Polyimide precursor composition, polyimide film, and polyimide film / substrate laminate

Abstract

The present invention discloses a kind of polyimide precursor composition, it contains a polyimide precursor represented by the following general formula (I) in a specified amount and at least one imidazole compound as an optional component of a repeating unit. Using the polyimide precursor composition, it is possible to manufacture a polyimide film in which the light transmittance and the adhesion in the polyimide film / substrate laminate are improved while utilizing the advantages of aromatic polyimide films such as heat resistance and linear thermal expansion coefficient. In the formula, X1 (i) includes the structure of formula (1-1) of more than 50 mol % and includes the structure of formula (1-1) and formula (1-2) of more than 70 mol %, or (ii) includes the structure of formula (1-1) of more than 70 mol % and / or the structure of formula (1-2), and Y1 includes the structure of formula (B) of more than 70 mol %. Wherein, in the case of above-mentioned (ii), 1 mol of repeating units relative to the above-mentioned polyimide precursor contains imidazole compounds in an amount of more than 0.01 mol and less than 1 mol.

Description

Technical Field

[0001] The present invention relates to a polyimide precursor composition, a polyimide film, and a polyimide film / substrate laminate which are suitable for use in electronic devices such as substrates of flexible devices. Background Art

[0002] Polyimide films are widely used in the fields of electrical / electronic devices, semiconductors, etc. due to their excellent heat resistance, chemical resistance, mechanical strength, electrical properties, dimensional stability, etc. On the other hand, in recent years, with the advent of a highly information-based society, the development of optical materials such as optical fibers and optical waveguides in the field of optical communications, and liquid crystal alignment films and protective films for color filters in the field of display devices is being promoted. In particular, in the field of display devices, as a substitute for glass substrates, research on lightweight and highly flexible plastic substrates and the development of displays that can be bent or curled are being actively carried out.

[0003] In displays such as liquid crystal displays and organic EL displays, semiconductor elements such as TFTs (thin film transistors) are formed to drive each pixel. Therefore, heat resistance and dimensional stability are required for the substrate. Polyimide films are expected to be used as substrates for display applications due to their excellent heat resistance, chemical resistance, mechanical strength, electrical properties, dimensional stability, etc.

[0004] Generally, it is difficult to maintain the planarity of a flexible film, and therefore it is difficult to uniformly and accurately form semiconductor elements such as TFTs, fine wiring, etc. on the flexible film. In order to solve this problem, for example, Patent Document 1 describes "a method for manufacturing a flexible device as a display device or a light receiving device, which includes the following steps: a step of applying a specific precursor resin composition to a carrier substrate and forming a film to form a solid polyimide resin film; a step of forming a circuit on the resin film; and a step of peeling the solid resin film with the circuit formed on the surface from the carrier substrate."

[0005] In addition, Patent Document 2 discloses a method for manufacturing a flexible device, which includes: after forming elements and circuits required for the device on a polyimide film / glass substrate laminate obtained by forming a polyimide film on a glass substrate, irradiating the glass substrate with laser from the glass substrate side to peel off the glass substrate.

[0006] In the methods for producing flexible electronic devices described in Patent Documents 1 and 2, in order to handle the polyimide film / glass substrate laminate, appropriate adhesion is required between the polyimide film and the glass substrate.

[0007] Polyimide is usually colored yellow-brown, so its use in transmissive devices such as liquid crystal displays with backlights is limited. However, in recent years, polyimide films that have excellent light transmittance in addition to mechanical and thermal properties have been developed, and expectations for them as substrates for display applications have further increased. For example, Patent Document 3 describes a semi-alicyclic polyimide that has excellent mechanical properties, heat resistance, etc. in addition to light transmittance.

[0008] On the other hand, as an aromatic polyimide for use in flexible electronic device substrates, for example, Patent Documents 4 and 5 disclose a polyimide using a diamine component containing a fluorinated aromatic diamine such as 2,2'-bis(trifluoromethyl)benzidine (TFMB). In addition, as this use, Patent Documents 6, 7, and 8 disclose examples of using a diamine component containing an aromatic diamine compound containing an ester bond. Polyimides containing an aromatic diamine compound containing an ester bond as a component are also known to be used in copper-clad laminates (for example, Patent Document 9) and for forming a peeling layer (Patent Document 10). In addition, Patent Documents 11 to 15 also disclose examples of using a diamine component containing an aromatic diamine compound containing an ester bond.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2010-202729

[0012] Patent Document 2: International Publication No. 2018 / 221607

[0013] Patent Document 3: International Publication No. 2012 / 011590

[0014] Patent Document 4: International Publication No. 2009 / 107429

[0015] Patent Document 5: International Publication No. 2019 / 188265

[0016] Patent Document 6: Japanese Patent Application Laid-Open No. 2021-175790

[0017] Patent Document 7: International Publication No. 2017 / 051827

[0018] Patent Document 8: China Patent Application Publication No. 110003470

[0019] Patent Document 9: Japanese Patent Application Publication No. 2021-195380

[0020] Patent Document 10: International Publication No. 2016 / 129546

[0021] Patent Document 11: International Publication No. 2021 / 261177

[0022] Patent Document 12: U.S. Patent Application Publication No. 2022 / 0135797

[0023] Patent Document 13: Japanese Patent Application Laid-Open No. 7-133349

[0024] Patent Document 14: Japanese Patent Application Publication No. 2020-164704

[0025] Patent Document 15: U.S. Patent Application Publication No. 2021 / 0017336 Summary of the invention

[0026] Problems to be solved by the invention

[0027] In recent years, the film formation method of TFT has been continuously improved. Compared with the past, the film formation temperature has been continuously lowered. However, high temperature processing is still required in certain processes. In addition, the greater the process margin, the better the yield. Therefore, it is preferred that the heat resistance of the substrate film is as high as possible. Aromatic polyimide has problems with coloring, but generally has excellent heat resistance. Therefore, if the coloring is reduced as much as possible, it may be used as a substrate for display purposes.

[0028] In particular, in smartphones equipped with under-screen cameras, light passes through the display to reach the camera, so the polyimide film used for the display is required to have high light transmittance, especially in the sensitive area of ​​the sensor. In addition, a high elastic modulus is required to prevent whitening of the bent portion of a bendable flexible display, for example.

[0029] As described above, Patent Documents 4 and 5 disclose examples of using 2,2'-bis(trifluoromethyl)benzidine (TFMB), but the present inventors have conducted research and found the following problem: in the process of forming an electronic device from a polyimide film / glass substrate laminate using TFMB as a monomer component, the polyimide film is easily peeled off from the glass substrate. After an inorganic thin film having a gas barrier function is formed on the polyimide film / glass substrate laminate, peeling is easily caused when the laminate is exposed to high temperature.

[0030] In addition, in the manufacture of flexible electronic devices, a process of cutting a large polyimide film / glass substrate laminate (including after the element is formed) into individual flexible electronic devices (intermediate products) is sometimes included. If the adhesion between the polyimide film and the glass substrate is not sufficient, peeling sometimes occurs between the polyimide film and the glass substrate in this process. It is believed that the reason is that polyimide easily absorbs moisture, so it absorbs moisture in the atmosphere from the end face after cutting (the upper part is a barrier film) and expands, and peeling occurs when the adhesion is weak. In addition, in the laser peeling process of peeling the polyimide film from the glass substrate, when the adhesion strength between the polyimide film and the glass substrate is high, the laser intensity is small, so the change of the processed polyimide is small (no change), on the other hand, when the adhesion is weak, it is necessary to increase the laser intensity, so sometimes the processed polyimide changes color or reduces the mechanical properties. Therefore, the adhesion between the polyimide film and the glass substrate, that is, the peeling strength is extremely high.

[0031] The above-mentioned documents 6 to 15 do not disclose the invention of the present application at all, and there are problems with the polyimide film used as a flexible display substrate. Patent documents 6 and 7 record examples of the use of diamine components containing 4-aminophenyl-4-aminobenzoate (APAB; referred to as 4-BAAB in the present application), but the colorability of the film is insufficient. In Patent Document 8, a diamine compound of a specific structure is required, and the colorability of the film and the elastic modulus of the film are insufficient. The polyimide precursor compositions described in Patent Documents 11, 14, and 15 also require a diamine compound of a specific structure, and are not satisfactory in terms of haze and other aspects of flexible display substrate use. In addition, the polyimide films obtained from the polyimide precursor compositions for other uses described in Patent Documents 9, 10, 12, and 13 do not meet the performance required for display uses, including adhesion.

[0032] Therefore, an object of the present invention is to provide a polyimide precursor composition for producing a polyimide film for flexible electronic device applications, particularly flexible display substrate applications, while utilizing the advantages of aromatic polyimide films such as heat resistance and linear thermal expansion coefficient, and having improved light transmittance, adhesion in a polyimide film / substrate laminate, etc. Furthermore, an object of the present invention is to provide a polyimide film and a polyimide film / substrate laminate obtained from the polyimide precursor.

[0033] Means for solving problems

[0034] The main disclosed matters of the present application are summarized as follows: The inventions concerning items A1 to A14 are referred to as the invention series A, and the inventions concerning items B1 to B12 are referred to as the invention series B.

[0035] The inventions of Invention Series A are as follows.

[0036] A1. A polyimide precursor composition comprising: a polyimide precursor having a repeating unit represented by the following general formula (I); and at least one imidazole compound as an optional component in an amount less than 1 mol relative to 1 mol of the repeating unit of the polyimide precursor;

[0037] [Chemistry 1]

[0038]

[0039] (In the general formula I, X1 is a tetravalent aliphatic group or aromatic group, Y1 is a divalent aliphatic group or aromatic group, R1 and R2 are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, wherein,

[0040] X1 satisfies either (i) or (ii),

[0041] (i) contains 50 mol% or more of the structure represented by formula (1-1) and contains 70 mol% or more of the structure represented by formula (1-1) and the structure represented by formula (1-2) in total,

[0042] (ii) contains 70 mol% or more of the structure represented by formula (1-1) and / or the structure represented by formula (1-2),

[0043] [Chemistry 2]

[0044]

[0045] Y1 contains 70 mol % or more of the structure represented by formula (B).

