coefficient, so it is preferable, and more preferably a Mw of 220,000 or more, which tends to have the above general formula The structure represented by (A-1) is remarkable as X2 in the general formula ( ₃ ). In the present invention, the weight average molecular weight is a value calculated using gel permeation chromatography (hereinafter also referred to as GPC) as a standard polystyrene conversion value.

{式中，X ₃表示四價有機基，X ₄表示二價有機基，且m為正之整數} 所表示之結構單元M之聚醯亞胺、或具有下述通式(16) [化80]

{式中，P ₁及P ₂與通式(I)或(II)中之P ₁及P ₂相同，m為正之整數} 所表示之結構之聚醯亞胺。 <Polyimide> As another aspect of the present invention, there is provided a polyimide comprising the following general formula (3): [Chem. 79]

{wherein, X ₃ represents a tetravalent organic group, X ₄ represents a divalent organic group, and m is a positive integer} The polyimide of the structural unit M represented by the following general formula (16) [Chem. ]

{wherein, P ₁ and P ₂ are the same as P ₁ and P ₂ in the general formula (I) or (II), m is a positive integer} Polyimide of the structure represented.

The polyimide is characterized by comprising a structure selected from the structure represented by the above-described general formula (A-3), a structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), and a structure derived from At least one of the group consisting of the structure of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) is used as X ₃ in the general formula (3).

X ₄ in the general formula (3) is as described as X ₄ in the above general formula (1) or (2). The diamine component constituting _X4 in general formula (3) is preferably any one of diamine composition or diamine type from the same viewpoint as _X4 in general formula (1) or (2) above Different, more preferably the composition or type of aromatic diamine, and further preferably X in the general formula ( ₃ ) is selected from the general formula (A-4) and general formula (A-5) described above , and at least one of the group consisting of the structure represented by the general formula (A-6).

The preferred P ₁ and P ₂ in the general formula (I) or (II) are also preferred in the polyimide of the general formula (16) for the same reason. The number m of repeating units of the general formula (16) is not particularly limited, and may be an integer of 2-150.

Furthermore, it is preferable that the polyimide obtained from the resin composition does not substantially contain the aprotic polar substance with a boiling point of 250° C. to 350° C. contained in the resin composition, and may contain 1000 ppm or less.

"Manufacturing Method of Resin Composition" The manufacturing method of the resin composition demonstrated above is not specifically limited, For example, the following method can be used.

＜Purification of silicon-containing compounds＞ The resin composition can be produced by subjecting a polycondensation component containing an acid dianhydride, a diamine, and a silicon-containing compound to a polycondensation reaction. As a method of reducing the total amount of the cyclic silicon-containing compound contained in the resin composition, for example, before the polycondensation reaction, the silicon-containing compound is purified to reduce the total amount of the cyclic silicon-containing compound. Alternatively, the resin composition may be purified after the polycondensation reaction to reduce the total amount of cyclic silicon-containing compounds.

As a method of purifying the silicon-containing compound, for example, blowing an inert gas, such as nitrogen, to the silicon-containing compound in an arbitrary container, and performing stripping. The stripping temperature is preferably from 200°C to 300°C, more preferably from 220°C to 300°C, still more preferably from 240°C to 300°C. As the stripping vapor pressure, the lower the better, it is 1000 Pa or less, more preferably 300 Pa or less, further preferably 200 Pa or less, still more preferably 133.32 Pa (1 mmHg) Pa or less. The stripping time is preferably from 4 hours to 12 hours, more preferably from 6 hours to 10 hours. By adjusting the above conditions, a cyclic silicon-containing compound can be efficiently removed, and the total amount of the cyclic silicon-containing compound can be controlled within a preferable range.

＜Synthesis of polyimide/polyimide precursor＞ The polyimide precursor can be synthesized by subjecting polycondensation components including acid dianhydride, diamine, and silicon-containing compound to polycondensation reaction. Regarding the synthesis of polyimide/polyimide precursor, for example, a method for manufacturing a resin composition comprising any of the following steps is provided: The step of subjecting at least one compound selected from the above-mentioned diamine compounds, at least one compound selected from the above-mentioned acid dianhydride compounds, and other compounds to a polycondensation reaction to provide a polyimide precursor and/or polyimide ; Polycondensation reaction of at least one compound selected from the above-mentioned diamine compounds, at least one compound selected from the above-mentioned acid dianhydride compounds, the silicon-containing compound represented by the general formula (13), and other compounds to provide polyamide Amine precursor and/or polyimide step. Also, it is preferable to use the above-mentioned purified silicon-containing compound. In a preferred aspect, the polycondensation component includes acid dianhydride, diamine, and silicon-containing compound. The polycondensation reaction is preferably carried out in an appropriate solvent. Specifically, for example, after dissolving a specific amount of a diamine component and a silicon-containing compound in a solvent, a method of adding a specific amount of acid dianhydride to the obtained diamine solution and stirring it may be mentioned. The imidization during the synthesis of polyimide may be thermal imidization or chemical imidization using an imidization catalyst.

From the viewpoint of increasing the molecular weight of the polyimide precursor resin and the slit coating properties of the resin composition, the molar ratio of acid dianhydride and diamine when synthesizing polyimide/polyimide precursor It is more preferably in the range of acid dianhydride:diamine=100:90～100:110 (0.90～1.10 mole parts of diamine relative to 1 mole part of acid dianhydride), and more preferably 100:95～100 : 105 (0.95 to 1.05 mole parts of diamine relative to 1 mole part of acid dianhydride).

The molecular weight of polyimide/polyimide precursor can be adjusted by the type of acid dianhydride, diamine and silicon-containing compound, the molar ratio of acid dianhydride and diamine, the addition of end-capping sealant, and the reaction Conditional adjustments, etc. are controlled. The closer the molar ratio of the acid dianhydride component to the diamine component is to 1:1, and the less the amount of end-capping agent is used, the higher the molecular weight of the polyimide precursor can be.

High-purity products are recommended as acid dianhydride components and diamine components. The purity thereof is preferably at least 98% by mass, more preferably at least 99% by mass, and still more preferably at least 99.5% by mass. It can also be highly purified by reducing the water content in acid dianhydride components and diamine components. When using multiple kinds of acid dianhydride components and/or multiple kinds of diamine components, it is preferable that the whole acid dianhydride components and the whole diamine components have the above-mentioned purity, and it is more preferable that all kinds of acid diamine components used The anhydride component and the diamine component each have the above-mentioned purity.

The reaction solvent is not particularly limited, as long as it can dissolve the acid dianhydride component, the diamine component, and the produced polyimide/polyimide precursor to obtain a high molecular weight polymer. As such a solvent, an aprotic solvent, a phenol type solvent, an ether, a glycol type solvent, etc. are mentioned, for example.

{式中，R ₁₂＝甲基所表示之Equamide M100(商品名：KJ CHEMICALS公司製造)、及R ₁₂＝正丁基所表示之Equamide B100(商品名：KJ CHEMICALS公司製造)}；γ-丁內酯、γ-戊內酯等內酯系溶劑；六甲基磷醯三胺、六甲基膦三醯胺等含磷系醯胺系溶劑；二甲基碸、二甲基亞碸、環丁碸等含硫系溶劑；環己酮、甲基環己酮等酮系溶劑；甲基吡啶、吡啶等三級胺系溶劑；乙酸(2-甲氧基-1-甲基乙基)等酯系溶劑等。 As an aprotic solvent, for example, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone ( NMP), N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea, and amide-based solvents of the following general formula: [Chemical 81]

{wherein, R ₁₂ = Equamide M100 represented by a methyl group (trade name: manufactured by KJ Chemicals), and R ₁₂ = Equamide B100 represented by a n-butyl group (trade name: manufactured by KJ Chemicals)}; γ-butyl Lactone-based solvents such as lactone and γ-valerolactone; phosphorus-containing amide-based solvents such as hexamethylphosphine triamide and hexamethylphosphine triamide; dimethylsulfide, dimethylsulfoxide, cyclic Sulfur-containing solvents such as butane; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; acetic acid (2-methoxy-1-methylethyl), etc. Ester solvents, etc.

As the phenolic solvent, for example, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, 6-xylenol, 3,4-xylenol, 3,5-xylenol, etc.

Examples of ether and glycol-based solvents include: 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy ) ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,4-dioxane, etc.

These solvents can be used individually or in mixture of 2 or more types.

The boiling point of the solvent used in the synthesis of polyimide/polyimide precursor is preferably 60-300°C, more preferably 140-280°C, and still more preferably 170-270°C under normal pressure. By keeping the boiling point of the solvent below 300°C, the drying step time is shorter. If the boiling point of the solvent is 60° C. or higher, unevenness on the surface of the resin film and mixing of air bubbles into the resin film are less likely to occur during the drying step, and a more uniform film can be obtained. From the viewpoint of reducing solubility and edge abnormalities during coating, it is particularly preferable to use a solvent having a boiling point of 170 to 270° C. and/or a vapor pressure at 20° C. of 250 Pa or less. More specifically, it is preferably one or more selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and the compound represented by the above general formula .

In order to make the polycondensation reaction proceed favorably, the water content in the solvent is preferably, for example, 3,000 mass ppm or less. In the resin composition, the content of molecules having a molecular weight of less than 1,000 is preferably less than 5% by mass. It is considered that the presence of molecules with a molecular weight of less than 1,000 in the resin composition is related to the moisture content of the solvent or raw materials (acid dianhydride, diamine) used in the synthesis. That is, it is considered that the acid anhydride groups of some acid dianhydride monomers are hydrolyzed by water to become carboxyl groups, and remain in a low molecular state without increasing the molecular weight. Therefore, the less moisture content of the solvent used in the above polycondensation reaction, the better. The water content of the solvent is preferably 3,000 mass ppm or less, more preferably 1,000 mass ppm or less. Similarly, the amount of water contained in the raw material is preferably 3,000 mass ppm or less, more preferably 1,000 mass ppm or less.

It is considered that the moisture content of the solvent is related to the grade of the solvent used (dehydration grade, general grade, etc.), solvent container (bottle, 18 L can, barrel, etc.), storage state of the solvent (whether rare gas is enclosed, etc.), since opening to The time before use (use immediately after opening or use after a certain period of time after opening, etc.) is related. It is also considered to be related to the replacement of the rare gas in the reactor before the synthesis, and the presence or absence of the circulation of the rare gas during the synthesis. Therefore, when synthesizing polyimide precursors, it is recommended to use high-purity products as raw materials, use solvents with low moisture content, and adopt a treatment that prevents moisture from the environment from mixing into the system before and during the reaction.

When dissolving each polycondensation component in a solvent, it may heat as needed. From the viewpoint of obtaining a polyimide precursor with a higher degree of polymerization, the reaction temperature during the synthesis of the polyimide precursor can be preferably 0°C to 120°C, 40°C to 100°C, or 60 to 100°C. °C, the polymerization time may preferably be 1 to 100 hours or 2 to 10 hours. By setting the polymerization time to 1 hour or more, a polyimide precursor with a uniform degree of polymerization can be obtained, and by setting it to 100 hours or less, a polyimide precursor with a high degree of polymerization can be obtained.

In addition to the polyimide/polyimide precursor described above, the resin composition may also contain other additional polyimide precursors. However, from the viewpoint of reducing the YI value of the polyimide film and the oxygen dependence of the total light transmittance, relative to the total amount of polyimide/polyimide precursor in the resin composition, an additional The mass ratio of polyimide/polyimide precursor is preferably 30% by mass or less, more preferably 10% by mass or less.

A part of the polyimide precursor may be imidized (partial imidized). Viscosity stability during preservation of the resin composition can be improved by partially imidizing the polyimide precursor. From the viewpoint of achieving a balance between the solubility of the polyimide precursor in the resin composition and the storage stability of the solution, the imidization rate in this case is preferably 5% or more, more preferably 8%. Above, preferably 80% or less, more preferably 70% or less, still more preferably 50% or less. The partial imidization can be obtained by dehydrating and ring-closing the polyimide precursor by heating. The heating can be performed at a temperature of preferably 120-200°C, more preferably 150-185°C, and still more preferably 150-180°C, preferably for 15 minutes to 20 hours, more preferably for 30 minutes to 10 hours.

It is also possible to add N,N-dimethylformamide dimethyl acetal or N,N-dimethylformamide to the polyimide/polyimide precursor obtained by the above reaction. Amide diethyl acetal and heating to esterify part or all of the carboxylic acids are used as polyimide precursors. The viscosity stability during storage can be improved by esterification. These ester-modified polyamic acids can also be obtained by making the above-mentioned acid dianhydride components sequentially mixed with one equivalent of a polyhydric alcohol relative to the acid anhydride group, and thionyl chloride, dicyclohexylcarbodiimide, etc. It can be obtained by condensation reaction with diamine component after reaction of dehydration condensation agent.

＜Synthesis of Polyimide＞ As a more preferable aspect, the polyimide varnish can dissolve the acid dianhydride component and the diamine component in a solvent, such as an organic solvent, add an azeotropic solvent such as toluene, and remove the water generated during imidization into the system In addition, it is manufactured in the form of a polyimide solution (also called polyimide varnish) containing polyimide and a solvent. Here, the conditions during the reaction are not particularly limited, for example, the reaction temperature is 0°C to 180°C, and the reaction time is 3 to 72 hours. In order to fully proceed with the reaction with the diamines containing phenyl group, it is preferable to heat the reaction at 180° C. for about 12 hours. Also, during the reaction, an inert atmosphere such as argon or nitrogen is preferred.

＜Preparation of resin composition＞ When the solvent used to synthesize the polyimide precursor is the same as the solvent contained in the resin composition, the synthesized polyimide/polyimide precursor solution can be directly used as a resin composition . Optionally, one or more solvents and additional components may be added to the polyimide precursor within a temperature range of room temperature (25° C.) to 80° C., and stirred and mixed to prepare a resin composition. This stirring and mixing can be carried out using a suitable device such as a Sany motor (manufactured by Shinto Chemical Co., Ltd.) equipped with stirring blades, and a self-rotation-revolution mixer. The resin composition may also be heated to 40°C to 100°C as needed.

On the other hand, when the solvent used in the synthesis of polyimide/polyimide precursor is different from the solvent contained in the resin composition, it can also be removed by appropriate methods such as reprecipitation and solvent distillation. The method is to isolate the polyimide/polyimide precursor after removing the solvent in the synthesized polyimide precursor solution. Then, a required solvent and, if necessary, additional components may be added to the isolated polyimide precursor at a temperature range of room temperature (25°C) to 80°C, and the resin composition may be prepared by stirring and mixing. .

It is especially preferable to add an aprotic polar substance with a boiling point of 250° C. to 350° C. after synthesizing the polyimide/polyimide precursor in the preparation of the resin composition. Thereby, the in-plane uniformity of the film thickness of the obtained polyimide resin film can be improved, and yellowness (YI value) can also be reduced.

After the resin composition is prepared in the above manner, the resin composition is heated at, for example, 130-200° C. for 5 minutes to 2 hours, so that the polyimide precursor can be made to the extent that the polymer does not precipitate. A part is dehydroimidized (partial imidized). The imidization rate can be controlled by controlling the heating temperature and heating time. Viscosity stability during preservation of the resin composition can be improved by partially imidizing the polyimide precursor.

From the viewpoint of slot coating performance, the solution viscosity of the resin composition is preferably 500-100,000 mPa·s, more preferably 1,000-50,000 mPa·s, and still more preferably 3,000-20,000 mPa·s. Specifically, it is preferably at least 500 mPa·s, more preferably at least 1,000 mPa·s, and still more preferably at least 3,000 mPa·s, in terms of the difficulty of liquid leakage from the slit nozzle. From the point that the slit nozzle is less likely to be clogged, it is preferably at most 100,000 mPa·s, more preferably at most 50,000 mPa·s, further preferably at most 20,000 mPa·s.

Regarding the solution viscosity of the resin composition during polyimide/polyimide precursor synthesis, if it exceeds 200,000 mPa·s, there may be a problem that stirring during synthesis becomes difficult. However, even if the solution becomes highly viscous at the time of synthesis, a resin composition with good workability can be obtained by adding a solvent and stirring after completion of the reaction. The solution viscosity of the resin composition is a value measured at 23° C. using an E-type viscometer (for example, VISCONICE HD, manufactured by Toki Sangyo).

From the viewpoint of viscosity stability when storing the resin composition, the moisture content of the resin composition is preferably at most 3,000 mass ppm, more preferably at most 2,500 mass ppm, still more preferably at most 2,000 mass ppm, and even more preferably at most It is not more than 1,500 mass ppm, more preferably not more than 1,000 mass ppm, more preferably not more than 500 mass ppm, more preferably not more than 300 mass ppm, particularly preferably not more than 100 mass ppm.