[0046] [Chemistry 3]

[0047]

[0048] In the case of (ii) above, the following condition is adopted: at least one imidazole compound is contained as an essential component in an amount of 0.01 mol or more and less than 1 mol per 1 mol of the repeating unit of the polyimide precursor.

[0049] A2. The polyimide precursor composition according to the above Item A1, wherein 60 mol % or more of X1 is a structure represented by formula (1-1).

[0050] A3. The polyimide precursor composition according to any one of the preceding items, wherein 80 mol % or more of Y1 is a structure represented by formula (B).

[0051] A4. The polyimide precursor composition according to any one of the preceding items, further comprising at least one imidazole compound in an amount of 0.01 mol or more and less than 1 mol per 1 mol of the repeating unit of the polyimide precursor.

[0052] A5. The polyimide precursor composition as described in item A4 above, characterized in that the imidazole compound is at least one selected from the group consisting of 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1-phenylimidazole, imidazole and benzimidazole.

[0053] A6. A polyimide precursor composition as described in any one of the preceding items, wherein the polyimide precursor composition contains an amount of more than 0 mass parts and less than 60 mass parts with respect to 100 mass parts of the total of tetracarboxylic dianhydride and diamine compound when the polyimide precursor composition is produced. a Structure (here R a is a hydrogen atom or a hydrocarbon group).

[0054] A7. The polyimide precursor composition as described in item A6 above, wherein the silane compound is of the following formula:

[0055] (R a O) n Si(R b ) 4-n

[0056] (where n is an integer from 1 to 4, R a is a hydrogen atom or a straight-chain or branched alkyl group having 1 to 8 carbon atoms, R b A compound represented by an alkyl group or an aryl group having 10 or less carbon atoms.

[0057] A8. A polyimide film obtained from the polyimide precursor composition described in any one of the preceding items.

[0058] A9. A polyimide film / substrate laminate, characterized in that it has:

[0059] A polyimide film obtained from the polyimide precursor composition described in any one of the preceding items; and

[0060] Base material.

[0061] A10. The laminate according to the above Item A9, further comprising an inorganic thin film layer on the polyimide film of the laminate.

[0062] A11. The laminate according to any one of the preceding items, wherein the base material is a glass substrate.

[0063] A12. A method for producing a polyimide film / substrate laminate, comprising the following steps:

[0064] (a) a step of coating the polyimide precursor composition described in any one of the above items on a substrate; and

[0065] (b) A step of heat-treating the polyimide precursor on the substrate to form a polyimide film on the substrate.

[0066] A13. The method for producing a laminate as described in the above item A12, further comprising, after the above step (b), the step of: (c) forming an inorganic thin film layer on the polyimide film of the above laminate.

[0067] A14. A method for manufacturing a flexible electronic device, comprising the following steps:

[0068] (d) a step of forming at least one layer selected from a conductor layer and a semiconductor layer on the inorganic thin film layer of the laminate produced in the above-mentioned item A13; and

[0069] (e) A step of peeling the substrate and the polyimide film.

[0070] A15. A flexible electronic device comprising the polyimide film described in item A8 above.

[0071] A16. A flexible electronic device substrate, which is composed of the polyimide film described in the above item A8.

[0072] The present application specification also discloses inventions of a different form from the above, namely, inventions of series B.

[0073] B1. A polyimide precursor composition comprising:

[0074] A polyimide precursor having a repeating unit represented by the following general formula (I); and

[0075] At least one imidazole compound is contained in an amount of 0.01 mol or more and less than 1 mol per 1 mol of the repeating units of the polyimide precursor.

[0076] [Chemistry 4]

[0077]

[0078] (In the general formula I, X1 is a tetravalent aliphatic group or aromatic group, Y1 is a divalent aliphatic group or aromatic group, R1 and R2 are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, wherein,

[0079] X1 contains 70 mol % or more of the structure represented by formula (1-1) and / or the structure represented by formula (1-2),

[0080] [Chemistry 5]

[0081]

[0082] Y1 contains 50 mol % or more of the structure represented by formula (B).

[0083] [Chemistry 6]

[0084]

[0085] B2. The polyimide precursor composition according to the above item B1, wherein 40 mol % or more of X1 is a structure represented by formula (1-1).

[0086] B3. The polyimide precursor composition according to any one of the preceding items, wherein 60 mol % or more of Y1 is a structure represented by formula (B).

[0087] The polyimide precursor composition as described in any one of the preceding items, wherein X1 contains a structure represented by formula (1-1) and a structure represented by formula (1-2) in a total amount of 60 mol% or more.

[0088] B5. The polyimide precursor composition as described in any one of the preceding items, wherein the imidazole compound is at least one selected from the group consisting of 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1-phenylimidazole, imidazole and benzimidazole.

[0089] B6. A polyimide film obtained from the polyimide precursor composition described in any one of the preceding items.

[0090] B7. A polyimide film / substrate laminate, characterized in that it has:

[0091] A polyimide film obtained from the polyimide precursor composition described in any one of the preceding items; and

[0092] Base material.

[0093] B8. The laminate according to item B7, further comprising an inorganic thin film layer on the polyimide film of the laminate.

[0094] B9. A laminate as described in any one of the preceding items, wherein the substrate is a glass substrate.

[0095] B10. A method for producing a polyimide film / substrate laminate, comprising the following steps:

[0096] (a) a step of coating the polyimide precursor composition described in any one of the above items on a substrate; and

[0097] (b) A step of heat-treating the polyimide precursor on the substrate to form a polyimide film on the substrate.

[0098] B11. The method for producing a laminate as described in the above item B10, which further comprises, after the above step (b), the step of: (c) forming an inorganic thin film layer on the polyimide film of the above laminate.

[0099] B12. A method for manufacturing a flexible electronic device, comprising the following steps:

[0100] (d) forming at least one layer selected from a conductor layer and a semiconductor layer on the inorganic thin film layer of the laminate produced in the above item B11; and

[0101] (e) A step of peeling the substrate and the polyimide film.

[0102] Effects of the Invention

[0103] According to the present invention, a polyimide precursor composition can be provided, which can manufacture a polyimide film having improved light transmittance and adhesion in a polyimide film / substrate laminate while utilizing the advantages of aromatic polyimide films such as heat resistance and linear thermal expansion coefficient. That is, the polyimide precursor composition of the present invention is most suitable for manufacturing a polyimide film used as a flexible display substrate. Furthermore, the present invention can provide a polyimide film obtained from the polyimide precursor and a polyimide film / substrate laminate.

[0104] Furthermore, according to one embodiment of the present invention, a polyimide precursor composition having a more stable viscosity can be provided.

[0105] Furthermore, according to one embodiment of the present invention, a polyimide film and a polyimide film / substrate laminate obtained using the polyimide precursor composition can be provided. Furthermore, according to another embodiment of the present invention, a method for producing a flexible electronic device using the polyimide precursor composition and a flexible electronic device can be provided. DETAILED DESCRIPTION

[0106] In the present application, "flexible (electronic) device" means that the device itself is flexible, and usually, a semiconductor layer (transistors, diodes, etc. as components) is formed on a substrate to complete the device. "Flexible (electronic) device" is different from existing devices such as COF (Chip On Film) that have "hard" semiconductor components such as IC chips mounted on FPC (flexible printed circuit board). However, in order to operate or control the "flexible (electronic) device" of the present application, there is no problem in mounting "hard" semiconductor components such as IC chips on a flexible substrate, or electrically connecting them, or fusing them for use. As preferred flexible (electronic) devices, there can be cited flexible displays such as liquid crystal displays and organic EL displays, display devices such as electronic paper, solar cells, and light receiving devices such as CMOS.

[0107] More specifically, the term "flexible (electronic) device substrate" does not include a flexible wiring substrate (also referred to as a flexible substrate, a flexible printed wiring board, etc.).

[0108] In this application, the terms "for flexible (electronic) device substrates" and "for flexible display substrates" mean that when used in a polyimide film, the polyimide film itself is the main component of the substrate present in the final product (or the substrate itself), and does not refer to a film or layer not present in the final product, or an accessory layer laminated on the substrate. If a specific example is given, the peeling layer is not the substrate.

[0109] The terms "for flexible (electronic) device substrates" and "for flexible display substrates" refer to polyimide precursor compositions that, when used in polyimide precursor compositions, directly produce polyimide films for the above-mentioned substrates. Specifically, the polyimide precursor compositions are applied to a substrate and imidized to obtain polyimide films for "flexible (electronic) device substrates (including flexible display substrates, the same below)". Therefore, for example, when two or more polyimide precursor compositions (intermediate compositions) are mixed and used for the production of polyimide films, each polyimide precursor composition is not "for flexible (electronic) device substrates" as defined in the present application. This is because the structure of the obtained polyimide film depends on the structure of the polyimide precursor composition that directly produces the polyimide film.

[0110] In addition, the copper-clad (or metal) laminate is used to manufacture a flexible wiring substrate (flexible substrate, flexible printed wiring board), but since a flexible (electronic) device is not manufactured, the polyimide precursor composition used for the manufacture of the copper-clad laminate is not a polyimide precursor composition for a "flexible (electronic) device substrate". It should be noted that the definitions of the above terms are sometimes further explained in detail in this specification.

[0111] The polyimide precursor composition of the present invention is described below, and then the method for producing a flexible electronic device is described. The invention series A is described below as the center, and the invention series B containing an imidazole compound as an essential component is described in the item of the imidazole compound. The description of the invention series A is also applicable to the invention of the invention series B unless there is a contradiction.

[0112] <<Polyimide Precursor Composition>>

[0113] The polyimide precursor composition for forming a polyimide film contains a polyimide precursor. In a preferred embodiment, the polyimide precursor composition further contains a solvent, and the polyimide precursor is dissolved in the solvent.

[0114] The polyimide precursor has a repeating unit represented by the following general formula (I).

[0115] [Chemistry 7]

[0116]

[0117] (In general formula I, X1 is a tetravalent aliphatic group or aromatic group, Y1 is a divalent aliphatic group or aromatic group, and R1 and R2 are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.)

[0118] In particular, polyamic acid in which R1 and R2 are hydrogen atoms is preferred. When X1 and Y1 are aliphatic groups, the aliphatic group is preferably a group having an alicyclic structure.

[0119] In all repeating units of the polyimide precursor, X1 contains 50 mol% or more of the structure represented by formula (1-1), and contains a total of 70 mol% or more of the structure represented by formula (1-1) and the structure represented by formula (1-2). Here, formula (1-1) and formula (1-2) are structures derived from oxydiphthalic dianhydride (abbreviated as ODPA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (abbreviated as s-BPDA), respectively.

[0120] [Chemistry 8]

[0121]

[0122] Furthermore, 70 mol% or more of Y1 is a structure represented by formula (B), that is, a structure derived from 4-aminophenyl-4-aminobenzoate (abbreviated as 4-BAAB).

[0123] [Chemistry 9]

[0124]

[0125] By using a composition containing such a polyimide precursor, a polyimide film having high light transmittance and a high elastic modulus and improved adhesion of the polyimide film / substrate laminate can be produced. In addition, the obtained polyimide film is also excellent in properties such as heat resistance and low linear thermal expansion coefficient, which are advantages of wholly aromatic polyimide films.

[0126] Regarding the polyimide precursor, monomers (tetracarboxylic acid component, diamine component, other components) that provide X1 and Y1 in the general formula (I) will be described, and then the manufacturing method will be described.

[0127] In this specification, the tetracarboxylic acid component includes tetracarboxylic acids, tetracarboxylic dianhydrides, and tetracarboxylic acid derivatives such as tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chlorides used as raw materials for producing polyimide. Although not particularly limited, it is convenient to use tetracarboxylic dianhydrides in production. In the following description, examples of using tetracarboxylic dianhydrides as the tetracarboxylic acid component will be described. In addition, the diamine component is a diamine compound having two amino groups (-NH2) used as a raw material for producing polyimide.

[0128] In addition, in this specification, the polyimide film refers to both a film formed on a (carrier) substrate and present in the laminate and a film after peeling off the substrate. In addition, a material obtained by heat-treating (imidizing) the material constituting the polyimide film, that is, the polyimide precursor composition, is sometimes referred to as a "polyimide material".

[0129] <X1 and the tetracarboxylic acid component>

[0130] As described above, (i) or (ii) is satisfied.

[0131] (i) In all repeating units of the polyimide precursor, preferably 50 mol% or more of X1 is a structure represented by the following formula (1-1) (derived from ODPA), and preferably the total amount of the structure represented by the formula (1-1) (derived from ODPA) and the structure represented by the formula (1-2) (derived from s-BPDA) is 70 mol% or more of X1.

[0132] (ii) On the condition that an imidazole compound described later is contained in an amount of 0.01 mol or more and less than 1 mol relative to 1 mol of the repeating unit of the polyimide precursor, the total amount of the structure represented by the formula (1-1) (derived from ODPA) and the structure represented by the formula (1-2) (derived from s-BPDA) is preferably 70 mol% or more of X1, and it may contain only either the structure of the formula (1-1) or the structure of the formula (1-2).

[0133] In either case (i) or (ii), X1 may consist only of the structure of formula (1-1) and the structure of formula (1-2) (ie, the total of the structure of formula (1-1) and the structure of formula (1-2) is 100 mol %).

[0134] More preferably, 60 mol% or more of X1 is a structure of formula (1-1), which is advantageous when high light transmittance is required. Further preferably, 70 mol% or more of X1, further more preferably 80 mol% or more, further more preferably 90 mol% or more is a structure of formula (1-1), and 100 mol% may be a structure of formula (1-1).

[0135] In X1, the total ratio of the structures of formula (1-1) and formula (1-2) is more preferably 75 mol% or more, further more preferably in the order of 80 mol% or more, 90 mol% or more, and further preferably 100 mol%. Therefore, the ratio of the structure of formula (1-2) is 50 mol% or less, and may also be 0%. By containing the structure of formula (1-2), the linear thermal expansion coefficient and mechanical properties (elastic modulus, etc.) can be improved, and by containing, for example, 10 mol% to 40 mol%, these properties and light transmittance can be improved in a balanced manner.

[0136] In the present invention, as X1, a tetravalent aliphatic group or aromatic group (referred to as "other X1") other than the structure shown in formula (1-1) and formula (1-2) can be contained in an amount that does not damage the effect of the present invention. As an aliphatic group, a tetravalent group having an alicyclic structure is preferred. Therefore, the tetracarboxylic acid component can contain "other tetracarboxylic acid derivatives" other than ODPA and s-BPDA in an amount of less than 30 mol%, more preferably less than 20 mol%, and more preferably less than 10 mol% relative to 100 mol% of the tetracarboxylic acid component. It is also a preferred embodiment that the amount of "other tetracarboxylic acid derivatives" is 0 mol%.

[0137] In addition, when the proportion of the structure of formula (1-1) (derived from ODPA) in X1 is less than 70 mol%, especially when it is less than 60 mol%, it is also preferred to contain "other X1" in a proportion exceeding 0 mol%, for example, more than 10 mol%, less than 30 mol%, for example, less than 20 mol%. In this case, the particularly preferred "other X1" is preferably a quaternary group of a tetracarboxylic dianhydride having an aromatic ring containing a fluorine atom, such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), and a quaternary group of 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA). It should be noted that, regarding "other X1" not limited to this case, it is described as follows.

[0138] As the "other X1", a tetravalent group having an aromatic ring is preferred, and a tetravalent group having an aromatic ring having 6 to 40 carbon atoms is preferred.

[0139] Examples of the tetravalent group having an aromatic ring include the following groups: However, groups corresponding to formulae (1-1) and (1-2) are excluded.

[0140] [Chemistry 10]

[0141]

[0142] (In the formula, Z1 is a direct bond or any of the following divalent groups.

[0143] [Chemistry 11]

[0144]

[0145] Wherein, Z2 in the formula is a divalent organic group, Z3 and Z4 are each independently an amide bond, an ester bond, or a carbonyl bond, and Z5 is an organic group containing an aromatic ring.

[0146] Specific examples of Z2 include an aliphatic hydrocarbon group having 2 to 24 carbon atoms and an aromatic hydrocarbon group having 6 to 24 carbon atoms.

[0147] Specific examples of Z5 include aromatic hydrocarbon groups having 6 to 24 carbon atoms.

[0148] As the tetravalent group having an aromatic ring, the following tetravalent groups are particularly preferred because the obtained polyimide film can achieve both high heat resistance and high light transmittance.

[0149] [Chemistry 12]

[0150]

[0151] (Wherein, Z1 is a direct bond or a hexafluoroisopropylidene bond.)

[0152] Here, Z1 is more preferably a direct bond because the obtained polyimide film can achieve high heat resistance, high light transmittance, and low linear thermal expansion coefficient.

[0153] In addition, as a preferred group, in the above formula (9), Z1 can be exemplified as the following formula (3A):

[0154] [Chemistry 13]

[0155]

[0156] The compound containing the fluorenyl group shown. 11 and Z 12 Each of them is independently preferably the same and is a single bond or a divalent organic group. 11 and Z 12, preferably an organic group containing an aromatic ring, preferably a structure represented by formula (3A1).

[0157] [Chemistry 14]

[0158]

[0159] (Z 13 and Z 14 are independently a single bond, -COO-, -OCO- or -O-, where Z 14 When it is bonded to a fluorenyl group, Z is preferably 13 is -COO-, -OCO- or -O- and Z 14 It is a single bond structure; R 91 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably a methyl group, and n is an integer of 0 to 4, preferably 1.

[0160] Examples of the tetracarboxylic acid component providing a repeating unit of the general formula (I) in which X1 is a tetravalent group having an aromatic ring include pyromellitic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 9,9-bis(3,4-dicarboxyphenyl)fluorene, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,4'-oxydiphthalic acid, bis(3,4-dicarboxyphenyl)sulfone, m-terphenyl-3,4,3',4'-tetracarboxylic acid, p-terphenyl-3,4,3',4'-tetracarboxylic acid, dicarboxyphenyldimethylsilane, bisdicarboxyphenoxydiphenyl sulfide, sulfonyldiphthalic acid, and derivatives thereof such as tetracarboxylic dianhydrides, tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chlorides. As the tetracarboxylic acid component providing the repeating unit of the general formula (I) in which X1 is a tetravalent group having an aromatic ring containing a fluorine atom, for example, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, its tetracarboxylic dianhydride, tetracarboxylic acid silyl ester, tetracarboxylic acid ester, tetracarboxylic acid chloride and other derivatives thereof can be mentioned. The tetracarboxylic acid component can be used alone or in combination of two or more.