"Polyimide resin film and its manufacturing method" A polyimide resin film (hereinafter also referred to as a polyimide film) can be provided using the above-described resin composition. The method for producing a polyimide film described above includes: a coating step of coating a resin composition on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film; and A peeling step of peeling the polyimide resin film from the support.

＜Coating procedure＞ In the coating step, the resin composition is coated on the surface of the support. The support is not particularly limited as long as it has heat resistance to the heating temperature in the subsequent film forming step (heating step) and has good peelability in the peeling step. As the support, for example, a glass substrate, such as an alkali-free glass substrate; a silicon wafer; PET (polyethylene terephthalate), OPP (extended polypropylene), polyethylene terephthalate ester, polyethylene glycol naphthalate, polycarbonate, polyimide, polyamideimide, polyetherimide, polyetheretherketone, polyether, polyphenylene, poly Resin substrates such as phenylene sulfide; metal substrates such as stainless steel, alumina, copper, nickel, etc.

In the case of forming a thin-film polyimide molded body, for example, glass substrates, silicon wafers, etc. are preferred, and in the case of forming a thick film-like polyimide molded body or a sheet-like polyimide, for example, it is preferable It is a support including PET (polyethylene terephthalate), OPP (extended polypropylene), etc.

As the coating method, usually, a knife coater, an air knife coater, a roll coater, a spin coater, a flow coater, a die coater, a bar coater, etc. Methods; coating methods such as spin coating, spray coating, and dip coating; printing technologies represented by screen printing and gravure printing, etc. For the resin composition, coating by slit coating is preferred. The coating thickness should be properly adjusted according to the required thickness of the resin film and the content of the polyimide precursor in the resin composition, preferably about 1-1,000 μm. The temperature in the coating step may be room temperature, but the resin composition may be heated to, for example, 40°C to 80°C in order to lower the viscosity and improve workability.

＜Any drying step＞ The drying step may be performed after the coating step, or the drying step may be skipped and the subsequent film forming step (heating step) may be directly performed. The drying step is performed to remove the organic solvent in the resin composition. In the case of performing the drying step, for example, appropriate devices such as a hot plate, a box-type dryer, and a conveyor-type dryer can be used. The temperature of the drying step is preferably from 80°C to 200°C, more preferably from 100°C to 150°C. The implementation time of the drying step is preferably 1 minute to 10 hours, more preferably 3 minutes to 1 hour. As described above, the coating film containing the polyimide precursor was formed on the support.

＜Film formation process＞ Next, a film forming step (heating step) is performed. The heating step is a step of removing the organic solvent contained in the above-mentioned coating film, and advancing the imidization reaction of the polyimide precursor in the coating film to obtain a polyimide resin film. This heating step can be performed, for example, using devices such as an inert gas oven, a hot plate, a box-type dryer, and a conveyor-type dryer. This step can be carried out simultaneously with the drying step, or the two steps can be carried out one by one.

The heating step can be carried out under air atmosphere, but in terms of obtaining safety, good transparency of the obtained polyimide film, lower thickness direction retardation (Rth) and lower YI value, it is better than Preferably, it is carried out under an inert gas atmosphere. As an inert gas, nitrogen gas, argon gas, etc. are mentioned, for example. The heating temperature is appropriately set according to the type of polyimide precursor and the type of solvent in the resin composition, preferably 250°C to 550°C, more preferably 300°C to 450°C. If it is 250° C. or higher, the imidization proceeds favorably, and if it is 550° C. or lower, disadvantages such as lowered transparency and worsened heat resistance of the obtained polyimide film can be avoided. The heating time is preferably about 0.1 to 10 hours.

Especially when the resin composition contains an aprotic polar substance with a boiling point of 250°C to 350°C, in the heating step of polyimide, even if the temperature is above 250°C, it will remain in the film and exert its high temperature. Acts as a plasticizer. Therefore, the resin becomes soft and has fluidity, and as a result, the in-plane uniformity of the film thickness of the obtained polyimide resin film is improved, and YI is also reduced.

From the viewpoint of the transparency and YI value of the obtained polyimide film, the oxygen concentration of the ambient atmosphere in the heating step is preferably 2,000 mass ppm or less, more preferably 100 mass ppm or less, and still more preferably 10 mass ppm or less. By heating in an atmosphere having an oxygen concentration of 2,000 mass ppm or less, the YI value of the obtained polyimide film can be made to be 30 or less.

＜Peel off procedure＞ In the peeling step, the polyimide resin film on the support is cooled to, for example, about room temperature (25° C.) to 50° C., and then peeled off. As this peeling process, the aspects of following (1)-(4) are mentioned, for example.

(1) After fabricating a structure comprising a polyimide resin film/support by the above method, irradiating laser from the support side of the structure, and performing ablation processing on the interface between the support and the polyimide resin film, In this way, the polyimide resin is peeled off. The type of laser may, for example, be a solid state (YAG) laser or a gas (UV excimer) laser. It is preferable to use a spectrum with a wavelength of 308 nm or the like (see Japanese Patent Publication No. 2007-512568, Japanese Patent Publication No. 2012-511173, etc.).

(2) Before coating the resin composition on the support, a peeling layer is formed on the support, and then a structure comprising polyimide resin film/peeling layer/support is obtained, and the polyimide resin film is peeled off method. As the peeling layer, Parylene (registered trademark, manufactured by Japan Parylene Co., Ltd.), tungsten oxide can be exemplified; release agents such as vegetable oil-based, polysiloxane-based, fluorine-based, alkyd-based, etc. can also be used (refer to Japanese Patent Laid-Open 2010-067957, Japanese Patent Laid-Open No. 2013-179306, etc.). This method (2) can also be used in combination with the laser irradiation of the method (1).

(3) A method of obtaining a polyimide resin film by using an etchable metal substrate as a support to obtain a structure including a polyimide resin film/support, and then etching the metal with an etchant. As the metal, for example, copper (as a specific example, electrolytic copper foil "DFF" manufactured by Mitsui Metal Mining Co., Ltd.), aluminum, and the like can be used. As an etchant, ferric chloride or the like is used for copper, and dilute hydrochloric acid or the like is used for aluminum.

(4) After the structure comprising the polyimide resin film/support is obtained by the above method, the adhesive film is attached to the surface of the polyimide resin film, and the adhesive film/polyimide resin film is self-supported Separation, and then the method of separating the polyimide resin film from the adhesive film.

Among these peeling methods, the method (1) or (2) is preferable from the viewpoint of the difference in refractive index between the front and back of the obtained polyimide resin film, the YI value, and the elongation. From the viewpoint of the difference in refractive index between the front and back surfaces of the obtained polyimide resin film, it is more preferable to perform an irradiation step of irradiating laser light from the support side before the method (1), that is, the peeling step. Furthermore, in method (3), when copper is used as a support body, the YI value of the obtained polyimide resin film tends to increase and elongation tends to decrease. This is considered to be due to the influence of copper ions.

The thickness of the obtained polyimide film is not limited, but is preferably 1-200 μm, more preferably 5-100 μm.

＜Polyimide film＞ In another aspect of the present invention, a polyimide film is provided, which is characterized in that, when measured with a film thickness of 10 μm, the tensile elastic modulus at 25° C. is 6 GPa or more, 350 The tensile elastic modulus at °C is 0.5 GPa or more, and the yellowness (YI value) is 12 or less.

The polyimide film is preferably prepared using the above-described polyamide acid-imide copolymer and/or polyimide copolymer as a raw material. From the viewpoint of achieving a balance with transparency, heat resistance and linear expansion coefficient, the haze (Haze value) of the polyimide film is preferably less than 0.5%, and/or in terms of obtaining a balance with the Haze value, heat resistance and From the viewpoint of the balance of the linear expansion coefficient, the change rate of the yellowness (YI value) of the polyimide film when kept at 430°C for 1 hour is preferably 20% or less.

The resin film produced by using the above-mentioned polyamic acid-imide copolymer, polyamic acid, polyimide, and resin composition can be used, for example, as a semiconductor insulating film, a TFT-LCD insulating film, and an electrode. In addition, protective films and the like can also be particularly preferably used as substrates in the manufacture of flexible devices. Here, examples of flexible devices to which resin films and laminates can be applied include flexible displays, flexible solar cells, flexible touch panel electrode substrates, flexible lighting, flexible battery etc.

"Use of Polyimide Membrane" The polyimide film obtained from the resin composition described above can be used, for example, as a semiconductor insulating film, a thin-film transistor liquid crystal display (TFT-LCD) insulating film, an electrode protective film, and can be used as a liquid crystal display, organic electrical Transparent substrates of display devices such as luminescent displays, field emission displays, and electronic paper.

In particular, polyimide film can be preferably used as thin film transistor (TFT) substrate, color filter substrate, touch panel substrate, transparent conductive film (ITO, Indium Thin Oxide) in the manufacture of flexible devices. (Indium Tin Oxide)) flexible substrate. Examples of flexible devices to which polyimide films can be applied include: TFT devices for flexible displays, flexible solar cells, flexible touch panels, flexible lighting, flexible batteries, Flexible printed substrates, flexible color filters, surface covers for smartphones, etc.

Typically, the step of forming a TFT on a flexible substrate using a polyimide film is performed at a temperature in a wide range of 150°C to 650°C. Specifically, in the case of manufacturing TFT devices using amorphous silicon, a process temperature of 250°C to 350°C is usually required, and the polyimide film must be able to withstand this temperature. The polymer structure above the glass transition temperature and thermal decomposition initiation temperature.

In the case of making TFT devices using metal oxide semiconductors (IGZO, etc.), a process temperature of 320°C to 400°C is usually required. The polyimide film must be able to withstand this temperature, so it must be properly selected with the highest TFT manufacturing process temperature. The polymer structure above the glass transition temperature and thermal decomposition initiation temperature.

In the case of making TFT devices using low-temperature polysilicon (LTPS), a process temperature of 380°C to 520°C is usually required. The polyimide film must be able to withstand this temperature, so it is necessary to properly select the glass above the maximum temperature of the TFT manufacturing process Transition temperature, thermal decomposition initiation temperature. On the other hand, due to these thermal histories, the more exposed to high-temperature processes, the lower the optical properties (especially light transmittance, retardation properties, and YI value) of the polyimide film tend to be. However, polyimides obtained from polyimide precursors have good optical properties even after thermal history.

Hereinafter, as an application example of the polyimide film, a method for producing a display and a laminate will be described.

<Manufacturing method of display> In one aspect of the present invention, the manufacturing method of the display includes: a coating step of coating the resin composition on the surface of the support; the resin composition is heated to form a polyimide film (polyimide resin film), a film forming step of forming an element on the polyimide film; and a peeling step of peeling the polyimide film on which the element is formed from the support.

Manufacturing example of flexible organic EL display FIG. 1 is a schematic diagram showing the structure of a top-emission type flexible organic EL display, which is an example of a display of an aspect of the present invention, above a polyimide substrate. The organic EL structure part 25 of FIG. 1 is demonstrated. For example, an organic EL element 250a emitting red light, an organic EL element 250b emitting green light, and an organic EL element 250c emitting blue light are arranged in a matrix as a unit, and are defined by partition walls (banks) 251 The light emitting area of each organic EL element. Each organic EL element includes a lower electrode (anode) 252 , a hole transport layer 253 , a light emitting layer 254 , and an upper electrode (cathode) 255 . A plurality of TFTs 256 for driving organic EL elements (selected from low temperature polysilicon (LTPS) ) or a metal oxide semiconductor (IGZO, etc.), an interlayer insulating film 258 having a contact hole 257 , and a lower electrode 259 . The organic EL elements are encapsulated by the sealing substrate 2b, and a hollow portion 261 is formed between each organic EL element and the sealing substrate 2b.

The manufacturing steps of the flexible organic EL display include: manufacturing a polyimide film on a glass substrate support, and manufacturing the organic EL substrate shown in Figure 1 on top of it; manufacturing a sealing substrate; laminating the two substrates The assembly step; and the peeling step of peeling off the organic EL display made on the polyimide film from the glass substrate support. Well-known manufacturing steps can be applied to the organic EL substrate manufacturing step, the sealing substrate manufacturing step, and the assembly step. An example thereof is given below, but is not limited thereto. The peeling procedure is the same as the peeling procedure of the above-mentioned polyimide film.

For example, if referring to FIG. 1, first, a polyimide film is formed on a glass substrate support by the above-mentioned method, and silicon nitride (SiN) and silicon oxide (SiO ) multi-layer structure multi-barrier layer (lower substrate 2a in Fig. 1), and use photoresist equal to its upper part to make the metal wiring layer for driving TFT. Use the CVD method to make an active buffer layer such as SiO on the upper part, and make TFT devices such as metal oxide semiconductor (IGZO) or low temperature polysilicon (LTPS) on the upper part (TFT256 in Figure 1). After fabricating the TFT substrate for a flexible display, an interlayer insulating film 258 having a contact hole 257 is formed using photosensitive acrylic resin or the like. An ITO film is formed by sputtering or the like, and the lower electrode 259 is formed so as to be opposed to the TFT.

Next, after forming partition walls (banks) 251 using photosensitive polyimide or the like, a hole transport layer 253 and a light emitting layer 254 are formed in each space divided by the partition walls. An upper electrode (cathode) 255 is formed to cover the light emitting layer 254 and the partition wall (bank) 251 . Thereafter, using a fine metal mask or the like as a mask, the red-emitting organic EL material (corresponding to the red-emitting organic EL element 250a in FIG. 1 ), the green-emitting organic EL material ( The organic EL element 250b that emits green light in FIG. 1) and the organic EL material that emits blue light (corresponds to the organic EL element 250c that emits blue light in FIG. 1) are vapor-deposited to produce an organic EL substrate. The organic EL substrate is sealed with a sealing film or the like (sealing substrate 2b in FIG. 1 ), and the upper part of the polyimide substrate is peeled off from the glass substrate support by a known peeling method such as laser peeling. This enables the fabrication of top-emission flexible organic EL displays. When the polyimide of one aspect of the present invention is used, a see-through flexible organic EL display can be produced. Bottom emission type flexible organic EL displays can also be produced by known methods.

Manufacturing example of flexible liquid crystal display A flexible liquid crystal display can be produced using the polyimide film of one aspect of the present invention. As a specific production method, a polyimide film is produced on a glass substrate support by the above-mentioned method, and a TFT substrate including, for example, amorphous silicon, metal oxide semiconductor (IGZO, etc.), and low-temperature polysilicon is produced using the above-mentioned method. In addition, according to the coating step and film forming step of one aspect of the present invention, a polyimide film is produced on a glass substrate support, and a polyimide film is produced using a color resist or the like according to a known method. Color filter glass substrate (CF substrate). Apply a sealing material including thermosetting epoxy resin on one of the TFT substrate and the CF substrate by screen printing to form a frame-shaped pattern that lacks the liquid crystal injection port, and scatter the other substrate with the same liquid crystal. The thickness of the layer is equivalent to the diameter and comprises spherical spacers of plastic or silicon dioxide.

Next, the TFT substrate and the CF substrate were bonded together, and the sealing material was cured. Next, the liquid crystal material is injected into the space surrounded by the TFT substrate, the CF substrate and the sealing material by a decompression method, a thermosetting resin is applied to the liquid crystal injection port, and the liquid crystal material is sealed by heating to form a liquid crystal Floor. Finally, the glass substrate on the CF side and the glass substrate on the TFT side were peeled off at the interface between the polyimide film and the glass substrate by the laser lift-off method, thereby fabricating a flexible liquid crystal display.

＜Manufacturing method of laminate＞ A method for producing a laminate according to an aspect of the present invention includes: a coating step of coating a resin composition on the surface of a support; a film forming step of heating the resin composition to form a polyimide film ( polyimide resin film); and an element forming step, which forms an element on the polyimide film.

The elements in the laminate may, for example, be those exemplified above for the production of flexible devices such as flexible displays. As the support, for example, a glass substrate can be used. The preferred specific sequence of the coating step and the film forming step is the same as that described above for the production method of the polyimide film. In the element forming step, the above-mentioned element is formed on a polyimide resin film as a flexible substrate formed on a support. Thereafter, the polyimide resin film on which the device is formed and the device may be peeled from the support in the peeling step optionally. In addition, a method for manufacturing a flexible device according to an aspect of the present invention includes manufacturing a laminate by the method for manufacturing a laminate described above.

As mentioned above, although embodiment of this invention was described, this invention is not limited to these, It can change suitably in the range which does not deviate from the summary of invention. [Example]

Hereinafter, the present invention will be described in more detail based on examples, but these are descriptions for illustration, and the scope of the present invention is not limited to the following examples.

Various evaluations in Examples and Comparative Examples were performed as follows.

<Determination of weight average molecular weight and number average molecular weight> Weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.

Use N,N-dimethylformamide (manufactured by Fuji Film Wako Pure Chemical Industries, for high-performance liquid chromatography, and add 24.8 mmol/L lithium bromide monohydrate (Fuji Film Wako Pure Chemical Industries) before the measurement. Manufactured, purity 99.5%) and 63.2 mmol/L phosphoric acid (manufactured by Fuji Film Wako Pure Chemical Industries, for high performance liquid chromatography) and dissolved) as solvents. A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (Easical Type PS-1, manufactured by Agilent Technologies). Device: HLC-8220GPC (manufactured by Tosoh Corporation) Column: Tsk gel Super HM-H 2 pieces (manufactured by Tosoh) Flow rate: 0.5 mL/min Column temperature: 40°C Detector: UV-8220 (UV-VIS: ultraviolet-visible absorbance meter, manufactured by Tosoh Corporation)

＜Evaluation of glass transition temperature (Tg)＞ The measurement of the glass transition temperature (Tg) in the temperature range of 50-500°C is carried out by thermomechanical analysis by cutting a polyimide film into a test piece with a size of 3 mm×20 mm. Using Seiko Electronics Co., Ltd. (EXSTAR6000) as the measuring device, under the conditions of a tensile load of 49 mN, a heating rate of 10°C/min, and a nitrogen flow (flow rate of 100 mL/min), the temperature is 50°C to 500°C. Determination of the elongation of the test piece within the range. The glass transition temperature of the polyimide film (thickness 10 μm) was calculated from the inflection point of the obtained curve. If the inflection point does not appear within the range of 50°C to 500°C, it is regarded as having a Tg of 500°C or higher, and it is sometimes shown in the form of "-" in the following table.

＜Evaluation of residual stress＞ On a 6-inch silicon wafer with a thickness of 625 μm±25 μm measured in advance for “warpage”, each resin composition was coated by a spin coater, and prebaked at 100°C for 7 minutes. Thereafter, the oxygen concentration in the chamber was adjusted so that it was 10 mass ppm or less, and heat hardening treatment (curing treatment) was performed at 430°C for 1 hour to produce a polyimide resin film with a film thickness of 10 μm after hardening. of silicon wafers.

The amount of warpage of the wafer was measured using a residual stress measuring device (manufactured by Tencor, model name FLX-230), and the residual stress generated between the silicon wafer and the resin film was evaluated. S: Residual stress exceeds -5 MPa and is 15 MPa or less (residual stress evaluation "excellent") A: Residual stress exceeds 15 MPa and is 25 MPa or less (evaluation of residual stress is "good") B: The residual stress exceeds 25 MPa (the evaluation of the residual stress is "poor")

＜Evaluation of yellowness (YI value) and haze (Haze value)＞ Each resin composition was coated on a 100 mm square (thickness 0.7 mm) Eagle XG glass with a spin coater, and prebaked at 80° C. for 30 minutes. Thereafter, the oxygen concentration in the chamber was adjusted so that it was 10 mass ppm or less, and heat hardening treatment (curing treatment) was performed at 430°C for 1 hour to produce a polyimide resin film with a film thickness of 10 μm after hardening. The glass substrate. For the obtained glass substrate of agglomerated imide, the yellowness (YI value) was measured using a Spectotometer (SE6000) manufactured by Nippon Denshoku Industry Co., Ltd. and using a D65 light source, and a spectrometer manufactured by Konica Minolta Co., Ltd. was used. Spectrophotometer (CM-3600A) and use D65 light source to measure haze (Haze value). S: YI value is above 8 and below 12 (YI value evaluation "S") A: YI value is above 12 and below 15 (YI value evaluation "A") B: YI value is 15 or more (YI value evaluation "B") S: Haze value is below 0.2% (Haze value evaluation "S") A: The Haze value exceeds 0.2% and is less than 0.5% (Haze value evaluation "A") B: Haze value exceeds 0.5% (Haze value evaluation "B")

＜Evaluation of bending resistance＞ On a 6-inch silicon wafer with a thickness of 625 μm±25 μm sputtered with about 100 nm of aluminum (Al) in advance, each resin composition was coated by a spin coater, and carried out at 100°C for 7 minutes Pre-baked. Thereafter, the oxygen concentration in the chamber was adjusted so that it was 10 mass ppm or less, and heat hardening treatment (curing treatment) was performed at 430°C for 1 hour to produce a polyimide resin film with a film thickness of 10 μm after hardening. Silicon wafer with Al sputtered film. The prepared sample was immersed in a 10% by mass hydrochloric acid aqueous solution for 1 day, and the polyimide resin film was peeled off from the silicon wafer. The stripped polyimide film was cut into a size of 15 mm×100 mm as a test piece.

Using the MIT-type repeated bending tester (MIT-DA, manufactured by Toyo Seiki), under the condition that a load of 250 g was applied to the produced test piece, the bending radius (R) was 2 mm, the bending angle was 135°, And under the condition of 90 times/minute, carry out the repeated bending test of 100,000 times. After the test, the sample was detached from the device, and those with no visual damage were evaluated as A, and those with damage were evaluated as B.

＜Evaluation of storage stability＞ The resin composition was preserved at 23°C, and after 1 week, a glass substrate of an agglomerated polyimide resin film was prepared with the same evaluation as <Evaluation of yellowness (YI value) and haze (Haze value), and the haze ( A Haze value) of 0.5% or less was evaluated as "A", and that of 0.5% or more was evaluated as "B".

＜Evaluation of modulus of elasticity＞ The elastic modulus was measured by cutting polyimide film with a size of 3 mm×20 mm as a test piece, and carried out by thermomechanical analysis. Use the Seiko Instruments Co., Ltd. (EXSTAR6000) as the measuring device, set the temperature at 25°C or 350°C, and apply a load from the initial tensile load of 20 mN in a nitrogen atmosphere at a load change rate of 100 mN/min. The elongation was measured with load changes up to a maximum of 1200 mN. The modulus of elasticity of the polyimide film (thickness: 10 μm) was determined from the slope of the obtained curve. In Table 4, those whose films were fragile and were broken during the measurement, or those whose Tg was low and broken halfway, were evaluated as "B". The evaluation criteria are as follows. Elastic modulus at 25°C S: Elastic modulus of 6 GPa or more (evaluation of elastic modulus "S") B: YI value is below 6 GPa (evaluation of elastic modulus "B") Elastic modulus at 350°C S: The modulus of elasticity is above 0.5 GPa (Evaluation of modulus of elasticity "S") B: YI value is below 0.5 GPa (evaluation of elastic modulus "B")

＜Sputter reheating test＞ An aluminum (Al) film of about 100 nm was sputtered on the glass substrate of the agglomerated imide resin produced by the same method as the above <Evaluation of yellowness (YI value) and haze (Haze value)>. The Al film is formed on the polyimide film.

The prepared samples were adjusted so that the oxygen concentration in the chamber was 10 mass ppm or less, and heat treatment was performed at 430°C for 1 hour to obtain a glass substrate with a polyimide resin film with a film thickness of 10 μm. Regarding the obtained glass substrate of agglomerated polyimide subjected to Al sputtering, the case where there was no swelling or cracking was evaluated as "S", and the case where cracking or swelling was present was evaluated as "B".

＜Evaluation of reheating test at 430℃＞ Evaluation was performed with the glass substrate and device of the agglomerated polyimide resin film produced by the method similar to <evaluation of yellowness (YI value) and haze (Haze value)> mentioned above.

Using the Spectotometer (SE6000) manufactured by Nippon Denshoku Industry Co., Ltd. and using the D65 light source to measure the YI value (YI(A)) of the glass substrate of agglomerated imide obtained by heating and hardening at 430°C, the value was measured in the library. The oxygen concentration was adjusted to be 10 mass ppm or less, and heat treatment was performed at 430°C for 1 hour to obtain a glass substrate with a polyimide resin film with a film thickness of 10 μm.

For the obtained glass substrate of agglomerated imide, use the Spectotometer (SE6000) manufactured by Nippon Denshoku Industry Co., Ltd. and use the D65 light source to measure the YI value (YI(B)) again, and compare the YI value before heating Evaluate the rate of change. The YI value (change rate) was calculated|required by the following formula. Change rate of YI value: ((YI(B)－YI(A))/YI(A)×100(%)) S: The change rate of YI value is 0% or more and 10% or less (YI value (change rate) evaluation "S") A: The change rate of YI value exceeds 10% and is less than 20% (YI value (change rate) evaluation "A") B: The change rate of YI value exceeds 20% (YI value (change rate) evaluation "B")

＜Evaluation of defects in IR curing＞ In this evaluation, on the assumption of mass production, the number of defects on the surface of the polyimide film when the resin composition is continuously subjected to IR (infrared ray) heat curing (curing) treatment was evaluated. On an alkali-free glass substrate of 100 mm long x 100 mm wide x 0.5 mm thick (hereinafter also referred to as "glass substrate" or simply "substrate"), harden the area within 5 mm from the end of the glass substrate The resin compositions of Examples and Comparative Examples were applied so that the subsequent film thickness would be 10 μm. The coating system used a slit coater (LC-R300G, manufactured by SCREEN Finetech Solutions). With respect to the obtained glass substrate with a coating film, the solvent was removed using a reduced-pressure dryer (manufactured by Tokyo Ohka Industry Co., Ltd.) under conditions of 80° C., 100 Pa, and 30 minutes to obtain a coating film sample.

Thereafter, using an IR curing furnace AMK-1707 (light source: ceramic heater, furnace volume 50 L, manufactured by AMK), a group of 10 coating film samples of the same resin composition were placed in a nitrogen atmosphere at 120°C After heating at low temperature for 10 minutes, the temperature was raised at 10°C/min, and heated at 430°C for 60 minutes. Using this as one batch, heat treatment was performed using five batches of the same resin composition (10 sheets * 5 batches of 50 sheets in total were processed). In addition, when processing other compositions, the IR curing furnace should be fired at 500°C for 5 hours or more, and the pipes such as pipes should be cleaned before use. Next, using the fifth polyimide resin film from the upper stage of the fifth batch, the defects on the surface of the polyimide resin film were evaluated using a defect inspection device (LCF-5505XU, manufactured by Takano Co., Ltd.). Check the number of defects larger than 10 μm. And evaluation was performed based on the following reference|standard. The number of defects is less than 25 : A (excellent) The number of defects is more than 25 and less than 50: B (excellent) The number of defects is more than 50 and less than 100: C (good) The number of defects is more than 100 and less than 200: D (pass) The number of defects is more than 200 : E (Unqualified)

＜Evaluation of outgassing＞ When a polyimide resin film is used as a TFT substrate, an inorganic film (for example, SiN) is formed on the obtained polyimide resin film, and an annealing treatment of the inorganic film is performed. If outgassing occurs during this annealing treatment, it will become a bad sample, so the higher the outgassing start temperature, the better. The evaluation of the degassing start temperature was carried out by the following method.

On an alkali-free glass substrate of 100 mm long x 100 mm wide x 0.5 mm thick (hereinafter also referred to as "glass substrate" or simply "substrate"), harden the area within 5 mm from the end of the glass substrate The resin compositions of Examples and Comparative Examples were applied so that the subsequent film thickness would be 10 μm. The coating system used a slit coater (LC-R300G, manufactured by SCREEN Finetech Solutions). With respect to the obtained glass substrate with a coating film, the solvent was removed using a reduced-pressure dryer (manufactured by Tokyo Ohka Industry Co., Ltd.) under conditions of 80° C., 100 Pa, and 30 minutes to obtain a coating film sample. Thereafter, the coating film samples of the resin composition were used as a group of 5 pieces, using an IR curing furnace AMK-1707 (light source: ceramic heater, furnace volume 50 L, manufactured by AMK), under a nitrogen atmosphere and at 120°C After heating for 10 minutes, the temperature was raised at 10°C/min, and heated at 430°C for 60 minutes to obtain a polyimide resin film formed on a glass substrate.

A SiN film with a thickness of 100 nm was formed on the obtained polyimide resin film by plasma CVD. With respect to the glass substrate on which the laminated body of the obtained SiN/polyimide resin film was formed, it heat-processed under the following conditions using IR curing furnace AMK-1707. a. Under nitrogen atmosphere, heat at 120°C for 10 minutes, then heat up at 10°C/min, and heat at 480°C for 60 minutes b. Under nitrogen atmosphere, heat at 120°C for 10 minutes, then heat up at 10°C/min, and heat at 470°C for 60 minutes c. Under nitrogen atmosphere, heat at 120°C for 10 minutes, then heat up at 10°C/min, and heat at 460°C for 60 minutes d. Under nitrogen atmosphere, heat at 120°C for 10 minutes, then heat up at 10°C/min, and heat at 450°C for 60 minutes e. Under nitrogen atmosphere, heat at 120°C for 10 minutes, then heat up at 10°C/min, and heat at 440°C for 60 minutes In addition, the presence or absence of outgassing was evaluated on the basis of the following criteria; Under the conditions of a. above, the SiN film has/does not bulge: A (excellent) Under the conditions of b. above, the SiN film bulges: B (excellent) Under the conditions of c. above, the SiN film bulges: C (good) Under the conditions of d. above, the SiN film bulges: D (qualified) Under the conditions of e. above, the SiN film bulges: E (Unqualified)

[Synthesis Examples 1 and 2] (Synthesis Example 1-1-1) After replacing the 500 ml four-necked flask equipped with a reflux tube and a Dean-Stark tube with nitrogen, add 20 g of N-methyl-2-pyrrolidone (NMP), 9,9-bis(4-amine phenyl) (44BAFL) 22.22 mmol, and stirred to dissolve 44BAFL. Thereafter, 20.00 mmol of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), 11.41 g of N-methyl-2-pyrrolidone (NMP), and 21.76 g of toluene were added at 40°C. After g, polymerization was carried out at 180° C. for 4 hours under nitrogen flow. One hour after reaching 180°C, a mixture of water and toluene was extracted from the Dean-Stark tube. The weight average molecular weight (Mw) of the imide after 4 hours of reaction was 19,178, and the number average molecular weight (Mn) was 8,283.

After reacting for 4 hours, cool until the internal temperature reaches 80°C, add 82.82 mmol of benzoic acid 4-aminophenyl-4'-amino ester (APAB) and 100 g of NMP, and stir to make APAB completely dissolve. After visually confirming that APAB is completely dissolved, 86.17 mmol of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added, and stirred at 80°C for 1 hour and 2 hours at 60°C under nitrogen flow Thereafter, polymerization was carried out overnight at room temperature. Then, the said NMP was added, and it adjusted so that the solid content might become 12 mass %, and the NMP solution (henceforth, also referred to as a varnish) of a polyimide-polyamide acid copolymer was obtained. The weight average molecular weight (Mw) of the obtained polyamic acid-imide copolymer was 155,382, and the number average molecular weight (Mn) was 64,063.

(Synthesis Example 1-1-2) (a) Synthesis of polyimide After replacing the 500 ml four-necked flask equipped with a reflux tube and a Dean-Stark tube with nitrogen, add 20 g of N-methyl-2-pyrrolidone (NMP), 9,9-bis(4-amine phenyl) (44BAFL) 22.22 mmol, and stirred to dissolve 44BAFL. Thereafter, 20.00 mmol of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), 11.41 g of N-methyl-2-pyrrolidone (NMP), and 21.76 g of toluene were added at 40°C. After g, polymerization was carried out at 180° C. for 4 hours under nitrogen flow. A mixture of water and toluene was extracted from the Dean-Stark tube 1 hour after reaching 180°C. The weight average molecular weight (Mw) of the imide after 4 hours of reaction was 19,804, and the number average molecular weight (Mn) was 8,886. After reacting for 4 hours, it cooled until the internal temperature became 80 degreeC, NMP was added, and the NMP solution (it is also called a polyimide varnish hereafter) of the density|concentration of 20 mass % of polyimide was obtained.