[0161] As the tetracarboxylic acid component that provides the repeating unit of formula (I) in which X1 is a tetravalent group having an alicyclic structure, examples include 1,2,3,4-cyclobutanetetracarboxylic acid, isopropylidenediphenoxy bisphthalic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-3,3',4,4'-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-2,3,3',4'-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-2,2',3,3'-tetracarboxylic acid, 4,4'-methylenebis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(propane-2,2-diyl)bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-oxybis(cyclohexane-1,2-dicarboxylic acid), 4,4'-thiobis(cyclohexane-1,2-dicarboxylic acid), 4,4'-sulfonylbis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(dimethylsilanediyl)bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(tetrafluoropropane-2,2-diyl)bis(cyclohexane-1,2-dicarboxylic acid), octahydrobicyclopentadiene-1,3,4,6-tetracarboxylic acid, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid, 6-(carboxymethyl)bicyclo[2.2.1]heptane-2,3,5-tricarboxylic acid, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]oct-5-ene-2,3,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]decane-3,4,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]dec-7-ene-3,4,9,10-tetracarboxylic acid, 9-oxatricyclo[4.2.1.02,5]nonane-3,4,7,8-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane 5,5'',6,6''-tetracarboxylic acid, (4arH,8acH)-decahydro-1t,4t:5c,8c-dimethanonaphthalene-2c,3c,6c,7c-tetracarboxylic acid, (4arH,8acH)-decahydro-1t,4t:5c,8c-dimethanonaphthalene-2t,3t,6c,7c-tetracarboxylic acid, decahydro-1,4-ethano-5,8-methanonaphthalene-2,3,6,7-tetracarboxylic acid, tetradecahydro-1,4:5,8:9,10-trimethanoanthracene-2,3,6,7-tetracarboxylic acid, and their derivatives such as tetracarboxylic dianhydrides, tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarbonyl chlorides. The tetracarboxylic acid component can be used alone, or two or more thereof can be used in combination.

[0162] <Y1 and diamine component>

[0163] As described above, in all the repeating units in the polyimide precursor, it is preferred that 70 mol% or more of Y1 has the structure of formula (B), and more preferably 80 mol% or more, still more preferably 90 mol% or more, and also preferably 100 mol% of Y1 has the structure of formula (B).

[0164] In the present invention, as Y1, a divalent aliphatic group or aromatic group other than the structure represented by formula (B) (referred to as "other Y1") may be contained in an amount within a range that does not impair the effect of the present invention. That is, in addition to 4-aminophenyl-4-aminobenzoate (4-BAAB), the diamine component may contain "other diamine compounds" in an amount of 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less relative to 100 mol% of the diamine component. It is also a preferred embodiment that the amount of "other diamine compounds" is 0 mol%.

[0165] In addition, when the proportion of the structure of formula (1-1) (derived from 4-BAAB) is less than 90 mol%, especially when it is 80 mol% or less, it is also preferred to contain "other Y1" in a proportion exceeding 0 mol%, for example, 10 mol% or more, 20 mol% or less, for example, 15 mol% or less. In this case, particularly preferred "other Y1" is preferably a diamine compound having an ether bond in the molecular chain direction such as 4,4-oxydiphenylamine (4,4-ODA) and 4,4'-bis(4-aminophenoxy)biphenyl (BAPB). It should be noted that "other Y1" not limited to this case is as follows.

[0166] When "other Y1" is a divalent group having an aromatic ring, it is preferably a divalent group having 6 to 40 carbon atoms, more preferably a divalent group having 6 to 20 carbon atoms.

[0167] Examples of the divalent group having an aromatic ring include the following groups.

[0168] [Chemistry 15]

[0169]

[0170] (W1 is a direct bond or a divalent organic group, n 11 ~n 13 Each independently represents an integer from 0 to 4, R 51 , R 52 , R 53 Each is independently an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group.)

[0171] Specific examples of W1 include a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6), except for the group corresponding to the formula (B).

[0172] [Chemistry 16]

[0173]

[0174] [Chemistry 17]

[0175]

[0176] (R in formula (6) 61 ~R 68 Each independently represents a direct bond or any one of the divalent groups represented by the above formula (5).

[0177] Here, since the obtained polyimide can take into account high heat resistance, high transparency, and low linear thermal expansion coefficient, W1 is particularly preferably a direct bond or one selected from the group consisting of groups represented by the formula: -NHCO-, -CONH-, -COO-, and -OCO-. In addition, W1 is also particularly preferably R 61 ~R 68 It is any one of the divalent groups represented by the above formula (6) which is a direct bond or one selected from the group consisting of groups represented by the formulas: -NHCO-, -CONH-, -COO-, and -OCO-.

[0178] In addition, as a preferred group, in the above formula (4), W1 can be exemplified as the following formula (3B):

[0179] [Chemistry 18]

[0180]

[0181] The compound containing the fluorenyl group shown. 11 and Z 12 Each of them is independently preferably the same and is a single bond or a divalent organic group. 11 and Z 12 , preferably an organic group containing an aromatic ring, preferably a structure represented by formula (3B1).

[0182] [Chemistry 19]

[0183]

[0184] (Z 13 and Z 14 Each independently represents a single bond, -COO-, -OCO- or -O-, where Z 14 When it is bonded to a fluorenyl group, Z is preferably 13 is -COO-, -OCO- or -O- and Z 14 It is a single bond structure; R 91 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably a phenyl group, and n is an integer of 0 to 4, preferably 1. )

[0185] As other preferred groups, in the above formula (4), compounds in which W1 is a phenylene group, that is, terphenylenediamine compounds can be mentioned, and compounds in which all of them are bonded at the para position are particularly preferred.

[0186] As other preferred groups, in the above formula (4), W1 can be exemplified as R in the structure where the first phenyl ring of formula (6) is 61 and R 62 A 2,2-propylene compound.

[0187] As another preferred group, in the above formula (4), there can be mentioned a compound where W1 is represented by the following formula (3B2).

[0188] [Chemistry 20]

[0189]

[0190] Examples of the diamine component that provides Y1 as a divalent group having an aromatic ring include p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)benzidine, m-tolidine, 3,4'-diaminobenzanilide, N,N'-bis(4-aminophenyl)terephthalamide, N,N'-p-phenylenebis(p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis(4-aminophenyl)terephthalate, biphenyl-4,4'-dicarboxylic acid bis(4 -aminophenyl) ester, p-phenylene bis(p-aminobenzoate), bis(4-aminophenyl)-[1,1'-biphenyl]-4,4'-dicarboxylate, [1,1'-biphenyl]-4,4'-diylbis(4-aminobenzoate), 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, p-methylenebis(phenylenediamine), 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)benzene, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, bis(4-aminophenyl)sulfone, 3,3'-bis(trifluoromethyl)benzidine, 3,3'-bis((aminophenoxy)phenyl)propane, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-(4-aminophenoxy)diphenyl)sulfone, bis(4-(3-aminophenoxy)diphenyl)sulfone, octafluorobiphenyl amine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,4-bis(4-aminoanilino)-6-amino-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-methylamino-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-ethylamino-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-anilino-1,3,5-triazine. Examples of the diamine component providing a repeating unit of the general formula (I) in which Y1 is a divalent group having an aromatic ring containing a fluorine atom include 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, and 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.Preferred diamine compounds include 9,9-bis(4-aminophenyl)fluorene, 4,4'-(((9H-fluorene-9,9-diyl)bis([1,1'-biphenyl]-5,2-diyl))bis(oxy))diamine, [1,1':4',1"-terphenyl]-4,4"-diamine, and 4,4'-([1,1'-binaphthyl]-2,2'-diylbis(oxy))diamine. The diamine components may be used alone or in combination of two or more.

[0191] When "other Y1" is a divalent group having an alicyclic structure, it is preferably a divalent group having an alicyclic structure having 4 to 40 carbon atoms, more preferably having at least one aliphatic 4- to 12-membered ring, and more preferably an aliphatic 6-membered ring.

[0192] Examples of the divalent group having an alicyclic structure include the following groups.

[0193] [Chemistry 21]

[0194]

[0195] (wherein, V1 and V2 are each independently a direct bond or a divalent organic group, n 21 ~n 26 Each independently represents an integer from 0 to 4, R 81 ~R 86 are each independently an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group, R 91 , R 92 , R 93 Each is independently selected from the group consisting of groups represented by the formula: -CH2-, -CH=CH-, -CH2CH2-, -O-, -S-.)

[0196] Specific examples of V1 and V2 include a direct bond and a divalent group represented by the above formula (5).

[0197] Examples of the diamine component that provides Y1 as a divalent group having an alicyclic structure include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, and 1,3-diaminocyclobutane. , 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxybicycloheptane, diaminomethoxybicycloheptane, isophoronediamine, diaminotricyclodecane, diaminomethyltricyclodecane, bis(aminocyclohexyl)methane, bis(aminocyclohexyl)isopropylidene, 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane. The diamine components may be used alone or in combination of two or more.

[0198] As the tetracarboxylic acid component and the diamine component providing the repeating unit represented by the general formula (I), any of aliphatic tetracarboxylic acids other than alicyclic ones (particularly dianhydrides) and / or aliphatic diamines can be used, and the content thereof is preferably less than 30 mol%, more preferably less than 20 mol%, and further preferably less than 10 mol% (including 0%) relative to 100 mol% of the total of the tetracarboxylic acid component and the diamine component.

[0199] By including a structure represented by formula (3B) as "other Y1" or a diamine compound such as 9,9-bis(4-aminophenyl)fluorene as a specific compound, Tg may be increased and the phase difference (retardation) in the film thickness direction may be reduced.

[0200] In the present invention, regardless of the above description, the polyimide precursor composition for producing a polyimide film may preferably not contain a specific tetracarboxylic acid compound and / or a specific diamine compound, or a specific compound.

[0201] (a) The diamine compound represented by H2N-Y2-N=N-Y2-NH2 or H2N-Y2-NHNH-Y2-NH2 (Y2 is a divalent organic group) is preferably very small (less than 5 mol in the repeating unit represented by the general formula (I)) or does not contain it.

[0202] (b) A surfactant and an alkoxysilane compound may be added, but it is also preferable that no surfactant is contained, and it is also preferable that no compound other than the preferred compound in the present invention is contained in the alkoxysilane compound.

[0203] (c) It is preferred that the compound does not contain any of a diamine compound having a -SO2- group, a diamine compound having a fluorene structure, and a fluorine-containing diamine compound.