(b) Polyamide Synthesis After replacing the 500 ml four-necked flask with nitrogen, 82.82 mmol of 4'-aminophenylbenzoic acid (APAB) 82.82 mmol and 100 g of NMP were added, and APAB was completely dissolved while stirring. After visually confirming that APAB was completely dissolved, 86.17 mmol of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added, stirred at 80°C for 5 hours under a nitrogen stream, and then adjusted at room temperature. Night polymerization. Then, the said NMP was added, and it adjusted so that the solid content might become 20 mass %, and the NMP solution (henceforth, also referred to as a polyamide acid varnish) of polyamide was obtained. The weight average molecular weight (Mw) of the obtained polyamic acid was 73,044, and the number average molecular weight (Mn) was 34,917.

(c) Polyamide-imide copolymer synthesis The polyimide varnish obtained in (a) is mixed with the polyamic acid varnish obtained in (b), and stirred at room temperature for 24 hours to obtain a polyamide acid-imide copolymer NMP solution.

(Synthesis Example 1-12) After replacing the 500 ml four-necked flask equipped with a reflux tube and a Dean-Stark tube with nitrogen, add 20 g of N-methyl-2-pyrrolidone (NMP), 9,9-bis(4-amine phenyl) (44BAFL) 22.22 mmol, and stirred to dissolve 44BAFL. Thereafter, 10.00 mmol of 9,9-bis(3,4-dicarboxyphenyl) phthalic anhydride (BPAF), 10.00 mmol of biphenyltetracarboxylic dianhydride, and N-methyl-2-pyrrole were added at 40°C. After 11.41 g of pyridone (NMP) and 21.76 g of toluene, a polymerization reaction was carried out at 180° C. for 4 hours under nitrogen flow. A mixture of water and toluene was extracted from the Dean-Stark tube 1 hour after reaching 180°C. The weight average molecular weight (Mw) of the imide after 4 hours of reaction was 19,342, and the number average molecular weight (Mn) was 9,242.

After 4 hours of reaction, cool until the internal temperature reaches 80°C, add 82.82 mmol of benzoic acid 4-aminophenyl-4'-amino ester (APAB) and 100 g of NMP, and completely dissolve APAB while stirring. . After visually confirming that APAB was completely dissolved, 86.17 mmol of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added, and polymerization reaction was performed at 80° C. for 1 hour under a nitrogen stream. Then, the said NMP was added and adjusted so that the solid content might become 12 mass %, and the NMP solution (henceforth, also referred to as a varnish) of a polyimide-polyamic acid copolymer was obtained. The weight average molecular weight (Mw) of the obtained polyamic acid-imide copolymer was 40,578, and the number average molecular weight (Mn) was 19,128.

(Synthesis Examples 1-2 to 1-11, and 1-13 to 1-30) In the above Synthesis Example 1-1-1, the types and addition amounts of the raw materials were changed as described in Table 1, except that, in the same manner as in Synthesis Example 1-1-1, polyamic acid- Imide copolymer varnish.

(Synthesis Example 1-1-3) To the NMP solution synthesized in the above Synthesis Example 1-1-1, 0.04 mol of 1-methylimidazole was added relative to 1 mol of the repeating unit of the polyimide-polyamide acid copolymer to obtain Polyamide acid-imide copolymer varnish.

(Synthesis Example 1-1-4) To the NMP solution synthesized in the above Synthesis Example 1-1-1, 0.13 mol of 1-methylimidazole was added relative to 1 mol of the repeating unit of the polyimide-polyamide acid copolymer to obtain Polyamide acid-imide copolymer varnish.

(Synthesis Example 1-1-5) To the NMP solution synthesized in the above Synthesis Example 1-1-1, 0.13 mol of N-Bоc-imidazole was added relative to 1 mol of the repeating unit of the polyimide-polyamide acid copolymer to obtain Polyamide acid-imide copolymer varnish.

(Synthesis Example 1-1-6) To the NMP solution synthesized in Synthesis Example 1-1-1 above, 0.04 moles of 1-methylimidazole, 0.04 Mole's N-Bоc-imidazole to obtain polyamide acid-imide copolymerized varnish.

(Synthesis Example 2-1) After nitrogen replacement was carried out in a 500 ml four-neck flask, 49.50 mmol of 4'-aminophenylbenzoate (APAB) and 80 g of NMP were added, and APAB was completely dissolved while stirring. After visually confirming that APAB was completely dissolved, 50.00 mmol of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added, stirred at 80°C for 5 hours under nitrogen flow, and then adjusted at room temperature. Night polymerization. Then, the said NMP was added and it adjusted so that the solid content might become 12 mass %, and the NMP solution (henceforth, also referred to as a polyamic acid varnish) of a polyamic acid was obtained. The weight average molecular weight (Mw) of the obtained polyamic acid was 63,353, and the number average molecular weight (Mn) was 29,472.

(Synthesis Example 2-2) After replacing the 500 ml four-neck flask with nitrogen, 31.68 mmol of 4'-aminobenzoic acid 4-aminophenyl ester (APAB), 7.92 mmol of 9,9-bis(aminophenyl) fluorene (BAFL), 70 g of NMP was stirred to completely dissolve APAB and BAFL. After visually confirming that APAB and BAFL are completely dissolved, add 32.00 mmol of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 9,9-bis(3,4-dicarboxyphenyl) Acid anhydride (BPAF) 8.00 mmol, NMP 22.29 g, stirred at 80° C. for 5 hours under a nitrogen stream, and then polymerized overnight at room temperature. Then, the said NMP was added and it adjusted so that the solid content might become 12 mass %, and the NMP solution (henceforth, also referred to as a polyamic acid varnish) of a polyamic acid was obtained. The weight average molecular weight (Mw) of the obtained polyamic acid was 72,118, and the number average molecular weight (Mn) was 33,741.

(Synthesis Example 2-3) The polyamic acid-imide copolymer varnish was synthesized in the same manner as in Example 1 of International Publication No. 2020/138360 Handbook.

(Synthesis Example 2-4) The polyimide varnish was synthesized in the same manner as in Example 1 of International Publication No. 2019/188305.

The abbreviations of the components in the following table have the following meanings respectively. BPDA: 3,3',4,4'-Biphenyltetracarboxylic dianhydride ODPA: 4,4'-oxydiphthalic dianhydride BPAF: 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride TAHQ: Terephthalic bis(trimellitic anhydride) BPF-PA: 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]stilbenic anhydride 6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride APAB: 4-Aminophenyl-4'-aminobenzoate pPD: p-phenylenediamine 44BAFL: 9,9-bis(4-aminophenyl) terpine 33BAFL: 9,9-bis(3-aminophenyl) terpene BFAF: 9,9-bis(3-fluoro-4-aminophenyl) fennel 33DAS: 3,3'-Diaminodiphenylsulfone 44DAS: 4,4'-Diaminodiphenylsulfone 44ODA: 4,4'-diaminodiphenyl ether 34ODA: 3,4'-diaminodiphenyl ether BAOFL: 9,9-bis [4- (aminophenoxy) phenyl] terpene BAHF: 9,9-bis[3-amino-4-hydroxyphenyl] fennel NMP: N-methyl-2-pyrrolidone DMF: N,N-Dimethylformamide

<Embodiment I> The varnish obtained in each synthesis example was directly used as a resin composition, and evaluated according to the above-mentioned method. The synthesis results are shown in Table 1, and the evaluation results are shown in Tables 2-4.

It is clear from Table 1 and Table 2 that the polyimide film (Comparative Example 1-1) composed only of the structural unit N (polyamic acid) is excellent in residual stress, but its YI value and Haze value are large. In addition, the polyamic acid obtained from the polyamic acid synthesized with the same composition as the polyamic acid-imide copolymer described in Comparative Example 1-2 (the molar ratio of the monomers constituting X ₁ to X ₄ is the same) Although the imide film has excellent YI value and Haze value, its residual stress is relatively large, and it does not exhibit sufficient performance to be used as a substrate for optical displays.

Furthermore, the polyamide obtained by not using general formula (A-1) or (A- ₂ ) as X in structural unit N and using the method described in Example 1 of International Publication No. 2020/138360 Handbook The polyimide film obtained from the acid-imide copolymer (Comparative Example 1-3) was colored yellow during the heat treatment step at 430°C, and the YI value and Haze value were relatively large. Also, a polyimide film composed only of the structural unit M (polyimide) and obtained from polyimide obtained by the method described in Example 1 of International Publication No. 2019/188305 Handbook (Comparative Example 1-4) The yellowing in the heat treatment step at 430°C is suppressed, but on the other hand, the residual stress is high, and the performance is insufficient when used as a substrate for an optical display.

On the other hand, the compounds represented by the general formula (A-1) or (A- ₂ ) including the structural unit represented by the general formula (1) and X2 described in Examples 1-1 to 1-30 The yellowness (YI value) of the polyimide film obtained by the polyamide acid-imide copolymer with the structure is as low as 15 or less, and the haze (Haze value) is also less than 0.5%, which is enough to be used as an optical display. The performance of the substrate used. In addition, the residual stress is also as low as 25 MPa or less, and the mechanical properties are sufficient. From the above, it was confirmed that the polyimide resin film obtained from the resin composition of the present invention is a resin film with less yellowness, less haze, and lower residual stress.

Specifically, in the present invention, a resin film having a residual stress of 25 MPa or less, a yellowness of 15 or less, and a haze of 0.5% or less is obtained.

Also, a polyamic acid-imide copolymer varnish obtained by separately synthesizing polyamic acid and polyimide as in Synthesis Example 1-1-2, and then mixing them for reaction can be obtained . The polyimide film that obtains by this varnish is as shown in embodiment 1-1-2, and embodiment 1-1-1 is equivalent performance. It means that (c) polyamic acid-imide copolymer can be obtained by mixing and reacting (a) polyamic acid and (b) polyimide synthesized at a specific molar ratio.

Also, in Table ₂ , the molar ratio of the structural unit N _of the polyamic acid comprising X1 and X2 to the structural unit M of the polyimide comprising _X3 and _X4 (the molar number of the structural unit N : Molar number of the structural unit M) in Examples 1-8 in which 60:40, a transparent film with excellent yellowness and haze can be obtained, the residual stress is also low at 25 MPa or less, and the mechanical properties are sufficient.

Also, in Table 2, as shown in Examples 1-6, 1-14, and 1-15, if the ratio of X ₄ /X ₃ is 1.01 to 2 and the ratio of diamine to acid dianhydride is increased, polyamide The ratio of the terminal of the amine to become an amine increases, so when it reacts with polyamic acid, the reactivity between polyamic acid and polyimide increases, and the polyimides are well dispersed with each other when forming a film, so yellowness can be obtained ( YI value) and haze (Haze value) excellent transparent film. Moreover, according to Examples 1-6, 1-14, and 1-15, the yellowness (YI value) of the composition whose ratio _X4 / _X3 becomes 1.11 is low and is especially preferable.

In addition, in Table 3, as shown in Examples 2-2 to 2-5, polyimide-polyamic acid copolymers containing 1-methylimidazole or N-Boc-imidazole as imidization catalysts The yellowness (YI value) of the obtained film is lower, and it can be preferably used as a substrate for a display.

Also, in Table 4, as shown in Comparative Example 2-1 (Synthesis Example 2-1), the elasticity of the polyimide film at 25°C and 350°C obtained from polyamic acid composed only of structural unit N The modulus is high, and even if it is heated to 430°C after Al sputtering, it will not bulge or crack, but the YI value is high, and its performance as a substrate for optical displays is insufficient.

Also, in Table 4, as shown in Comparative Example 2-2 (Synthesis Example 2-2), when the modulus of elasticity at 350°C is low, if it is heated to 430°C after Al sputtering, the Bulging or cracking occurs. The reason for this is considered to be that the elastic modulus at high temperature is low due to the high content of polyimide, so that the difference in shrinkage force between Al and polyimide increases at a high temperature range above 350°C. Crack or bulge.

On the other hand, when the modulus of elasticity at 350°C is 0.5 GPa or more, even if the difference in shrinkage force increases in the high-temperature region, the strength of the film is high, so there is no crack or bulge, and it can be compared Ideally used as a substrate for displays. Furthermore, as shown in Examples 3-1 to 3-3 in Table 4, the film with a high elastic modulus at 350°C and a haze (Haze value) of 0.5% or less without phase separation was reheated at 430°C The change rate of YI value in the test is small, and it can be preferably used as a substrate for displays.

Specifically, in the present invention, a resin film having an elastic modulus at 25° C. of 6 GPa or more, an elastic modulus at 350° C. of 0.5 GPa or more, and a haze of 0.5% or less can be obtained.

[Table 1] Table 1 serial number Polyamide Department Polyimide Department Amide part content Morby Tetracarboxylic dianhydride (A-1) [Mole%] Diamine (B-1) [Mole %] Tetracarboxylic dianhydride (A-2) [Mole%] Diamine (B-2) [Mole %] BPDA ODPA TAHQ APAB PPD 44BAFL BPAF BPDA ODPA BPF-PA 6FDA APAB 44BAFL 33BAFL BFAF 33DAS 44DAS 44ODA 34ODA BAOFL BAHF mol% [B-2]/[A-2] [B-1]/[A-1] ([Bl]＋[B-2])/ ([A-1A-2]) Synthesis Example 1 1-1 100 100 100 100 20 1.11 0.96 0.988 1-2 100 100 100 100 20 1.11 0.96 0.988 1-3 100 100 100 100 20 1.11 0.96 0.988 1-4 100 100 100 100 20 1.11 0.96 0.988 1-5 100 100 100 100 20 1.11 0.96 0.988 2 100 100 100 100 20 1.11 0.96 0.99 3 100 100 100 100 20 1.11 0.96 0.988 4 100 100 100 100 20 1.11 0.969 0.996 5 100 100 100 100 30 1.11 0.95 0.996 6 100 100 100 100 5 1.01 0.99 0.996 7 100 100 100 100 40 1.11 0.92 0.992 8 100 100 100 100 20 1.11 0.969 0.996 9 100 100 100 100 20 1.11 0.969 0.996 10 100 100 100 100 20 1.11 0.969 0.996 11 100 100 100 100 20 1.11 0.96 0.988 12 100 100 50 50 100 20 1.11 0.96 0.988 13 100 100 50 50 100 20 1.11 0.96 0.988 14 100 100 50 50 100 20 1.25 0.94 0.991 15 100 100 50 50 100 20 2 0.84 0.99 16 100 100 100 50 50 20 1.11 0.969 0.996 17 100 100 100 50 50 20 1.11 0.96 0.988 18 100 100 100 50 50 30 1.11 0.96 0.988 19 100 100 50 50 100 20 1.11 0.96 0.988 20 100 100 100 50 50 20 1.11 0.969 0.996 twenty one 100 100 50 50 100 20 1.11 0.96 0.988 twenty two 100 100 50 50 100 20 1.11 0.96 0.988 twenty three 100 100 75 25 100 20 1.11 0.969 0.996 twenty four 80 20 100 100 100 20 1.11 0.96 0.988 25 100 100 100 100 20 1.11 0.96 0.988 26 100 80 20 100 100 20 1.11 0.96 0.988 27 100 80 20 100 100 20 1.11 0.96 0.988 28 50 50 100 100 100 20 1.11 0.96 0.988 29 100 100 100 100 20 1.11 0.969 0.996 30 100 100 100 65 35 20 1.11 0.969 0.996

[Table 2] Table 2 Synthesis example Yellowness (YI value) Haze (Haze value) residual stress Example 1 1-1 1-1-1 A S A 1-2 1-1-2 A S A 1-3 1-1-3 S S A 1-4 1-1-4 S S A 1-5 1-1-5 S S A 1-6 1-1-6 S S A 2 1-2 A S A 3 1-3 A S A 4 1-4 S S S 5 1-5 S S A 6 1-6 A S S 7 1-7 S S A 8 1-8 A S A 9 1-9 A S S 10 1-10 A S S 11 1-11 A S A 12 1-12 S S A 13 1-13 S S A 14 1-14 A S A 15 1-15 A S A 16 1-16 A S A 17 1-17 S A A 18 1-18 S A A 19 1-19 A S A 20 1-20 A S A twenty one 1-21 S S A twenty two 1-22 A A S twenty three 1-23 A S A twenty four 1-24 A S A 25 1-25 A A A 26 1-26 A A S 27 1-27 A S A 28 1-28 A S A 29 1-29 A S A 30 1-30 A S A Comparative example 1 1 2-1 B B A 2 2-2 A A B 3 2-3 B B A 4 2-4 A A B

[table 3] table 3 Synthesis example storage stability Example 2 1 1-1 A 2 1-3 A 3 1-4 A 4 1-5 A 5 1-6 A

[Table 4] Table 4 Synthesis example YI value Elastic modulus at 25℃ 350℃ modulus of elasticity Sputtering reheat test 430℃ reheating test Example 3 1 1-4 S S S S S 2 1-12 S S S S S 3 1-13 S S S S S Comparative example 2 1 2-1 B S S S S 2 2-2 S B B B B

<Embodiment IV>

(Synthesis Example 1-31) Except having changed the quantity of APAB of said synthesis example 1-1-1 to 83.02 mmol, it carried out similarly to synthesis example 1-1-1. The weight average molecular weight (Mw) of the obtained polyamic acid-imide copolymer was 173,000.

(Synthesis Example 1-32) Except changing the BAFL of the said synthesis example 1-1-1 to 33DAS, and changing the quantity of APAB to 83.02 mmol, it carried out similarly to the synthesis example 1-1-1. The weight average molecular weight (Mw) of the obtained polyamic acid-imide copolymer was 171,000.

(Synthesis Example 1-33) Except having changed the quantity of APAB of said synthesis example 1-1-1 into 83.45 mmol, it carried out similarly to synthesis example 1-1-1. The weight average molecular weight (Mw) of the obtained polyamic acid-imide copolymer was 224,000.

(Synthesis Example 1-34) Except having changed the BAFL of the said synthesis example 1-1-1 into 33DAS, and the quantity of APAB into 83.45 mmol, it carried out similarly to the synthesis example 1-1-1. The weight average molecular weight (Mw) of the obtained polyamic acid-imide copolymer was 221,000.

(Synthesis Example 3-1) N-methyl-2-pyrrolidone (NMP) (water content 250 mass ppm), 180.77 g (800 mmol) of 4-aminophenyl 4-aminobenzoate (APAB, purity 99.5%, manufactured by Junyoshi Pharmaceutical Co., Ltd.) was added, and APAB was dissolved by stirring. Thereafter, 235.38 g (792 mmol) of biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA, purity 99.5%, manufactured by Manac Co., Ltd.) was added, and at 70° C. And the polymerization reaction was carried out under stirring for 5 hours. Thereafter, it was cooled to room temperature and left to stand under a nitrogen stream for 8 days. The said NMP was added and adjusted so that the solution viscosity might become 10,000 mPa*s, and the NMP solution (henceforth also referred to as varnish) of polyamic acid was obtained by this. The weight average molecular weight (Mw) of the obtained polyamic acid was 152,000.

(Synthesis Example 3-2) N-methyl-2-pyrrolidone (NMP) (water content 250 mass ppm), 181.69 g (800 mmol) of 4-aminophenyl 4-aminobenzoate (APAB, purity 99.5%, manufactured by Junyoshi Pharmaceutical Co., Ltd.) was added, and APAB was dissolved by stirring. Thereafter, 235.38 g (792 mmol) of biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA, purity 99.5%, manufactured by Manac Co., Ltd.) was added, and at 70° C. And the polymerization reaction was carried out under stirring for 5 hours. Thereafter, it was cooled to room temperature and left to stand under a nitrogen stream for 8 days. The said NMP was added and adjusted so that the solution viscosity might become 10,000 mPa*s, and the NMP solution (henceforth also referred to as varnish) of polyamic acid was obtained by this. The weight average molecular weight (Mw) of the obtained polyamic acid was 175,000.

(Synthesis Example 3-3) N-methyl-2-pyrrolidone (NMP) (water content 250 mass ppm), 145.35 g (800 mmol) of 4-aminophenyl 4-aminobenzoate (APAB, purity 99.5%, manufactured by Japan Junyo Pharmaceutical Co., Ltd.), and 4,4'-diaminobis 39.53 g (159 mmol) of phenylsulfone (4,4'-DAS, purity 99.5%, Seika Co., Ltd.) was stirred to dissolve APAB and 4,4'-DAS. Thereafter, 235.38 g (800 mmol) of biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA, purity 99.5%, manufactured by Manac Co., Ltd.) was added, and at 70° C. And the polymerization reaction was carried out under stirring for 5 hours. Thereafter, it was cooled to room temperature and left to stand under a nitrogen stream for 8 days. The said NMP was added and adjusted so that the solution viscosity might become 10,000 mPa*s, and the NMP solution (henceforth also referred to as varnish) of polyamic acid was obtained by this. The weight average molecular weight (Mw) of the obtained polyamic acid was 173,000.

(Synthesis Example 3-4) N-methyl-2-pyrrolidone (NMP) (water content 250 mass ppm), 181.69 g (800 mmol) of 4-aminophenyl 4-aminobenzoate (APAB, purity 99.5%, manufactured by Junyoshi Pharmaceutical Co., Ltd.) was added, and APAB was dissolved by stirring. Thereafter, 235.38 g (796 mmol) of biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA, purity 99.5%, manufactured by Manac Co., Ltd.) was added, and at 70° C. And the polymerization reaction was carried out under stirring for 5 hours. Thereafter, it was cooled to room temperature and left to stand under a nitrogen stream for 8 days. The said NMP was added and adjusted so that the solution viscosity might become 10,000 mPa*s, and the NMP solution (henceforth also referred to as varnish) of polyamic acid was obtained by this. The weight average molecular weight (Mw) of the obtained polyamic acid was 242,000.

(Synthesis Example 3-5) N-methyl-2-pyrrolidone (NMP) (water content 250 mass ppm), 182.42 g (800 mmol) of 4-aminophenyl 4-aminobenzoate (APAB, purity 99.5%, manufactured by Junyoshi Pharmaceutical Co., Ltd.) was added, and APAB was dissolved by stirring. Thereafter, 235.38 g (799 mmol) of biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA, purity 99.5%, manufactured by Manac Co., Ltd.) was added, and at 70° C. And the polymerization reaction was carried out under stirring for 5 hours. Thereafter, it was cooled to room temperature and left to stand under a nitrogen stream for 8 days. The said NMP was added and adjusted so that the solution viscosity might become 10,000 mPa*s, and the NMP solution (henceforth also referred to as varnish) of polyamic acid was obtained by this. The weight average molecular weight (Mw) of the obtained polyamic acid was 241,000.

(Synthesis Example 3-6) N-methyl-2-pyrrolidone (NMP) (water content 250 mass ppm), 80 mmol of 4-aminophenyl 4-aminobenzoate (APAB, purity 99.5%, manufactured by Japan Junyo Pharmaceutical Co., Ltd.) was added and stirred to dissolve APAB. Thereafter, bis(1,3-dioxa-1,3-dihydroisobenzofuran-5-carboxylic acid) 2,2',3,3',5,5'-hexamethylbiphenyl - 79.6 mmol of 4,4'-diyl (manufactured by Honshu Chemical Industry Co., Ltd.), was subjected to a polymerization reaction at 70° C. under stirring for 5 hours under nitrogen flow. Thereafter, it was cooled to room temperature and left to stand under a nitrogen stream for 8 days. The said NMP was added and adjusted so that the solution viscosity might become 10,000 mPa*s, and the NMP solution (henceforth also referred to as varnish) of polyamic acid was obtained by this. The weight average molecular weight (Mw) of the obtained polyamic acid was 172,000.

(reference example 4-1) The NMP solution of the polyimide-polyamic acid copolymer (hereinafter also referred to as PAI) synthesized in Synthesis Example 1-1-1 was used to perform the above-mentioned IR curing defect evaluation and outgassing evaluation. The results are described in Table 6.

(Example 4-1) Using the NMP solution of the polyimide-polyamic acid copolymer synthesized in Synthesis Example 1-32, add 1 mass part of the table with respect to 100 mass parts of the polyimide-polyamic acid copolymer. The imidization catalyst 1 (1-methylimidazole) described in 6 was stirred at room temperature for 24 hours to obtain a polyamic acid-imide copolymerized varnish. Using this varnish, the above-mentioned IR curing defect evaluation and outgassing evaluation were performed. The results are described in Table 6.

(Example 4-2 to 30) Using the NMP solution of the polyimide-polyamic acid copolymer described in Table 6, add the imidization catalyst described in Table 5 in the amount of addition described in Table 6, and in addition, the same as in the examples 4-1 Obtain polyamic acid-imide copolymerized varnish in the same manner. Using the obtained varnish, the above-mentioned IR curing defect evaluation and outgassing evaluation were performed. The results are described in Table 6.

(Example 4-31) Using the NMP solution of the polyimide-polyamic acid copolymer described in Table 6, add the imidization catalyst described in Table 5 in the addition amount described in Table 6, and then add 100 parts by mass of NMP with respect to A polyamic acid-imide copolymerized varnish was obtained in the same manner as in Example 4-1 except that 20 parts by mass of cyclobutane which is an aprotic polar substance having a boiling point of 250-350° C. was used. Using the obtained varnish, the above-mentioned IR curing defect evaluation and outgassing evaluation were performed. The results are described in Table 6.

(Comparative Example 5-1) The NMP solution of polyamic acid (hereinafter also referred to as PAA) synthesized in Synthesis Example 3-1 was used to perform the above-mentioned IR curing defect evaluation and outgassing evaluation. The results are described in Table 7.

(Example 5-1) Using the NMP solution of the polyamic acid synthesized in Synthesis Example 3-2, add the imidization catalyst 1 (1 -methylimidazole), and stirred at room temperature for 24 hours to obtain a polyamic acid varnish. Using this varnish, the above-mentioned IR curing defect evaluation and outgassing evaluation were performed. The results are described in Table 7.

(Examples 5-2 to 29, Comparative Example 5-2) Using the NMP solution of polyamic acid described in Table 7, and adding the imidization catalyst described in Table 5 in the amount described in Table 7, it was obtained in the same manner as in Example 5-1. Polyamide varnish. Using the obtained varnish, the above-mentioned IR curing defect evaluation and outgassing evaluation were performed. The results are described in Table 7.

(Example 5-30) Using the NMP solution of polyamic acid described in Table 7, add the imidization catalyst described in Table 5 in the amount added in Table 7, and then add 20 parts by mass relative to 100 parts by mass of NMP. A polyamic acid varnish was obtained in the same manner as in Example 5-1, except that cyclobutane, which is an aprotic polar substance having a boiling point of 250-350° C., was used. Using the obtained varnish, the above-mentioned IR curing defect evaluation and outgassing evaluation were performed. The results are described in Table 7.

[table 5] table 5 imidization catalyst Compound name 1 1-Methylimidazole 2 N-BOC imidazole 3 2-Methylimidazole 4 2-Phenylimidazole 5 Benzimidazole 6 2-Ethyl-4-methylimidazole 7 4-Ethyl-2-methylimidazole 8 4-Methyl-2-phenylimidazole 9 2-Undecylimidazole 10 1-Benzyl-2-methylimidazole 11 1-Benzyl-2-phenylimidazole 12 1H-imidazole 13 1,2-Dimethylimidazole 14 4-Dimethylaminopyridine 15 2,2'-bipyridine 16 Nicotinic acid-pyridine carboxylic acid 17 Isoquinoline 18 pyridine 19 2-Methylpyridine 20 1,8-Diazabicyclo[5.4.0]-7-undecene twenty one 1,4-Diazabicyclo[2.2.2]octane twenty two N-Methylmorpholine twenty three Triethylamine

[Table 6] Table 6 Reference example/Example/Comparative example resin Weight average molecular weight [Mw] imidization catalyst bp250- 350 ^o C aprotic polar substance evaluation item Synthesis example polymer structure type Amount added (parts by mass) IR Curing Defect Evaluation Outgassing evaluation Reference example 4 1 1-1-1 PAI 155,382 none - - E. E. Example 4 1 1-31 PAI 173,000 none - - D. D. Example 4 2 1-31 PAI 173,000 1 1 - B C Example 4 3 1-32 PAI 171,000 2 1 - B C Example 4 4 1-32 PAI 171,000 1 5 - B B Example 4 5 1-31 PAI 173,000 2 5 - B B Example 4 6 1-31 PAI 173,000 1 10 - B B Example 4 7 1-32 PAI 171,000 2 10 - B B Example 4 8 1-31 PAI 173,000 3 10 - C C Example 4 9 1-32 PAI 171,000 4 10 - C C Example 4 10 1-31 PAI 173,000 5 10 - C C Example 4 11 1-32 PAI 171,000 6 10 - C C Example 4 12 1-31 PAI 173,000 7 10 - C C Example 4 13 1-32 PAI 171,000 8 10 - C C Example 4 14 1-31 PAI 173,000 9 10 - C C Example 4 15 1-32 PAI 171,000 10 10 - C C Example 4 16 1-31 PAI 173,000 11 10 - C C Example 4 17 1-31 PAI 173,000 12 10 - D. C Example 4 18 1-32 PAI 171,000 13 10 - D. C Example 4 19 1-31 PAI 173,000 14 10 - C C Example 4 20 1-32 PAI 171,000 15 10 - C C Example 4 twenty one 1-31 PAI 173,000 16 10 - C C Example 4 twenty two 1-32 PAI 171,000 17 10 - C C Example 4 twenty three 1-31 PAI 173,000 18 10 - D. C Example 4 twenty four 1-31 PAI 173,000 19 10 - C C Example 4 25 1-32 PAI 171,000 20 10 - C C Example 4 26 1-31 PAI 173,000 twenty one 10 - C C Example 4 27 1-32 PAI 171,000 twenty two 10 - C C Example 4 28 1-32 PAI 171,000 twenty three 10 - D. C Example 4 29 1-33 PAI 224,000 1 10 - A B Example 4 30 1-34 PAI 221,000 2 10 - A B Example 4 31 1-33 PAI 224,000 2 10 cyclotin A A

[Table 7] Table 7 Example/Comparative example resin Weight average molecular weight [Mw] imidization catalyst Aprotic polar substances with bp250-350℃ evaluation item Synthesis example polymer structure type Amount added (parts by mass) IR Curing Defect Evaluation Outgassing evaluation Comparative Example 5 1 3-1 PAAA 152,000 none - - E. E. Example 5 1 3-2 PAAA 175,000 1 1 - C C Example 5 2 3-3 PAAA 173,000 2 1 - C C Example 5 3 3-2 PAAA 175,000 1 5 - C B Example 5 4 3-3 PAAA 173,000 2 5 - C B Example 5 5 3-2 PAAA 175,000 1 10 - B B Example 5 6 3-3 PAAA 173,000 2 10 - B B Example 5 7 3-2 PAAA 175,000 3 10 - D. D. Example 5 8 3-3 PAAA 173,000 4 10 - D. D. Example 5 9 3-2 PAAA 175,000 5 10 - D. D. Example 5 10 3-3 PAAA 173,000 6 10 - D. D. Example 5 11 3-2 PAAA 175,000 7 10 - D. D. Example 5 12 3-3 PAAA 173,000 8 10 - D. D. Example 5 13 3-2 PAAA 175,000 9 10 - D. D. Example 5 14 3-3 PAAA 173,000 10 10 - D. D. Example 5 15 3-2 PAAA 175,000 11 10 - D. D. Example 5 16 3-3 PAAA 173,000 12 10 - D. D. Comparative Example 5 2 3-2 PAAA 175,000 13 10 - E. E. Example 5 17 3-3 PAAA 173,000 14 10 - D. D. Example 5 18 3-2 PAAA 175,000 15 10 - D. D. Example 5 19 3-3 PAAA 173,000 16 10 - D. D. Example 5 20 3-2 PAAA 175,000 17 10 - D. D. Example 5 twenty one 3-3 PAAA 173,000 18 10 - D. D. Example 5 twenty two 3-2 PAAA 175,000 19 10 - D. D. Example 5 twenty three 3-3 PAAA 173,000 20 10 - D. D. Example 5 twenty four 3-2 PAAA 175,000 twenty one 10 - D. D. Example 5 25 3-3 PAAA 173,000 twenty two 10 - D. D. Example 5 26 3-2 PAAA 175,000 twenty three 10 - D. D. Example 5 27 3-6 PAAA 172,000 1 10 - B B Example 5 28 3-5 PAAA 241,000 2 10 - A B Example 5 29 3-4 PAAA 242,000 1 10 - A B Example 5 30 3-5 PAAA 241,000 2 10 cyclotin A A

<Embodiment II> The varnish obtained in each synthesis example was directly used as a resin composition, and evaluated according to the above-mentioned method. The synthesis results are shown in Table 8, and the evaluation results are shown in Tables 9 and 10.

It is clear from Table 8 and Table 9 that the polyimide film (Comparative Example II-1-1) composed only of the structural unit N (polyamic acid) has excellent residual stress, but has a large YI value and Haze value. Also, the polyamic acid described in Example II-1-1 was obtained from the polyamic acid synthesized with the same composition as the polyamic acid-imide copolymer (the molar ratio of the monomers constituting X ₁ to X ₄ is the same). Although the polyimide film was excellent in YI value and Haze value, the residual stress increased, and neither of them showed sufficient performance to be used as a substrate for an optical display.