[0204] (d) The diamine compound having a benzamide structure such as 3,5-diaminobenzamide is preferably not contained in an amount of 5 mol% or more in the diamine component, and is also preferably not contained at all.

[0205] (e) The diamine compound represented by the following formula is preferably not contained in an amount of 10:30 (=25:75) or more in a molar ratio relative to 4-BAAB. Even if contained, the molar ratio is more preferably 15:85 or less, further preferably 10:90 or less, and preferably not contained at all.

[0206] [Chemistry 22]

[0207]

[0208] (f) It is preferred that the combination of a tetracarboxylic dianhydride and a diamine compound contain no repeating unit having a structure of the following formula.

[0209] [Chemistry 23]

[0210]

[0211] (g) The diamine component preferably does not contain either 2,2′-bistrifluoromethylbenzidine or 1,4-diaminocyclohexane.

[0212] (h) The diamine component preferably does not contain a diamine monomer containing a nitrogen heterocyclic structure in an amount of 3 mol% to 8 mol%, and preferably does not contain it at all.

[0213] The polyimide precursor can be prepared from the above-mentioned tetracarboxylic acid component and diamine component. According to the chemical structure taken by R1 and R2, the polyimide precursor used in the present invention (including at least one of the repeating units represented by the above formula (I)) can be classified as follows:

[0214] 1) Polyamic acid (R1 and R2 are hydrogen);

[0215] 2) polyamic acid ester (at least a part of R1 and R2 is an alkyl group);

[0216] 3) 4) Polyamic acid silyl ester (at least a part of R1 and R2 is an alkylsilyl group).

[0217] And the polyimide precursor can be easily produced by the following production method according to this classification. However, the production method of the polyimide precursor used in the present invention is not limited to the following production method.

[0218] 1) Polyamic acid

[0219] The polyimide precursor can be suitably obtained as a polyimide precursor solution by the following reaction: tetracarboxylic dianhydride and diamine component as tetracarboxylic acid components are reacted in a solvent in approximately equimolar ratios, preferably in a ratio where the molar ratio of the diamine component to the tetracarboxylic acid component [the number of moles of the diamine component / the number of moles of the tetracarboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, at a relatively low temperature of, for example, 120° C. or less while suppressing imidization.

[0220] There is no limitation, more specifically, diamine is dissolved in an organic solvent or water, tetracarboxylic dianhydride is slowly added to the solution while stirring, and stirred in the range of 0 to 120°C, preferably 5°C to 80°C for 1 hour to 72 hours, thereby obtaining a polyimide precursor. In the case of reaction above 80°C, the molecular weight varies depending on the temperature history during polymerization, and imidization is performed by heat, so it may not be possible to stably produce a polyimide precursor. The order of addition of diamine and tetracarboxylic dianhydride in the above-mentioned production method is easy to increase the molecular weight of the polyimide precursor, so it is preferred. In addition, the order of addition of diamine and tetracarboxylic dianhydride in the above-mentioned production method can also be reversed, which is preferred because the precipitate is reduced. When water is used as a solvent, it is preferred to add imidazoles such as 1,2-dimethylimidazole or bases such as triethylamine in an amount of 0.8 times or more of the carboxyl group of the generated polyamic acid (polyimide precursor).

[0221] 2) Polyamic acid ester

[0222] Tetracarboxylic dianhydride is reacted with any alcohol to obtain a dicarboxylic acid diester, which is then reacted with a chlorinating agent (thionyl chloride, oxalyl chloride, etc.) to obtain a diester dicarboxylic acid chloride. The diester dicarboxylic acid chloride and diamine are stirred at -20°C to 120°C, preferably in the range of -5°C to 80°C for 1 hour to 72 hours to obtain a polyimide precursor. In the case of a reaction above 80°C, the molecular weight varies depending on the temperature history during polymerization, and imidization is performed by heat, so it may not be possible to stably manufacture a polyimide precursor. In addition, a polyimide precursor can also be easily obtained by dehydrating and condensing a dicarboxylic acid diester and a diamine using a phosphorus-based condensing agent, a carbodiimide condensing agent, etc.

[0223] Since the polyimide precursor obtained by this method is stable, it can also be purified by adding a solvent such as water or alcohol and performing reprecipitation.

[0224] 3) Polyamic acid silyl ester (indirect method)

[0225] A diamine is reacted with a silylating agent in advance to obtain a silylated diamine. The silylated diamine is purified by distillation or the like as needed. Then, the silylated diamine is dissolved in a dehydrated solvent in advance, tetracarboxylic dianhydride is slowly added while stirring, and stirred at 0 to 120°C, preferably in the range of 5°C to 80°C for 1 hour to 72 hours, thereby obtaining a polyimide precursor. In the case of a reaction above 80°C, the molecular weight varies depending on the temperature history during polymerization, and imidization is carried out by heat, so it may not be possible to stably produce a polyimide precursor.

[0226] 4) Polyamic acid silyl ester (direct method)

[0227] The polyamic acid solution obtained in the method 1) is mixed with a silylating agent and stirred at 0 to 120° C., preferably in the range of 5 to 80° C., for 1 to 72 hours to obtain a polyimide precursor. When reacting at 80° C. or higher, the molecular weight varies depending on the temperature history during polymerization, and imidization proceeds by heat, so there is a possibility that the polyimide precursor cannot be stably produced.

[0228] As the silylating agent used in the method 3) and the method 4), when a silylating agent that does not contain chlorine is used, it is not necessary to purify the silylated polyamic acid or the obtained polyimide, so it is preferred. As the silylating agent that does not contain chlorine atoms, N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane can be cited. Because it does not contain fluorine atoms and has low cost, N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferred.

[0229] In the silylation reaction of diamine in the method 3), an amine catalyst such as pyridine, piperidine, triethylamine, etc. may be used to promote the reaction. The catalyst may be used directly as a polymerization catalyst for the polyimide precursor.

[0230] The solvent used in preparing the polyimide precursor is preferably water, or a non-protonic solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, etc. Any type of solvent can be used without problem as long as it can dissolve the raw monomer components and the generated polyimide precursor, so there is no particular limitation on its structure. As the solvent, it is preferred to use water, or amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and N-ethyl-2-pyrrolidone, cyclic ester solvents such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, and 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclopentane, dimethyl sulfoxide, and the like. In addition, other common organic solvents may be used, i.e., phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, turpentine, mineral spirits, naphtha-based solvents, etc. It should be noted that two or more solvents may be used in combination.

[0231] In the production of the polyimide precursor, there are no particular restrictions, and a monomer and a solvent are added so that the solid content concentration of the polyimide precursor (polyimide-converted mass concentration) is, for example, 5% by mass to 45% by mass to carry out the reaction.

[0232] The logarithmic viscosity of the polyimide precursor is not particularly limited, but preferably the logarithmic viscosity in a 0.5 g / dL N-methyl-2-pyrrolidone solution at 30° C. is 0.2 dL / g or more, more preferably 0.3 dL / g or more, and particularly preferably 0.4 dL / g or more. When the logarithmic viscosity is 0.2 dL / g or more, the molecular weight of the polyimide precursor is high, and the obtained polyimide has excellent mechanical strength and heat resistance.

[0233] <Imidazole compounds>

[0234] The polyimide precursor composition can contain at least one imidazole compound. The imidazole compound is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1-phenylimidazole, imidazole and benzimidazole. The imidazole compound can be used in combination with a plurality of compounds. In one embodiment, the imidazole compound is preferably selected from imidazole compounds other than 1,2-dimethylimidazole, preferably dimethyl substituted imidazole compounds other than 1,2-substituted, monomethyl substituted imidazole compounds, aromatic substituted imidazole compounds, particularly preferably 2-phenylimidazole, 1-phenylimidazole, imidazole and benzimidazole.

[0235] The content of the imidazole compound in the polyimide precursor composition can be appropriately selected in consideration of the balance between the addition effect and the stability of the polyimide precursor composition. When the imidazole compound is added, its amount (total content) exceeds 0 mole relative to 1 mole of the repeating unit of the polyimide precursor. In order to exert a certain degree of addition effect, it is 0.01 mole or more, preferably 0.02 mole or more. On the other hand, from the perspective of the viscosity stability of the polyimide precursor composition, it is preferably less than 1 mole, more preferably less than 0.8 mole. The addition of the imidazole compound has an effect on improving the adhesion under long-term high temperature environments such as the increase in light transmittance and annealing treatment.

[0236] In particular, when the ratio of the structure of the formula (1-1) (derived from ODPA) in X1 is less than 90 mol %, particularly less than 80 mol %, it is preferred to add an imidazole compound.

[0237] Imidazole compounds can solve the problem when the proportion of the structure of formula (1-1) (from ODPA) in X1 is small, and when the total proportion of the structure of formula (1-1) (from ODPA) and the structure of formula (1-2) (from s-BPDA) is small. When adding imidazole compounds, the proportion of the structure of formula (1-1) (from ODPA) in X1 can be made to be 0 mol% or more. That is, as long as the total proportion of the structure of formula (1-1) in X1 and the structure of formula (1-2) is 70 mol% or more, only any one of them can be included, and the proportion of the structure of formula (1-1) can be zero.

[0238] To summarize, the present application discloses, as specified in 1. of the invention series A, an embodiment that does not require an imidazole compound (the case of condition (i)) and an embodiment that requires an imidazole compound (the case of condition (ii)).

[0239] In addition, the present application discloses the following other invention, namely, the invention series B, which requires the addition of an imidazole compound.

[0240] A polyimide precursor composition, comprising a polyimide precursor having a repeating unit represented by the general formula (I), wherein:

[0241] X1 contains 70 mol% or more (preferably 80 mol% or more or 90 mol% or more) of the structure represented by formula (1-1) and / or the structure represented by formula (1-2),

[0242] Y1 contains 50 mol% or more (preferably 60 mol% or more, 70 mol% or more, or 80 mol% or more) of the structure represented by formula (B),

[0243] Furthermore, at least one imidazole compound is contained in an amount of 0.01 mol or more and less than 1 mol based on 1 mol of the repeating unit of the polyimide precursor.