Furthermore, the polymer obtained by not using the general formula (A-1) or (A- ₂ ) as X in the structural unit N and using the method described in Example 1 described in the International Publication No. 2020/138360 manual The polyimide film (comparative example II-1-3) obtained from the amide acid-imide copolymer was colored yellow during the heat treatment step at 430° C., and its YI value and Haze value were relatively large. Also, a polyimide film composed of only the structural unit M (polyimide) and obtained from polyimide obtained by using the method described in Example 1 described in International Publication No. 2019/188305 handbook ( Comparative Example II-1-4) The yellowing in the heat treatment step at 430° C. was suppressed, but on the other hand, the residual stress was high, and the performance as a substrate for an optical display was insufficient.

On the other hand, as in Example II-1-1-1, by comprising a structure selected from general formula (A-1) and represented by 4,4'-oxydiphthalic dianhydride ( ODPA) and at least one polyamic acid as _X3 in the group consisting of the structure derived from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA)- The yellowness (YI value) of the polyimide film obtained from the imide copolymer is as low as 15 or less, and the haze (Haze value) is also less than 0.5%, which is sufficient for use as a substrate for optical displays. In addition, the residual stress is also as low as 25 MPa or less, the bending resistance is also excellent, and the mechanical properties are also sufficient. From the above, it was confirmed that the polyimide resin film obtained from the resin composition of the present invention is a resin film with less yellowness, less haze, and lower residual stress.

Specifically, in the present invention, a resin film having a residual stress of 25 MPa or less, a yellowness of 15 or less, a haze of 0.5% or less, and excellent bending resistance can be obtained.

Also, a polyamic acid-imide copolymer varnish obtained by separately synthesizing polyamic acid and polyimide as in Synthesis Example 1-1-2, and then mixing them for reaction can be obtained . The polyimide film that obtains by this varnish is as shown in embodiment II-1-1-2, and embodiment II-1-1-1 is equivalent performance. It means that (c) polyamic acid-imide copolymer can be obtained by mixing and reacting (b) polyamic acid and (a) polyimide synthesized at a specific molar ratio.

On the other hand, in Table 9, as shown in Comparative Example II-1-1, the residual stress of the polyimide film obtained from the polyamic acid of only the structural unit N is excellent, but on the other hand, the bending resistance Insufficient sex. This is considered to be due to the fact that the polyimide film composed only of structural unit N is very rigid, and therefore in-plane crystallization proceeds during the bending test, resulting in damage. Therefore, the polyimide copolymer film obtained from the polyamic acid-imide copolymer comprising the structural unit N and the structural unit M has excellent yellowness and haze, low residual stress, and excellent bending resistance .

Also, as shown in Examples II-1-6, II-1-12, and II-1-13, if the ratio of X ₄ /X ₃ is 1.01 to 2 and the ratio of diamine to acid dianhydride is increased, Then the ratio of the terminal of polyimide to amine increases, so when it reacts with polyamic acid, the reactivity between polyamic acid and polyimide increases, and polyimides are well dispersed with each other when forming a film, so it is obtained Transparent film with excellent yellowness (YI value) and haze (Haze value), excellent bending resistance. Also, according to Examples II-1-6, II-1-12, and II-1-13, it is found that the ratio of X ₄ /X ₃ is 1.11, and the yellowness (YI value) of the composition is low and is particularly preferable.

Also, in Table 10, as shown in Examples II-2-1 to II-2-5, the polyimide-poly The yellowness (YI value) of the film obtained by the amide acid copolymer is low, and it can be preferably used as a substrate for a display.

[Table 8] Table 8 serial number Polyamide Department Polyimide Department Amide part content Morby Tetracarboxylic dianhydride (A-1) [Mole%] Diamine (B-1) [Mole%] Tetracarboxylic dianhydride (A-2) [Mole%] Diamine (B-2) [Mole%] Synthesis Example 1 BPDA ODPA TAHQ APAB PPD 44BAFL BPAF BPDA ODPA BPF-PA 6FDA APAB 44BAFL 33BAFL BFAF 33DAS 44DAS 44ODA 34ODA BAOFL BAHF mol% [B-2]/[A-2] [B-1]/[A-1] ([Bl]＋[B-2])/ ([Al]＋[A-2]) 1-1 100 100 100 100 20 1.11 0.96 0.988 1-2 100 100 100 100 20 1.11 0.96 0.988 1-3 100 100 100 100 20 1.11 0.96 0.988 1-4 100 100 100 100 20 1.11 0.96 0.988 1-5 100 100 100 100 20 1.11 0.96 0.988 2 100 100 100 100 20 1.11 0.96 0.99 3 100 100 100 100 20 1.11 0.96 0.988 4 100 100 100 100 20 1.11 0.969 0.996 5 100 100 100 100 30 1.11 0.95 0.996 6 100 100 100 100 5 1.01 0.99 0.996 7 100 100 100 100 40 1.11 0.92 0.992 8 100 100 100 100 20 1.11 0.969 0.996 9 100 100 100 100 20 1.11 0.969 0.996 10 100 100 100 100 20 1.11 0.969 0.996 11 100 100 100 100 20 1.11 0.96 0.988 12 100 100 50 50 100 20 1.11 0.96 0.988 13 100 100 50 50 100 20 1.11 0.96 0.988 14 100 100 50 50 100 20 1.25 0.94 0.991 15 100 100 50 50 100 20 2 0.84 0.99 16 100 100 100 50 50 20 1.11 0.969 0.996 17 100 100 100 50 50 20 1.11 0.96 0.988 18 100 100 100 50 50 30 1.11 0.96 0.988 19 100 100 50 50 100 20 1.11 0.96 0.988 20 100 100 100 50 50 20 1.11 0.969 0.996 twenty one 100 100 50 50 100 20 1.11 0.96 0.988 twenty two 100 100 50 50 100 20 1.11 0.96 0.988 twenty three 100 100 75 25 100 20 1.11 0.969 0.996 twenty four 80 20 100 100 100 20 1.11 0.96 0.988 25 100 100 100 100 20 1.11 0.96 0.988 26 100 80 20 100 100 20 1.11 0.96 0.988 27 100 80 20 100 100 20 1.11 0.96 0.988 28 50 50 100 100 100 20 1.11 0.96 0.988 29 100 100 100 100 20 1.11 0.969 0.996 30 100 100 100 65 35 20 1.11 0.969 0.996

[Table 9] Table 9 Synthesis example Yellowness (YI value) Haze (Haze value) residual stress Bending resistance Example II-1 1-1 1-1-1 A S A A 1-2 1-1-2 A S A A 1-3 1-1-3 S S A A 1-4 1-1-4 S S A A 1-5 1-1-5 S S A A 1-6 1-1-6 S S A A 2 1-2 A S A A 3 1-3 A S A A 4 1-4 S S S A 5 1-5 S S A A 6 1-6 A S S A 7 1-7 S S A A 8 1-8 A S A A 9 1-9 A S A A 10 1-10 A S S A 11 1-11 A S A A 12 1-12 S S A A 13 1-13 S S A A 14 1-14 A S A A 15 1-15 A S A A 16 1-16 A S A A 17 1-17 S A A A 18 1-18 S A A A 19 1-19 A S A A 20 1-20 A S A A twenty one 1-21 S S A A twenty two 1-22 A A S A twenty three 1-23 A S A A twenty four 1-24 A S A A 25 1-25 A A A A 26 1-26 A A S A 27 1-27 A S A A 28 1-28 A S A A 29 1-29 A S A A 30 1-30 A S A A Comparative Example II-1 1 2-1 B B A B 2 2-2 A A B A 3 2-3 B B A B 4 2-4 A A B B

[Table 10] Table 10 Synthesis example storage stability Example II-2 1 1-1-1 A 2 1-1-3 A 3 1-1-4 A 4 1-1-5 A 5 1-1-6 A

<Embodiment III> [Example III-1] A 500 ml separable flask was replaced with nitrogen, and N-methylpyrrolidone (N-methylpyrrolidone ( NMP: water content 250 ppm), 15.69 g (49.0 mmol) of 2,2'- bis (trifluoromethyl) benzidine (TFMB) was added, it stirred, and TFMB was dissolved. Then, 9.27 g (42.5 mmol) of pyromellitic dianhydride (PMDA) and 3.33 g (7.5 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) were added, Stir at 80°C under nitrogen flow for 4 hours, cool to room temperature, add (mass of solvent + mass of cyclobutane) to 3 wt% as 100 wt% as boiling point 250°C to 350°C Cyclobutane, an aprotic polar substance, was further stirred for 1 hour to obtain a solution of polyamic acid (hereinafter, also referred to as varnish).

The varnish was spin-coated on a 6-inch silicon wafer and a 10 cm square EAGLE glass by MIKASA Coater, pre-baked on a heating plate at 100°C for 6 minutes, then placed in a furnace under nitrogen flow and It heat-hardened at 380 degreeC for 1 hour, and obtained the polyimide resin film. For the polyimide resin film formed on the silicon wafer, use Lambda ACE to measure the film thickness of 39 parts in the plane, [(film thickness most deviated from the average value) - (average film thickness)] divided by the average film thickness The obtained value (hereinafter also referred to as in-plane film thickness uniformity) was 6.0%.

For the polyimide resin film formed on EAGLE glass, the YI was measured with a haze meter, and the result was 7.9 in terms of a film thickness of 10 μm. Furthermore, when the polyimide resin film formed on the EAGLE glass was reheated to 400°C, and the gas components generated were analyzed by GCMS, cyclobutene was not detected.

[Example III-2] In Example III-1, except that the amount of cyclobutane added was changed from 3 wt% to 20 wt%, a solution of polyamic acid was obtained in the same manner as in Example III-1. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.0%, 7.3, and 0 ppm respectively .

[Example III-3] A 500 ml separable flask was replaced with nitrogen, and N-methylpyrrolidone (N-methylpyrrolidone ( NMP: water content 250 ppm), 15.69 g (49.0 mmol) of 2,2'- bis (trifluoromethyl) benzidine (TFMB) was added, it stirred, and TFMB was dissolved. Then, 9.27 g (42.5 mmol) of pyromellitic dianhydride (PMDA) and 3.33 g (7.5 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) were added, It was stirred at 80° C. for 4 hours under a nitrogen stream, cooled to room temperature, and while stirring the solution, it was added dropwise to water in an amount 6 times that of the solution to precipitate a polymer. After the polymer was separated by filtration, it was vacuum-dried at 40° C. for 24 hours using a vacuum dryer. Thereafter, the polymer was dissolved in cyclobutane so that it became 15% by weight to obtain a solution of polyamic acid. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.0%, 7.3, and 600 ppm respectively .

[Comparative Example III-1] In Example III-1, except that cyclobutane was not added, the solution of the polyamic acid was obtained in the same manner as Example III-1. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 12.0%, 8.1, and 0 ppm respectively .

[Example III-4] In Example III-2, except that cyclobutane was changed to 3-methylcyclobutane, a solution of polyamic acid was obtained in the same manner as in Example III-2. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.0%, 7.6, and 0 ppm respectively .

[Example III-5] In Example III-2, except that cyclobutane was changed into benzophenone, a solution of polyamic acid was obtained in the same manner as in Example III-2. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 4.2%, 7.4, and 0 ppm respectively .

[Example III-6] In Example III-2, except that cyclobutane was changed into 2-phenoxyethyl acetate, a solution of polyamide acid was obtained in the same manner as in Example III-2. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 3.3%, 7.6, and 0 ppm respectively .

[Example III-7] In Example III-2, except that cyclobutylene was changed into diphenyl carbonate, a solution of polyamic acid was obtained in the same manner as in Example III-2. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 3.0%, 7.5, and 0 ppm respectively .

[Example III-8] In Example III-2, except that cyclobutane was changed into adipamide, a polyamide solution was obtained in the same manner as in Example III-2. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 4.1%, 7.6, and 0 ppm respectively .

[Example III-9] In Example III-2, except that cyclobutane was changed into adiponitrile, a solution of polyamic acid was obtained in the same manner as in Example III-2. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 4.0%, 7.5, and 0 ppm respectively .

[Example III-10] In Example III-2, except that cyclobutane was changed into dibutyl arylene, a solution of polyamic acid was obtained in the same manner as in Example III-2. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 3.0%, 7.6, and 0 ppm respectively .

[Comparative Example III-2] In Example III-2, except that cyclobutane was changed into dimethylsulfone, a solution of polyamic acid was obtained in the same manner as in Example III-2. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 12.0%, 8.1, and 0 ppm respectively .

[Comparative Example III-3] In Example III-2, except that cyclobutane was changed into diphenylsulfone, a solution of polyamic acid was obtained in the same manner as in Example III-2. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 4.0%, 7.5, and 1500 ppm respectively .

[Example III-11] A 500 ml separable flask was replaced with nitrogen, and N-methylpyrrolidone (N-methylpyrrolidone ( NMP: Moisture content 250 ppm), add 4-aminophenyl 4-aminobenzoate (APAB) 8.95 g (39.2 mmol) and 4,4'-diaminophenylsulfone (4,4'-DAS) 2.43 g (9.8 mmol), and stirred to dissolve the two. Thereafter, 14.71 g (50 mmol) of 4,4'-diphthalic dianhydride (BPDA) was added, stirred at 80° C. for 4 hours under a nitrogen flow, and cooled to room temperature, so that (mass of solvent + The mass of cyclobutane) was added so that it might become 20 wt% from 100 wt%, and further stirred for 1 hour to obtain a polyamic acid solution (hereinafter, also referred to as varnish). The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.2%, 12.6, and 0 ppm respectively .

[Comparative Example III-4] In Example 11, except that cyclobutane was not added, the solution of polyamic acid was obtained in the same manner as Example III-11. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 11.0%, 13.5, and 0 ppm respectively .

[Example III-12] A 500 ml separable flask was replaced with nitrogen, and 22.2 g of N-methylpyrrolidone (NMP: moisture content: 250 ppm) in a 18 L can was added as a solvent to the separable flask, and 3 , 2.61 g (10.53 mmol) of 3'-diaminophenylsulfone (3,3'-DAS) was stirred and dissolved, and 2.94 g (ODPA) of 4,4'-oxydiphthalic dianhydride (ODPA) was added ( 9.47 mmol), toluene 20 g, the reflux tube and the Dean-Stark tube were installed in the flask, under nitrogen flow and at 180 ° C, the water produced was drawn out from the Dean-Stark tube, and at the same time The reaction was carried out under nitrogen flow for 2 hours, and then heated at 180° C. for 1 hour, and all the added toluene was extracted from the Dean-Stark tube. Thereafter, the reaction solution was cooled to room temperature, and 81.96 g of N-methylpyrrolidone (NMP: water content 250 ppm) and 4,4'-diphthalic diphthalamide were added as solvents immediately after opening the 18 L can. 11.77 g (40 mmol) of formic acid dianhydride (BPDA) and 8.72 g (38.2 mmol) of 4-aminophenylbenzoic acid (APAB) were stirred and dissolved. Thereafter, under nitrogen flow and react at 80°C for 4 hours, after cooling to room temperature, add cyclobutane to reach 20 wt% relative to (mass of solvent + mass of cyclobutane) 100 wt%, and then stir for 1 A polyamide acid-soluble polyimide solution (hereinafter, also referred to as varnish) was obtained. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.3%, 12.9, and 0 ppm respectively .

[Comparative Example III-5] Except that no cyclobutane was added in Example III-12, a polyamic acid-soluble polyimide solution was obtained in the same manner as in Example III-12. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 12.0%, 13.6, and 0 ppm respectively .

[Example III-13] A 500 ml separable flask was replaced with nitrogen, and N-methylpyrrolidone (N-methylpyrrolidone ( NMP: water content 250 ppm), 17.07 g (49 mmol) of 9,9- bis (4-aminophenyl) terrene (BAFL) was added, it stirred, and BAFL was dissolved. Thereafter, 22.92 g (50 mmol) of 9,9-bis(3,4-dicarboxyphenyl) phthalic acid dianhydride (BPAF) was added, stirred at 80° C. for 4 hours under nitrogen flow, and cooled to room temperature , add cyclobutane to reach 20 wt% relative to (mass of solvent + mass of cyclobutane) 100 wt%, and then stir for 1 hour to obtain a solution of polyamic acid (hereinafter, also referred to as varnish). The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.1%, 12.8, and 0 ppm respectively .

[Comparative Example III-6] A solution of polyamideimide was obtained in the same manner as in Example III-13, except that cyclobutylene was not added in Example III-13. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 12.0%, 13.5, and 0 ppm respectively .

[Example III-14] A 300 ml separable flask was replaced with nitrogen, and dimethylacetamide (DMAc) was added as a solvent in an amount equivalent to only 26 wt% of the solid content in the separable flask, and 4,4' - 2.27 g (10 mmol) of diaminobenzamide aniline (DABAN) was stirred to dissolve DABAN. Thereafter, 3.84 g of nor-2-spiro-α-cyclopentanone-α'-spiro-2'-nor-5,5',6,6'-tetracarboxylic dianhydride (CpODA) was added (10 mmol), under nitrogen stream and after stirring at room temperature for 12 hours, add 3-methylcyclobutane to reach 20 wt%, and then stirred for 1 hour to obtain a solution of polyamic acid (hereinafter, also referred to as varnish). The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.4%, 1.5, and 0 ppm respectively .

[Comparative Example III-7] Except that 3-methylcyclobutane was not added in Example III-14, the solution of polyamic acid was obtained in the same manner as in Example III-14. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 11.0%, 2.3, and 0 ppm respectively .

[Example III-15] A 500 ml separable flask was replaced with nitrogen, and N-methylpyrrolidone (N-methylpyrrolidone ( NMP: water content 250 ppm), 5.6 g (49 mmol) of 1,4-cyclohexanediamine (1,4-CHDA) was added, it stirred, and it etc. were melt|dissolved. Thereafter, 13.8 g (47.5 mmol) of 4,4'-diphthalic dianhydride (BPDA) and 0.7 g (1.5 mmol) of terephthalic dianhydride (TMHQ) were added, and the Stir at 80°C for 1 hour, and after stirring at room temperature for 5 hours, add cyclobutane to reach 20 wt% relative to (mass of solvent + mass of cyclobutane) 100 wt%, and then stir for 1 hour to obtain The solution of polyamide acid (hereinafter also referred to as varnish). The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.2%, 1.6, and 0 ppm respectively .

[Example III-16] A 500 ml separable flask was replaced with nitrogen, and N-methylpyrrolidone (N-methylpyrrolidone ( NMP: water content 250 ppm), 5.6 g (49 mmol) of 1,4-cyclohexanediamine (1,4-CHDA) was added, it stirred, and it etc. were melt|dissolved. Thereafter, 13.8 g (47.5 mmol) of 4,4'-diphthalic dianhydride (BPDA) and 0.7 g (1.5 mmol) of terephthalic dianhydride (TMHQ) were added, and the mixture was placed under a nitrogen stream at After stirring at 80° C. for 1 hour and at room temperature for 5 hours, the solution was added dropwise to water of 6 times the amount of the solution while stirring to precipitate a polymer. After the polymer was separated by filtration, it was vacuum-dried at 40° C. for 24 hours using a vacuum dryer. Thereafter, the polymer was dissolved in cyclobutane so that it became 15% by weight to obtain a polyamic acid solution. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.2%, 1.6, and 600 ppm respectively .

[Comparative Example III-8] Except that no cyclobutane was added in Example III-15, a solution of polyamic acid was obtained in the same manner as in Example III-15. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 12.0%, 2.3, and 0 ppm respectively .

[Example III-17] 168 g of γ-butyrolactone (GBL) and 15.2 g (100 mmol) of 3,5-diaminobenzoic acid (DABA) were added to a 500 ml separable flask, stirred and dissolved, and then added nor- 2-spiro-α-cyclopentanone-α'-spiro-2'-northane-5,5',6,6'-tetracarboxylic dianhydride (CpODA) 38.4 g (100 mmol), toluene 30 g . Install the reflux tube and the Dean-Stark tube in the flask, draw out the water produced at 180°C under the nitrogen flow from the Dean-Stark tube on the one hand, and react under the nitrogen flow for 2 hours, and then at 180°C After heating at °C for 1 hour, all the added toluene was extracted from the Dean-Stark tube. Cyclobutane was added so as to reach 20 wt% relative to (mass of solvent + mass of cyclobutane) 100 wt%, and further stirred for 1 hour to obtain a solution of soluble polyimide (hereinafter, also referred to as varnish). The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.5%, 1.4, and 0 ppm respectively .

[Example III-18] Except that in Example III-17, the amount of cyclobutane added was changed from 20 wt% to 50 wt%, the solution of polyamic acid was obtained in the same manner as in Example III-17. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.5%, 1.4, and 600 ppm respectively .

[Comparative Example III-9] 168 g of γ-butyrolactone (GBL) and 15.2 g (100 mmol) of 3,5-diaminobenzoic acid (DABA) were added to a 500 ml separable flask, stirred and dissolved, and then added nor- 2-spiro-α-cyclopentanone-α'-spiro-2'-northane-5,5',6,6'-tetracarboxylic dianhydride (CpODA) 38.4 g (100 mmol), toluene 30 g . Install the reflux tube and the Dean-Stark tube in the flask, draw out the water produced at 180°C under the nitrogen flow from the Dean-Stark tube on the one hand, and react under the nitrogen flow for 2 hours, and then at 180°C After heating at °C for 1 hour, all the added toluene was extracted from the Dean-Stark tube. Thereafter, while stirring the solution, it was added dropwise to water in an amount 6 times that of the solution to precipitate a polymer. After the polymer was separated by filtration, it was vacuum-dried at 40° C. for 24 hours using a vacuum dryer. Thereafter, the polymer was dissolved in cyclobutane so that it became 15% by weight to obtain a solution of soluble polyimide. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.5%, 1.4, and 1500 ppm respectively .

[Comparative Example III-10] A solution of polyamic acid was obtained in the same manner as in Example III-17, except that cyclobutane was not added in Example III-17. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 12.6%, 2.2, and 0 ppm respectively .

[Example III-19] Add 130 g of N-methylpyrrolidone (NMP: water content 250 ppm) to a 500 ml separable flask, add 2,2'-bis(trifluoromethyl)-4,4'-diaminobis Phenyl ether (6FODA) 32.858 g (97.7 mmol) and stirred to dissolve, add nor-alane-2-spiro-α-cyclopentanone-α'-spiro-2'-nor-alane-5,5',6 , 22.936 g (60 mmol) of 6'-tetracarboxylic dianhydride (CpODA), 30 g of toluene. Install the reflux tube and the Dean-Stark tube in the flask, draw out the water produced at 180°C under the nitrogen flow from the Dean-Stark tube on the one hand, and react under the nitrogen flow for 2 hours, and then at 180°C After heating at °C for 1 hour, all the added toluene was extracted from the Dean-Stark tube. After cooling this solution to 50° C., 25 g of NMP and 11.704 g (40 mmol) of 4,4′-diphthalic dianhydride (BPDA) were added, stirred at 50° C. for 4 hours, and cooled to room temperature. Further, 7.723 g (2 mmol) of polysiloxanediamine X-22-1660-B-3 manufactured by Shin-Etsu Chemical Co., Ltd. was added and stirred for 1 hour. Thereafter, cyclobutylene was added to reach 20 wt% relative to (mass of solvent+cyclobutylene mass) 100 wt%, and then stirred for 1 hour to obtain a solution of polyamic acid-soluble polyimide (hereinafter , also known as varnish). The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.2%, 1.3, and 0 ppm respectively .

[Example III-20] Add 130 g of N-methylpyrrolidone (NMP: water content 250 ppm) to a 500 ml separable flask, add 2,2'-bis(trifluoromethyl)-4,4'-diaminobis Phenyl ether (6FODA) 32.858 g (97.7 mmol) and stirred to dissolve, add nor-alane-2-spiro-α-cyclopentanone-α'-spiro-2'-nor-alane-5,5',6 , 22.936 g (60 mmol) of 6'-tetracarboxylic dianhydride (CpODA), 30 g of toluene. Install the reflux tube and the Dean-Stark tube in the flask, draw out the water produced at 180°C under the nitrogen flow from the Dean-Stark tube on the one hand, and react under the nitrogen flow for 2 hours, and then at 180°C After heating at °C for 1 hour, all the added toluene was extracted from the Dean-Stark tube. After cooling this solution to 50° C., 25 g of NMP and 11.704 g (40 mmol) of 4,4′-diphthalic dianhydride (BPDA) were added, stirred at 50° C. for 4 hours, and cooled to room temperature. Further, 7.723 g (2 mmol) of polysiloxanediamine X-22-1660-B-3 manufactured by Shin-Etsu Chemical Co., Ltd. was added and stirred for 1 hour. Thereafter, while stirring the solution, it was added dropwise to water in an amount 6 times that of the solution to precipitate a polymer. After the polymer was separated by filtration, it was vacuum-dried at 40° C. for 24 hours using a vacuum dryer. Thereafter, the polymer was dissolved in cyclobutane so that it became 15% by weight to obtain a polyamic acid-soluble polyimide solution. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.2%, 1.3, and 500 ppm respectively .

[Comparative Example III-11] Except that no cyclobutane was added in Example III-19, a solution of polyamic acid-soluble polyimide was obtained in the same manner as in Example III-19. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 12.0%, 2.2, and 0 ppm respectively .

[Example III-21] A 500 ml separable flask was replaced with nitrogen, and N-methylpyrrolidone (N-methylpyrrolidone ( NMP: Moisture content 250 ppm), add 1,4-cyclohexanediamine (1,4-CHDA) 3.4576 g (30.3 mmol), 4,4'-bis(aminophenoxy)biphenyl (BAPB) 26.0326 g (70.7 mmol), and stirred to dissolve it. Thereafter, 30.5098 g (100.9 mmol) of decahydro-1,4:5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylic dianhydride (DNDA) was added, and the After stirring overnight at room temperature, add cyclobutane to reach 20 wt% relative to (mass of solvent + mass of cyclobutane) 100 wt%, and then stir for 1 hour to obtain a solution of polyamic acid (hereinafter, also called varnish). The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 2.1%, 1.8, and 0 ppm respectively .

[Comparative Example III-12] Except that no cyclobutane was added in Example III-21, a solution of polyamic acid-soluble polyimide was obtained in the same manner as in Example III-21. The varnish was cured in the same manner as in Example III-1, and the in-plane film thickness uniformity, YI, and outgassing amount during reheating of the polyimide resin film were measured, and the results were 12.2%, 2.9, and 0 ppm respectively . Tables 11 to 13 collectively show the results of the above-mentioned Examples and Comparative Examples.

[Table 11] Example III Example 1 Example 2 Example 3 Comparative example 1 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative example 2 Comparative example 3 Anhydride (wt%) PMDA(85) ← ← ← ← ← ← ← ← ← ← ← ← 6 FDA (15) ← ← ← ← ← ← ← ← ← ← ← ← Diamine(wt%) TFMB ← ← ← ← ← ← ← ← ← ← ← ← solvent NMP ← ← ← ← ← ← ← ← ← ← ← ← polymer structure PAAA ← ← ← ← ← ← ← ← ← ← ← ← Aprotic polar substances with a boiling point of 250°C to 350°C type cyclotin ← ← ← 3-Methylcyclobutane Benzophenone 2-phenoxyethyl acetate Diphenyl carbonate Adipamide Adiponitrile Dibutylene oxide Dimethylsulfone Diphenylsulfone Boiling point °C 285 ← ← ← 276 305 260 302 263 295 250 238 379 Add amount 3wt% 20wt% 100wt% 0 wt% 20wt% 20wt% 20wt% 20wt% 20wt% 20wt% 20wt% 20wt% 20wt% In-plane film thickness uniformity 6.0% 2.0% 2.0% 12.0% 2.0% 4.2% 3.3% 3.0% 4.1% 4.0% 3.0% 12.0% 4.0% YI 7.9 7.3 7.3 8.1 7.6 7.4 7.6 7.5 7.6 7.5 7.6 8.1 7.5 Concentration of aprotic polar substances remaining in the cured film ppm 0 0 600 0 0 0 0 0 0 0 0 0 1500

[Table 12] Example III Example 11 Comparative example 4 Example 12 Comparative Example 5 Example 13 Comparative example 6 Example 14 Comparative Example 7 Example 15 Example 16 Comparative Example 8 Anhydride BPDA ← BPDA(80) ← BPAF ← CpODA ← BPDA(97) ← ← ODPA(20) ← TMHQ(3) ← ← diamine APAB(80) ← APAB(80) ← BAFL ← DABAN ← CHDA ← ← 44DAS(20) ← 33DAS(20) ← solvent NMP ← ← ← ← ← DMAc ← NMP ← ← polymer structure PAAA ← PI-PAA ← PAAA ← PAAA ← PAAA ← ← Aprotic polar substances with a boiling point of 250°C to 350°C type cyclotin ← cyclotin ← cyclotin ← 3-Methylcyclobutane ← cyclotin ← ← Boiling point °C 285 ← 285 ← 285 ← 276 ← 285 ← ← Amount added 20wt% 0 wt% 20wt% 0 wt% 20wt% 0 wt% 20wt% 0 wt% 20wt% 100wt% 0 wt% In-plane film thickness uniformity 2.2% 11.0% 2.3% 12.0% 2.1% 12.0% 2.4% 11.0% 2.2% 2.2% 12.0% YI 12.6 13.5 12.9 13.6 12.8 13.5 1.5 2.3 1.6 1.6 2.3 Concentration of aprotic polar substances remaining in the cured film ppm 0 0 0 0 0 0 0 0 0 600 0

[Table 13] Example III Example 17 Example 18 Comparative Example 9 Comparative Example 10 Example 19 Example 20 Comparative Example 11 Example 21 Comparative Example 12 Anhydride CpODA ← ← ← CpODA ← ← DNDA ← diamine DABA ← ← ← 6FODA ← ← BAPB ← SiDA ← ← solvent GBL ← ← ← NMP ← ← ← ← polymer structure P.I. ← ← ← PI-PAA ← ← PAAA ← Aprotic polar substances with a boiling point of 250C to 350C type cyclotin ← ← ← cyclotin ← ← cyclotin ← Boiling point °C 285 ← ← ← 285 ← ← 285 ← Amount added 20wt% 50wt% 100wt% 0 wt% 20wt% 100wt% 0 wt% 20wt% 0 wt% In-plane film thickness uniformity 2.5% 2.5% 2.5% 12.6% 2.2% 2.2% 12.0% 2.1% 12.2% YI 1.4 1.4 1.4 2.2 1.3 1.3 2.2 1.8 2.9 Concentration of aprotic polar substances remaining in the cured film ppm 0 600 1500 0 0 500 0 0 0

As mentioned above, compared with the comparative example, the resin composition of the example is soft and has fluidity, and when it is made into a polyimide resin film, the in-plane uniformity of the film thickness is improved, and the YI is also reduced. Excellent properties required for display applications.

2a: Lower substrate 2b: Sealing substrate 25:Organic EL structure department 250a: Organic EL element emitting red light 250b: Organic EL element emitting green light 250c: Organic EL element emitting blue light 251: Partition wall (dam) 252: Lower electrode (anode) 253: Hole transport layer 254: luminous layer 255: Upper electrode (cathode) 256:TFT 257: contact hole 258: interlayer insulating film 259: Lower electrode 261: hollow part

FIG. 1 is a schematic diagram showing the structure of a top-emission type flexible organic EL (Electroluminescence, electroluminescence) display as an example of a display according to an embodiment of the present invention above a polyimide substrate.