[0244] In this other invention, elements and matters other than those specified above are in accordance with the description of the invention series A in the main text of the present application.

[0245] <Silane Compound>

[0246] It is also preferred to add a Si-OR a Structure (R a A silane compound containing a hydrogen atom or a hydrocarbon group (hereinafter sometimes referred to as a "silane compound") is used as an additive. The addition of the silane compound has the effect of improving light transmittance.

[0247] R a It is preferably a hydrocarbon group with 10 or less carbon atoms, preferably an alkyl group or an aryl group, particularly a linear or branched alkyl group with 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. a O) n Si(R b ) 4-n (n is an integer of 1 to 4). a As described above, n is preferably 1 to 3, more preferably 2 or 3. b It is a hydrocarbon group having 10 or less carbon atoms, preferably an alkyl group or an aryl group, more preferably an aryl group, and particularly preferably a phenyl group.

[0248] Specifically, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, trihexylmethoxysilane, trihexylethoxysilane, triphenylmethoxysilane and triphenylethoxysilane can be mentioned. The silane compound can also be used in combination of two or more.

[0249] The addition amount of the silane compound can be appropriately selected in consideration of the addition effect. In the case of adding a silane compound, its amount (total content) exceeds 0 mass parts relative to a total of 100 mass parts of tetracarboxylic acid components and diamine components, in order to exert a certain degree of addition effect, it is 0.05 mass parts or more, preferably 0.1 mass parts or more, more preferably 0.3 mass parts or more, and more preferably 0.5 mass parts or more, and more preferably 1 mass parts or more. From the aspect of the balance of physical properties, for example, 60 mass parts or less, preferably 50 mass parts or less, more preferably 40 mass parts or less, and more preferably 35 mass parts or less, and more preferably 30 weight parts or less, and more preferably 25 weight parts or less.

[0250] <Blending of polyimide precursor composition and "polyimide precursor composition for flexible electronic device substrate">

[0251] The polyimide precursor composition used in the present invention contains at least one polyimide precursor as described above and preferably contains a solvent. Furthermore, as described above, it also preferably contains at least one imidazole compound.

[0252] As a solvent, the above-mentioned solvent described as a solvent used in preparing a polyimide precursor can be used. Usually, the solvent used in preparing a polyimide precursor can be used directly, that is, in the state of a polyimide precursor solution, but it can also be diluted or concentrated and used as needed. The imidazole compound (when added) is dissolved and present in the polyimide precursor composition. There is no particular limitation on the concentration of the polyimide precursor, and it is usually 5% to 45% by mass in terms of polyimide conversion mass concentration (solid content concentration). Here, the polyimide conversion mass refers to the mass when all repeating units are completely imidized.

[0253] The viscosity (rotational viscosity) of the polyimide precursor composition of the present invention is not particularly limited, and is measured using an E-type rotational viscometer at a temperature of 25° C. and a shear rate of 20 sec. -1The rotational viscosity measured under the conditions of is preferably 0.01 to 1000 Pa·sec, more preferably 0.1 to 100 Pa·sec. In addition, thixotropy can be imparted as required. In the above-mentioned range of viscosity, it is easy to handle during coating or film formation, and shrinkage cavities are suppressed and leveling properties are excellent, so a good coating can be obtained.

[0254] The polyimide precursor composition of the present invention may contain, as required, a chemical imidizing agent (acid anhydrides such as acetic anhydride, amine compounds such as pyridine and isoquinoline), an antioxidant, an ultraviolet absorber, a filler (inorganic particles such as silica, etc.), a dye, a pigment, a coupling agent such as a silane coupling agent, a primer, a flame retardant, a defoamer, a leveling agent, a rheology control agent (flow aid), etc. It should be noted that when the polyimide precursor composition of the present invention is imidized, thermal imidization is preferably performed, and in this case, it is preferably not to contain an acid anhydride such as acetic anhydride as a chemical imidizing agent.

[0255] The polyimide precursor composition can be prepared by adding an imidazole compound or a solution of an imidazole compound to the polyimide precursor solution obtained by the above method and mixing them. The tetracarboxylic acid component and the diamine component can be reacted in the presence of the imidazole compound.

[0256] The polyimide precursor composition of the present invention can be used as a "flexible electronic device substrate (particularly preferably a flexible display substrate. The same shall apply hereinafter.)". As described above, in the present invention, the polyimide precursor composition "for a flexible electronic device substrate" refers to a composition to be directly applied on a substrate as described below.

[0257] <<Manufacturing of polyimide film / substrate laminate and flexible electronic device>>

[0258] The polyimide precursor composition of the present invention (i.e., a polyimide precursor composition for a flexible electronic device substrate) can be used to manufacture a polyimide film / substrate laminate. The polyimide film / substrate laminate can be manufactured by the following steps: (a) a step of applying the polyimide precursor composition to a substrate; (b) heat-treating the polyimide precursor on the substrate to manufacture a laminate having a polyimide film laminated on the substrate (polyimide film / substrate laminate). In addition, after forming the polyimide film on the substrate, it is also preferred to further include a step of forming an inorganic thin film on the surface of the polyimide film as step (b2).

[0259] The method for manufacturing a flexible electronic device of the present invention uses a polyimide film / substrate laminate manufactured by the above-mentioned steps (a) and (b) (preferably a further step (b2)), and further comprises the following steps: (c) a step of forming at least one layer selected from a conductor layer and a semiconductor layer on the polyimide film of the above-mentioned laminate; and (d) a step of peeling the above-mentioned substrate from the above-mentioned polyimide film.

[0260] First, in step (a), a polyimide precursor composition is cast on a substrate, and imidization and solvent removal are performed by heat treatment to form a polyimide film, thereby obtaining a laminate of the substrate and the polyimide film (polyimide film / substrate laminate).

[0261] As the substrate, a heat-resistant material is used, for example, a plate-like or sheet-like substrate of a ceramic material (glass, alumina, etc.), a metal material (iron, stainless steel, copper, aluminum, etc.), a semiconductor material (silicon, compound semiconductor, etc.), or a film or sheet-like substrate of a heat-resistant plastic material (polyimide, etc.). Generally, a flat and smooth plate is preferred, and generally, a glass substrate of soda-lime glass, borosilicate glass, alkali-free glass, sapphire glass, etc.; a semiconductor substrate (including compound semiconductor) of silicon, GaAs, InP, GaN, etc.; a metal substrate of iron, stainless steel, copper, aluminum, etc. is used.

[0262] As the substrate, a glass substrate is particularly preferred. Flat, smooth and large-area glass substrates have been developed and can be easily obtained. There is no limitation on the thickness of plate-like substrates such as glass substrates. From the perspective of ease of handling, it is, for example, 20 μm to 4 mm, preferably 100 μm to 2 mm. In addition, there is no particular limitation on the size of the plate-like substrate. One side (the long side in the case of a rectangle) is, for example, about 100 mm to about 4000 mm, preferably about 200 mm to about 3000 mm, and more preferably about 300 mm to about 2500 mm.

[0263] These glass substrates and other base materials may have an inorganic thin film (eg, a silicon oxide film) or a resin thin film formed on the surface.

[0264] The method for casting the polyimide precursor composition on the substrate is not particularly limited, and examples thereof include slit coating, die coating, blade coating, spray coating, inkjet coating, nozzle coating, spin coating, screen printing, rod coating, electrodeposition and the like.

[0265] In step (b), the polyimide precursor composition is heat-treated on the substrate to convert it into a polyimide film, thereby obtaining a polyimide film / substrate laminate. The heat treatment conditions are not particularly limited, but it is preferably dried at a temperature range of 50°C to 150°C, and then treated at a maximum heating temperature of, for example, 150°C to 600°C, preferably 200°C to 550°C, and more preferably 250°C to 500°C.

[0266] The thickness of the polyimide film is preferably 1 μm or more, more preferably 2 μm or more, and further preferably 5 μm or more. When the thickness is less than 1 μm, the polyimide film cannot maintain sufficient mechanical strength. For example, when used as a substrate for a flexible electronic device, it is sometimes unable to fully withstand stress and is damaged. In addition, the thickness of the polyimide film is preferably 100 μm or less, more preferably 50 μm or less, and further preferably 20 μm or less. If the thickness of the polyimide film becomes thicker, it sometimes becomes difficult to thin the flexible device. In order to maintain sufficient tolerance as a flexible device and further thin the film, the thickness of the polyimide film is preferably 2 μm to 50 μm.

[0267] In the present invention, the polyimide film / substrate laminate preferably has small warpage. The properties of the polyimide film can be evaluated by the residual stress between the polyimide film and the silicon substrate in the polyimide film / silicon substrate (wafer) laminate. The residual stress that can be achieved in the present invention will be described later.

[0268] The polyimide film in the polyimide film / substrate laminate may also have a second layer such as an inorganic thin film on the surface. Therefore, as step (b2), it is preferred to have a step of forming an inorganic thin film on the surface of the polyimide film formed on the substrate. The inorganic thin film is particularly preferred to function as a barrier layer for water vapor or oxygen (air). As the water vapor barrier layer, for example, a layer selected from silicon nitride (SiN x ), silicon oxide (SiO x ), silicon oxynitride (SiO x N y), aluminum oxide (Al2O3), titanium oxide (TiO2), zirconium oxide (ZrO2) and other metal oxides, metal nitrides and metal oxynitrides. In general, known methods for forming these thin films include physical vapor deposition methods such as vacuum evaporation, sputtering, and ion plating, and chemical vapor deposition methods (CVD: chemical vapor deposition) such as plasma CVD and catalytic chemical vapor deposition (Cat-CVD). In these film formation methods including the CVD method, in order to improve the barrier function, after the film is formed, high-temperature annealing is performed at, for example, 350°C to 450°C to densify the film. It should be noted that in the present application, "inorganic thin film" refers to two states before and after annealing. When only one is indicated, it is explicitly indicated or made clear according to the context. Similarly, "polyimide film / substrate laminate" refers to both having and not having an "inorganic thin film".