Claims (39)

A kind of resin composition, it is characterized in that comprising polyamide acid-imide copolymer, (d) organic solvent and (e) imidization catalyst, and above-mentioned (e) imidization catalyst is selected from At least one of the group consisting of imidazole compounds, pyridine compounds, and tertiary amine compounds, the above-mentioned polyamic acid-imide copolymers include structural units represented by the following general formula (1): ]

{In the formula, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, n, m, and l are positive integers, and include the following general formula (A-1): 2]

(wherein, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, a and b are independently an integer of 0 to 4, and * represents a bonding portion) The structure is X ₂ } in the above general formula (1). The resin composition as claimed in item 1, wherein the above-mentioned imidazole compound is selected from 1-methylimidazole, N-tertiary butoxycarbonylimidazole (N-Boc-imidazole), 2-methylimidazole, 2-phenylimidazole , benzimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 4-methyl-2-phenylimidazole, 2-undecylimidazole, 1-benzyl -at least one of the group consisting of 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1H-imidazole, and 1,2-dimethylimidazole, The pyridine compound is at least one selected from the group consisting of 4-dimethylaminopyridine, 2,2'-bipyridine, nicotinic acid, isoquinoline, pyridine, and 2-picoline, and /or The above tertiary amine compounds are selected from 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane, N-methylmorpholine , and at least one of the group consisting of triethylamine. The resin composition according to claim 1 or 2, wherein the above-mentioned (e) imidization catalyst is the above-mentioned imidazole compound. The resin composition according to any one of claims 1 to 3, wherein the content of the imidization catalyst (e) is 5 parts by mass or more relative to 100 parts by mass of the polyamic acid-imide copolymer. A kind of resin composition, it comprises polyamic acid-imide copolymer and (d) organic solvent, and above-mentioned polyamic acid-imide copolymer comprises the structural unit represented by following general formula (1): [chemical 3]

{In the formula, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, n, m, and l are positive integers, and include the following general formula (A-1): 4]

(wherein, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, a and b are independently an integer of 0 to 4, and * represents a bonding portion) The structure is X ₂ } in the above-mentioned general formula (1), and the weight-average molecular weight of the above-mentioned polyamic acid-imide copolymer is 170,000 or more. The resin composition according to any one of claims 1 to 4, wherein the weight average molecular weight of the above-mentioned polyamic acid-imide copolymer is 170,000 or more. A kind of resin composition, it comprises polyamic acid, (d) organic solvent and (e) imidization catalyst, and above-mentioned polyamic acid comprises the structural unit represented by following general formula (3): 5]

{In the _formula , X1 represents _a tetravalent organic group, X2 represents a divalent organic group, and n is a positive integer, and includes the following general formula (A-1): [Chemical 6]

(wherein, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, a and b are independently an integer of 0 to 4, and * represents a bonding portion) Structure As X ₂ } in the above-mentioned general formula (3), the above-mentioned (e) imidization catalyst is selected from 1-methylimidazole, N-tert-butoxycarbonylimidazole (N-Boc-imidazole), 2-methylimidazole, 2-phenylimidazole, benzimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 4-methyl-2-phenylimidazole, 2 -Undecylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1H-imidazole, 4-dimethylaminopyridine, 2,2'-bipyridine, Nicotinic acid, isoquinoline, pyridine, 2-picoline, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane At least one of the group consisting of alkanes, N-methylmorpholine, and triethylamine. A kind of resin composition, it comprises polyamic acid, (d) organic solvent and (e) imidization catalyst, and above-mentioned polyamic acid comprises the structural unit represented by following general formula (3): 7]

{In the _formula , X1 represents _a tetravalent organic group, X2 represents a divalent organic group, and n is a positive integer, and includes the following general formula (A-1): [Chemical 8]

(wherein, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, a and b are independently an integer of 0 to 4, and * represents a bonding portion) Structure As X ₂ } in the above-mentioned general formula (3), the above-mentioned (e) imidization catalyst is an imidazole compound, and the content of the above-mentioned (e) imidization catalyst is relative to the above-mentioned polyamic acid 100 mass The part is 5 parts by mass or more. A kind of resin composition, it comprises polyamic acid, (d) organic solvent and (e) imidization catalyst, and above-mentioned polyamic acid comprises the structural unit represented by following general formula (3): 9]

{In the _formula , X1 represents _a tetravalent organic group, X2 represents a divalent organic group, and n is a positive integer, and includes the following general formula (A-1): [Chem. 10]

(wherein, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, a and b are independently an integer of 0 to 4, and * represents a bonding portion) Structure As X ₂ } in the above-mentioned general formula (3), the above-mentioned (e) imidization catalyst is an imidazole compound, and the weight-average molecular weight of the above-mentioned polyamic acid is 170,000 or more. The resin composition according to claim 7 or 8, wherein the weight average molecular weight of the polyamide acid is above 170,000. The resin composition according to any one of claims 1 to 10, wherein the content of the above-mentioned (e) imidization catalyst is relative to 100 parts by mass of the above-mentioned polyamic acid-imide copolymer or the above-mentioned polyamic acid 100 parts by mass is 10 parts by mass or more. The resin composition according to any one of claim items 1 to 11, wherein the above-mentioned (e) imidization catalyst system comprises N-tertiary butoxycarbonylimidazole (N-Boc-imidazole) and/or 1-methanol The imidazole compound of imidazole. The resin composition according to any one of claims 1 to 12, wherein the weight average molecular weight of the above-mentioned polyamic acid-imide copolymer or the above-mentioned polyamic acid is 220,000 or more. The resin composition according to any one of claims 1 to 13, further comprising an aprotic polar substance with a boiling point of 250°C to 350°C. The resin composition according to claim 14, wherein the above-mentioned aprotic polar substance is cyclobutene. The resin composition according to any one of claims 1 to 15, wherein X in the above general formula ( ₁ ) or X in ( ₃ ) is selected from the following general formula (A-4), the following general formula Formula (A-5) and the following general formula (A-6): [Chemical 11]

{In the formula, R ₈ to R ₁₁ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, and h to k each independently represent an integer of 0 to 4, Z ₂ represents a bonding group, and * Indicates the bonding part} [Chem. 12]

{In the formula, R ₁₂ and R ₁₃ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, l and m each independently represent an integer of 0 to 4, and * represents a bonding portion} [Chem. 13 ]

{In the formula, R ₁₄ and R ₁₅ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, n and o are each independently an integer of 0 to 4, and * represents a bonding portion} At least one of the group of structures. The resin composition according to any one of claims 1 to 6, 11 to 16, wherein X in the above general formula ( ₁ ) is selected from the following general formula (A-3): [Chemical 14]

{In the formula, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents The structure represented by the bonding portion}, the structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), the structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride Anhydride (6FDA) structure, structure derived from biphenyl tetracarboxylic dianhydride (BPDA), and structure derived from 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ) At least 1 species in the group. The resin composition according to any one of claims 1 to 6, 11 to 17, wherein the content of the above-mentioned (e) imidization catalyst is 1 mole relative to the repeating unit of the above-mentioned polyamic acid-imide copolymerization It is in the range of 0.02 to 0.15 mol%. A polyamide acid-imide copolymer is characterized in that comprising the structural unit L represented by the following general formula (1): [Chemical 15]

{In the formula, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, n, m, and l are positive integers, and the structural unit containing X ₁ and X ₂ is called a structural unit N, and the structural unit comprising X ₃ and X ₄ is called structural unit M, and when X ₂ is a base derived from 4-aminobenzoic acid 4-amino-3-fluorophenyl ester, the following constitution 1. Except for 2: 1. In the case where X ₃ is derived from the base of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), X ₂ is derived from 4,4'- Diaminodiphenylene, and/or 2,2'-bis(trifluoromethyl)benzidine; and 2.X ₃ is derived from nor-2-spiro-α-cyclopentanone- α'-spiro-2''-nor-alane-5,5'',6,6''-tetracarboxylic dianhydride base}, and has the following general formula (A-1): [Chemical 16]

{In the formula, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, a and b each independently represent an integer of 0 to 4, and * represents a bonding portion} or the following General formula (A-2): [Chem. 17]

{wherein, R ₃ represents a valent organic group having 1 to 20 carbon atoms, or a halogen, and c is an integer of 0 to 4; * represents a bonding portion} The structure represented by it is taken as the above-mentioned X ₂ . Such as the polyamic acid-imide copolymer of claim 19, wherein X in the above-mentioned general formula ( ₁ ) is selected from the following general formula (A-3): [Chemical 18]

{In the formula, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents The structure represented by the bonding portion}, the structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), and the structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride (ODPA) At least one of the group consisting of the structure of formic anhydride (6FDA). As the polyamic acid-imide copolymer of claim item 19 or 20, wherein X in the above-mentioned general formula (1) ₄ has to be selected from following general formula (A-4), following general formula (A-5 ) and the following general formula (A-6): [Chemical 19]

{In the formula, R ₈ to R ₁₁ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, and h to k each independently represent an integer of 0 to 4, Z ₂ represents a bonding group, and * Indicates the bonding part} [Chem. 20]

{In the formula, R ₁₂ and R ₁₃ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, l and m each independently represent an integer of 0 to 4, and * represents a bonding part, wherein in the above When _X3 is derived from the base of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), the above general formula (A-5) is derived from 4,4'-diamine Except for the case of the base of the diphenyl group} [Chem. 21]

{In the formula, R ₁₄ and R ₁₅ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, n and o are each independently an integer of 0 to 4, and * represents a bonding portion} At least one of the group of structures. A polyamide acid-imide copolymer is characterized in that comprising the structural unit L represented by the following general formula (1): [Chemical 22]

{In the formula, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, n, m, and l are positive integers, and the structural unit containing X ₁ and X ₂ is called a structural unit N, the structural unit comprising X ₃ and X ₄ is called structural unit M, and X ₄ is derived from 4,4'-diaminodiphenylene and/or 2,2'-bis(trifluoroform base) except for the base of benzidine}, and include the group selected from the following general formula (A-3): [Chemical 23]

{In the formula, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents The structure represented by the bonding portion}, the structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), and the structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride (ODPA) At least one of the group consisting of the structure of formic anhydride (6FDA) is X ₃ . Such as the polyamic acid-imide copolymer of claim 22, wherein X in the above-mentioned general formula (1) is selected from following general formula (A- ₄ ), following general formula (A-5) and The following general formula (A-6): [Chem. 24]

{In the formula, R ₈ to R ₁₁ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, and h to k each independently represent an integer of 0 to 4, Z ₂ represents a bonding group, and * Indicates the bonding part} [Chem. 25]

{In the formula, R ₁₂ and R ₁₃ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, i and j are each independently an integer of 0 to 4, and * represents a bonding part, wherein in the above When _X3 is derived from the base of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), the above general formula (A-5) is derived from 4,4'-diamine Except for the case of the base of the diphenyl group} [Chem. 26]

{In the formula, R ₁₄ and R ₁₅ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, n and o are each independently an integer of 0 to 4, and * represents a bonding portion} At least one of the group of structures. As the polyamic acid-imide copolymer according to any one of claims 19 to 23, wherein the diamine component constituting X2 in the above general formula ( ₁ ) and the diamine component constituting _X4 are composed of or diamine types are different. The polyamic acid-imide copolymer as any one of claim 19 to 24, wherein X in the above general formula ( ₁ ) is selected from the structure derived from biphenyltetracarboxylic dianhydride (BPDA) , a structure derived from 4,4'-oxydiphthalic acid dianhydride (ODPA), and a structure derived from 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ) At least 1 species in the group. The polyamide-imide copolymer as claimed in any one of items 19 to 25, wherein the molar ratio (X ₂ /X ₁ ) of X ₁ and X ₂ included in the above-mentioned general formula (1) is 0.84 to 1.00, and the molar ratio of X ₃ and X ₄ (X ₄ /X ₃ ) contained in the above general formula (1) is 1.01 to 2.00. As the polyamic acid-imide copolymer according to any one of claims 19 to 26, wherein the structural unit N of the polyamic acid comprising X1 and X2 in the above general _formula ( ₁ ) and comprising _X3 And the molar ratio of the structural unit M of the polyimide of _X4 (the molar number of the structural unit N: the molar number of the structural unit M) is in the range of 60:40 to 95:5. A resin composition comprising the polyamide-imide copolymer according to any one of claims 19 to 27, and (d) an organic solvent. The resin composition according to claim 28, wherein in all the polymers contained in the above resin composition, the ratio of structural unit N of polyamic acid comprising X ₁ and X ₂ is 60-95 mol%. The resin composition according to claim 28 or 29, further comprising (e) an imidization catalyst. A kind of polyimide copolymer, it is characterized in that comprising the structural unit represented by following general formula (2): [Chemical 27]

{wherein, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, and n and m are positive integers, the structural unit comprising X ₁ and X ₂ is called a structural unit N, And the structural unit comprising X ₃ and X ₄ is called structural unit M, and when X ₂ is a group derived from 4-aminobenzoic acid 4-amino-3-fluorophenyl ester, the following constitution 1 , 2 except: 1. In the case where X ₃ is derived from the base of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), X ₂ is derived from 4,4'-bis Aminodiphenylamine, and/or 2,2'-bis(trifluoromethyl)benzidine; and 2.X ₃ is derived from nor-2-spiro-α-cyclopentanone a- α'-spiro-2''-nor-alane-5,5'',6,6''-tetracarboxylic dianhydride base}, and has the following general formula (A-1): [Chemical 28]

{In the formula, R ₁ and R ₂ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, a and b each independently represent an integer of 0 to 4, and * represents a bonding portion} or the following General formula (A-2): [Chemical 29]

{wherein, R ₃ represents a valent organic group having 1 to 20 carbon atoms, or a halogen, c is an integer of 0 to 4, and * represents a bonding portion} The structure represented by the above-mentioned X ₂ . Such as the polyimide copolymer of claim 31, wherein X in the above general formula ( ₂ ) is selected from the following general formula (A-3): [Chemical 30]

{In the formula, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents The structure represented by the bonding portion}, the structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), and the structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride (ODPA) At least one of the group consisting of the structure of formic anhydride (6FDA). A kind of polyimide copolymer, it is characterized in that having the structural unit represented by following general formula (2): [Chemical 31]

{wherein, X ₁ and X ₃ represent a tetravalent organic group, X ₂ and X ₄ represent a divalent organic group, n and m are positive integers, the structural unit comprising X ₁ and X ₂ is called structural unit N, and The structural unit comprising X ₃ and X ₄ is called structural unit M, and X ₄ is derived from 4,4'-diaminodiphenylene, 2,2'-bis(trifluoromethyl)benzidine Except for the base}, and comprising the group selected from the following general formula (A-3):

{In the formula, R ₄ to R ₇ independently represent a valent organic group with 1 to 20 carbon atoms or a halogen, d to g each independently represent an integer of 0 to 4, Z ₁ represents a bonding group, and * represents The structure represented by the bonding portion}, the structure derived from 4,4'-oxydiphthalic dianhydride (ODPA), and the structure derived from 4,4'-(hexafluoroisopropylidene)diphthalic acid dianhydride (ODPA) At least one of the group consisting of the structure of formic anhydride (6FDA) is X ₃ . Such as the polyimide copolymer of claim 33, wherein X in the above general formula ( ₂ ) is selected from the following general formula (A-4), following general formula (A-5) and following general formula (A-6): [Chemical 32]

{In the formula, R ₈ to R ₁₁ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, and h to k each independently represent an integer of 0 to 4, Z ₂ represents a bonding group, and * Indicates the bonding part} [Chem. 33]

{In the formula, R ₁₂ and R ₁₃ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, l and m each independently represent an integer of 0 to 4, and * represents a bonding portion, and in the above X When ₃ is derived from the base of 9,9-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF), the above general formula (A-5) is derived from 4,4'-diamine Except in the case of the base of diphenylphenylene} [Chem. 34]

{In the formula, R ₁₄ and R ₁₅ each independently represent a valent organic group with 1 to 20 carbon atoms, or a halogen, n and o are each independently an integer of 0 to 4, and * represents a bonding portion} At least one of the group of structures. As the polyimide copolymer of any one of claims 31 to 34, wherein X in the above general formula ( ₂ ) is selected from a structure derived from biphenyltetracarboxylic dianhydride (BPDA), derived from 4 , the structure of 4'-oxydiphthalic dianhydride (ODPA) and the structure derived from 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ) at least 1 species. The polyimide copolymer according to any one of claims 31 to 35, wherein the molar ratio (X ₂ /X ₁ ) of X ₁ and X ₂ included in the above general formula (2) is 0.84 to 1.00, And the molar ratio of X ₃ and X ₄ (X ₄ /X ₃ ) included in the above general formula (2) is 1.01-2.00. The polyimide copolymer of any one of claims 31 to 36, wherein the structural unit N of the polyimide comprising X1 and X2 in the above general _formula ( ₂ ) and the polyimide comprising _X3 and _X4 The molar ratio of the structural unit M of the polyimide (the molar number of the structural unit N:the molar number of the structural unit M) is in the range of 60:40 to 95:5. A resin composition, characterized in that it has a polyimide precursor represented by the following general formula (I), or a polyimide precursor skeleton represented by the following general formula (I) and the following general formula The polyimide skeleton represented by (II) contains an aprotic polar substance with a boiling point of 250°C to 350°C, [Chemical 35]

{In the formula, P ₁ represents a divalent organic group, P ₂ represents a tetravalent organic group, and p represents a positive integer} [化36]

{wherein, P1 represents _a divalent organic group, P2 represents a tetravalent organic group, and _p represents a positive integer}. A resin composition comprising polyimide represented by the following general formula (II), a solvent, and an aprotic polar substance with a boiling point of 250°C to 350°C: [Chemical 37]

{wherein, P1 represents _a divalent organic group, P2 represents a tetravalent organic group, and _p represents a positive integer}.

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