[0269] The second layer may also be a plurality of layers. In this case, different types of inorganic thin films may be formed, and resin films and inorganic thin films may be composited. As an example of the latter, a three-layer structure of barrier layer / polyimide layer / barrier layer may be formed on the polyimide film in a polyimide film / substrate laminate.

[0270] In step (c), at least one layer selected from a conductor layer and a semiconductor layer is formed on the polyimide film (including the case where a second layer such as an inorganic thin film is laminated on the surface of the polyimide film) using the polyimide / substrate laminate obtained in step (b). These layers may be formed directly on the polyimide film (including the case where the second layer is laminated), or may be formed indirectly after laminating other layers required for the device.

[0271] The conductor layer and / or semiconductor layer are selected appropriately according to the elements and circuits required by the target electronic device. In step (c) of the present invention, when at least one of the conductor layer and the semiconductor layer is formed, it is also preferred to form at least one of the conductor layer and the semiconductor layer on a polyimide film formed with an inorganic film.

[0272] The conductor layer and the semiconductor layer include both the case where they are formed on the entire surface of the polyimide film and the case where they are formed on a portion of the polyimide film. The present invention may be transferred to step (d) immediately after step (c), or may be transferred to step (d) after forming at least one layer selected from the conductor layer and the semiconductor layer in step (c), further forming a device structure, and then transferring to step (d).

[0273] In the case of manufacturing a TFT liquid crystal display device as a flexible device, for example, metal wiring, TFT using amorphous silicon or polycrystalline silicon, and transparent pixel electrodes are formed on a polyimide film having an inorganic film formed on the entire surface as required. The TFT includes, for example, a semiconductor layer such as a gate metal layer, an amorphous silicon film, a gate insulating layer, wiring connected to the pixel electrode, etc. In addition, the structure required for the liquid crystal display can be further formed by a known method. In addition, a transparent electrode and a color filter can also be formed on the polyimide film.

[0274] When manufacturing an organic EL display, for example, TFTs may be formed as needed on a polyimide film having an inorganic film formed on the entire surface in addition to transparent electrodes, a light-emitting layer, a hole transport layer, an electron transport layer, etc.

[0275] The polyimide film preferred in the present invention is excellent in various properties such as heat resistance and toughness, and therefore the method of forming circuits, elements, and other structures required for the device is not particularly limited.

[0276] Next, in step (d), the substrate and the polyimide film are peeled off. The peeling method may be a mechanical peeling method in which an external force is applied to physically peel the substrate, but the polyimide film / substrate laminate of the present invention has excellent adhesion, so it is particularly preferred to peel the substrate by irradiating a laser from the substrate surface to perform the peeling.

[0277] The structure or components required for the device are further formed or assembled on the (semi-)product using the polyimide film after the substrate is peeled off as a substrate to complete the device.

[0278] As described above, a flexible electronic device including the polyimide film is completed, and in the flexible electronic device, the polyimide film functions as a flexible electronic device substrate.

[0279] It should be noted that as another method for manufacturing flexible electronic devices, after manufacturing the polyimide film / substrate laminate through the above-mentioned step (b), the polyimide film can be peeled off, and at least one layer selected from a conductor layer and a semiconductor layer and the necessary structure can be formed on the polyimide film as in the above-mentioned step (c), to manufacture a (semi) product using the polyimide film as a substrate.

[0280] <<Polyimide Film Properties in Polyimide Film / Base Laminate>>

[0281] When the polyimide film / substrate laminate as described above is produced from the polyimide precursor composition of the present invention, the polyimide film and the substrate have excellent adhesion, and therefore the laminate is particularly preferably used for such an application.

[0282] The ranges of the properties of the polyimide film achieved in the present invention are described below, and preferred ranges are shown in the order of a first range, a second range, a third range, ..., and an nth range.

[0283] The polyimide film produced from the polyimide precursor composition of the present invention is excellent in light transmittance, thermal properties, and heat resistance, as well as adhesion to a substrate such as a glass substrate.

[0284] Adhesion can be evaluated by peel strength. The peel strength between the polyimide film and the substrate in the polyimide film / substrate laminate is preferably 50 gf / cm (0.49 N / cm) or more (the first range) in a tensile speed of 2 mm / min and a 90° peel test, and more preferably 100 gf / cm (0.98 N / cm) or more (the second range), 150 gf / cm (1.47 N / cm) or more (the third range), 200 gf / cm (1.96 N / cm) or more (the fourth range), 300 gf / cm (2.94 N / cm) or more (the fifth range), 400 gf / cm (3.92 N / cm) or more (the sixth range), and 500 gf / cm (4.9 N / cm) or more (the seventh range) in sequence. The upper limit is usually 5 kgf / cm (49.0 N / cm) or less, preferably 3 kgf / cm (29.4 N / cm) or less. The peel strength is usually measured in air or in the atmosphere.

[0285] As described above, the polyimide film / substrate laminate preferably has a small warp, and the properties of the polyimide film can be evaluated by the residual stress between the polyimide film and the silicon substrate in the polyimide film / silicon substrate (wafer) laminate. The details of the measurement are recorded in Japanese Patent Gazette No. 6798633. Among them, the polyimide film is placed at 23°C in a dry state. The residual stress thus evaluated is preferably 20MPa or less (the first range), and further preferably 15MPa or less (the second range), 12MPa or less (the third range), and 10MPa or less (the fourth range).

[0286] In one embodiment of the present invention, when measured using a film having a thickness of 10 μm, the 450 nm light transmittance of the polyimide film is preferably 73% or more (the first range), and more preferably 74% or more (the second range), and more preferably 75% or more (the third range). In addition, when measured using a film having a thickness of 10 μm, the yellowness (YI) of the polyimide film is preferably 13 or less (the first range), and more preferably 12 or less (the second range), 11 or less (the third range), 10 or less (the fourth range), and 9 or less (the fifth range). In addition, the yellowness (YI) is preferably 0 or more.

[0287] In addition, when measured using a film with a thickness of 10 μm, the haze value of the polyimide film is preferably less than 1.0% (first range), and more preferably below 0.9% (second range), below 0.8% (third range), below 0.7% (fourth range), and below 0.6% (fifth range).

[0288] The polyimide film of the present invention has an extremely low linear thermal expansion coefficient (CTE). In one embodiment of the present invention, when measured using a film with a thickness of 10 μm, the linear thermal expansion coefficient of the polyimide film from 150° C. to 250° C. is preferably 27 ppm / K or less (first range), and further preferably 25 ppm / K or less (second range), 20 ppm or less (third range), 15 ppm / K or less (fourth range), and 13 ppm / K or less (fifth range).

[0289] The polyimide film of the present invention (or the polyimide constituting the polyimide) has excellent heat resistance, and the 1% weight loss temperature is preferably 512°C or higher (first range), and more preferably 515°C or higher (second range), 520°C or higher (third range), and 522°C or higher (fourth range).

[0290] In one embodiment of the present invention, the glass transition temperature (Tg) of the polyimide film (or the polyimide constituting the polyimide) is preferably above 350°C, more preferably above 370°C, further more preferably above 390°C, further more preferably above 400°C, further more preferably above 410°C, further more preferably above 420°C, further more preferably above 430°C, further more preferably above 435°C, and most preferably above 440°C.

[0291] The polyimide film of the present invention shows a very large elastic modulus. In one embodiment of the present invention, the elastic modulus of the polyimide film is preferably 6.5 GPa or more (the first range), and further preferably 6.9 GPa or more (the second range), 7.3 GPa or more (the third range), 7.5 GPa or more (the fourth range), 7.6 GPa or more (the fifth range), 8.0 GPa or more (the sixth range), 8.3 GPa or more (the seventh range). The elastic modulus can be, for example, a value obtained by a film having a film thickness of about 8 μm to 12 μm.

[0292] Furthermore, in one embodiment of the present invention, the elongation at break of the polyimide film is preferably 10% or more (first range) when measured using a film with a thickness of 10 μm, and more preferably 20% or more (second range), 25% or more (third range), and 30% or more (fourth range), respectively.

[0293] In another preferred embodiment of the present invention, the breaking strength of the polyimide film is preferably 200 MPa or more (first range), and further preferably 250 MPa or more (second range), 270 MPa or more (third range), and 300 MPa or more (fourth range). The breaking strength can be, for example, a value obtained from a film having a film thickness of about 5 μm to 100 μm.

[0294] Regarding the properties of the polyimide film, it is preferred that the adhesion, light transmittance, and elastic modulus simultaneously satisfy the "preferred ranges", and it is particularly preferred that the linear thermal expansion coefficient and 1% weight loss temperature also simultaneously satisfy the "preferred ranges".

[0295] The polyimide film having such characteristics, that is, the polyimide film for flexible electronic device substrates, is novel in itself and independently patentable. Particularly preferred embodiments are as follows.

[0296] (1) The polyimide film has a light transmittance at 450 nm of 74% or more (second range), an elastic modulus of 6.9 GPa or more (second range), preferably 7.3 GPa or more (third range), and a linear thermal expansion coefficient and a breaking elongation within the first range.

[0297] (2) The polyimide film has a light transmittance at 450 nm of 75% or more (the third range), preferably 76% (the fourth range), an elastic modulus of 7.3 GPa or more (the third range), and a linear thermal expansion coefficient and a breaking elongation within the first range.

[0298] (3) The 450nm light transmittance of the polyimide film is greater than 74% (the second range), preferably greater than 75% (the third range), and the peel strength between the polyimide film and the substrate in the polyimide film / substrate laminate is greater than 200 gf / cm (the fourth range), preferably greater than 300 gf / cm (the fifth range).

[0299] The polyimide precursor composition of the present invention can also be used to manufacture other types of polyimide and a separate polyimide film. The manufacturing method is not particularly limited, and known imidization methods can be suitably used. The form of the obtained polyimide can suitably include a film, a coating film, a powder, a bead, a molded body, a foam, etc.

[0300] A separate polyimide film can be manufactured using a known method. A representative method is the following method: a polyimide precursor composition is cast onto a substrate, and then, the substrate is heated and imidized, and then the polyimide film is peeled off. Alternatively, the polyimide precursor composition may be cast onto a substrate, and then heated and dried to produce a self-supporting film, and then the self-supporting film is peeled off from the substrate, for example, by holding the film with a tenter, and heating and imidizing in a state where degassing can be performed from both sides of the film to obtain a polyimide film.

[0301] The thickness of the polyimide film alone also depends on the application, but is preferably 1 μm or more, more preferably 2 μm or more, further preferably 5 μm or more, for example 250 μm or less, preferably 150 μm or less, more preferably 100 μm or less, and further preferably 50 μm or less.

[0302] Example

[0303] The present invention is further described below by way of examples and comparative examples. It should be noted that the present invention is not limited to the following examples.

[0304] In the following examples, evaluation was performed by the following method.

[0305] <Evaluation of Polyimide Precursor Composition>

[0306] [Viscosity stabilization and maximum viscosity rate retention evaluation]

[0307] After polymerization, when the polyimide precursor composition is stored at 23°C, the viscosity increases, reaches the maximum viscosity and then decreases. When the maximum viscosity is reached, it is evaluated as "viscosity stabilization". In addition, although the viscosity decreases after reaching the maximum viscosity, the ratio of the viscosity 30 days after the day when the maximum viscosity is reached to the maximum viscosity is taken as the "maximum viscosity retention rate", and the case of a viscosity of 50% or more relative to the maximum viscosity is evaluated as "0", and the case of a viscosity of less than 50% is evaluated as "×".

[0308] In addition, the viscosity was measured using an E-type viscometer TVE-25 manufactured by Toki Sangyo Co., Ltd. at a measurement temperature of 25°C.

[0309] <Evaluation of polyimide film>

[0310] [450nm transmittance]

[0311] In Examples and Comparative Examples, the transmittance at 450 nm was measured using a UV-visible spectrophotometer / V-650DS (manufactured by JASCO Corporation) for polyimide films having a thickness of about 10 μm when the film thickness was not described and for polyimide films having the described film thickness when the film thickness was described.

[0312] [Yellowness (YI)]

[0313] The b* (=YI; yellowness) of a 10 μm thick, 5 cm square polyimide film was measured using a UV-visible spectrophotometer / V-650DS (manufactured by JASCO Corporation) in accordance with ASTM E313. The light source was D65 and the viewing angle was 2°.

[0314] [Haze]

[0315] The haze of the polyimide film was measured using a turbidity meter / NDH2000 (manufactured by Nippon Denshoku Industries) in accordance with JIS K7136.

[0316] [Coefficient of linear thermal expansion (CTE)]

[0317] A polyimide film with a film thickness of about 10 μm was cut into strips with a width of 4 mm to prepare test pieces, and the temperature was cooled from 400°C to 50°C using TMA / SS6100 (manufactured by SII Nanotechnology Co., Ltd.) under the conditions of a chuck length of 15 mm, a load of 2 g, and a cooling rate of 20°C / min. The linear thermal expansion coefficient from 150°C to 250°C was obtained from the obtained TMA curve.

[0318] [1% weight loss temperature]

[0319] A polyimide film having a thickness of about 10 μm was used as a test piece and heated from 25° C. to 600° C. at a heating rate of 10° C. / min in a nitrogen stream using a calorimeter measuring apparatus (Q5000IR) manufactured by TA INSTRUMENTS. From the obtained weight curve, the weight at 150° C. was set as 100%, and the 1% weight loss temperature was determined.

[0320] [Peel strength]

[0321] The peel strength in the 90° direction was measured in the atmosphere at a tensile speed of 2 mm / min using TENSILON RTA-500 manufactured by ORIENTEC.

[0322] [Measurement of residual stress]

[0323] As a reference substrate for evaluating the polyimide film, a 6-inch silicon wafer (625 μm thick, (100) substrate) was used. The polyimide precursor composition was coated on the silicon wafer using a spin coater, and heated directly on the silicon wafer from room temperature to the same temperature as in the examples and comparative examples in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to perform thermal imidization to obtain a polyimide film / reference substrate laminate. The thickness of the polyimide film in the laminate was about 10 μm.

[0324] According to the description of Japanese Patent Gazette No. 6798633, for the obtained polyimide film / silicon wafer laminate, the curvature radius of the warp is measured at 150°C, 140°C, 130°C, 120°C and 110°C using FLX-2320 manufactured by KLA Tencor. Measure 20 times at each temperature and find the average value. In addition, the curvature radius of the silicon wafer alone is also measured at the same temperature. Based on the obtained curvature radius, the residual stress (S) at each temperature is calculated according to the following mathematical formula 1, and the residual stress at 23°C is approximated by a straight line based on the least squares method.

[0325] [Number 1]

[0326]

[0327] Here,

[0328] E / (1-ν): Biaxial elastic modulus of substrate (reference base material: silicon wafer) (Pa),

[0329] (100) Silicon is 1.805E11Pa,

[0330] h: thickness of substrate (m)

[0331] t: Thickness of polyimide film (m)

[0332] R: Radius of curvature of the test specimen (m)

[0333] 1 / R=1 / R2-1 / R1

[0334] R1: Radius of curvature of the substrate (silicon wafer) before film formation

[0335] R2: The radius of curvature of the film after film formation

[0336] S: Average value of residual stress (Pa)

[0337] [Elastic modulus, elongation at break, breaking strength]

[0338] A polyimide film with a thickness of about 10 μm was punched into a dumbbell shape according to the IEC450 standard to prepare a test piece. The initial elastic modulus, elongation at break and breaking strength were measured using TENSILON manufactured by ORIENTEC at a chuck length of 30 mm and a tensile speed of 2 mm / min.

[0339] <Raw materials>

[0340] The abbreviations of the raw materials used in the following examples are as follows.

[0341] [Tetracarboxylic acid component]

[0342] PMDA: pyromellitic dianhydride

[0343] DSDA: 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride

[0344] ODPA: 4,4'-oxydiphthalic anhydride

[0345] s-BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

[0346] 6FDA: 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride

[0347] [Diamine component]

[0348] 4-BAAB: 4-aminophenyl-4-aminobenzoate

[0349] BAPB: 4,4'-bis(4-aminophenoxy)biphenyl

[0350] 4,4-ODA: 4,4-oxydiphenylamine

[0351] [Imidazole compounds]

[0352] 2-Pz: 2-phenylimidazole

[0353] Bz: benzimidazole

[0354] Im:imidazole

[0355] 1-Pz: 1-phenylimidazole

[0356] KBM-103: Phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0357] KBM-202SS: Diphenyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0358] HIVAC-F-5: 1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) [Solvent]

[0359] NMP: N-methyl-2-pyrrolidone

[0360] Table 1-1 describes the tetracarboxylic acid component and the diamine component, and Table 1-2 describes the structural formula of the imidazole compound.

[0361] [Table 1-1]

[0362]

[0363] [Table 1-2]

[0364]

[0365] [Table 1-3]

[0366]

[0367] <Example 1>

[0368] [Preparation of polyimide precursor composition]

[0369] 2.28 g (10 mmoles) of 4-BAAB was added to a nitrogen-purged reaction vessel, and 37.69 g of N-methyl-2-pyrrolidone was added to reach 12.5% ​​by mass of the total mass of the monomers (the sum of the diamine component and the carboxylic acid component), and stirred at room temperature for 1 hour. 3.10 g (10 mmoles) of ODPA was slowly added to the solution. Stirring at room temperature for 6 hours, a uniform and viscous polyimide precursor composition was obtained. The viscosity stability of the polyimide precursor composition is shown in Table 2.

[0370] [Manufacturing of polyimide film / substrate laminate]

[0371] As a glass substrate, a 6-inch Eagle-XG (registered trademark) manufactured by Corning Incorporated (500 μm thick) was used. The polyimide precursor composition was applied to the glass substrate using a spin coater, and was directly heated from room temperature to 420°C on the glass substrate under a nitrogen atmosphere (oxygen concentration of less than 200 ppm), and imidization was performed thermally to obtain a polyimide film / substrate laminate. Regarding peel strength, a test sample with a width of 5 mm was prepared from the obtained polyimide film / glass laminate for measurement. Regarding other film properties, the laminate was immersed in water at 40°C (for example, a temperature in the range of 20°C to 100°C), the polyimide film was peeled off from the glass substrate, and after drying, the properties of the polyimide film were evaluated. The film thickness of the polyimide film is about 10 μm. The evaluation results are shown in Table 2.

[0372] <Examples 2 to 6, Comparative Examples 1 to 4>

[0373] In Example 1, a polyimide precursor composition was obtained in the same manner as in Example 1 except that the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratio) shown in Table 2. Thereafter, a polyimide film was produced in the same manner as in Example 1, and the film properties were evaluated.

[0374] <Examples 7, 11, Comparative Examples 6 to 8>

[0375] In Example 1, the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratio) shown in Table 3, and the reaction was carried out in the same manner as in Example 1 to obtain a polyimide precursor composition. Using the obtained polyimide precursor composition, a polyimide film was produced in the same manner as in Example 1 except that the maximum heating temperature for imidization was changed to 450° C., and the film properties were evaluated.

[0376] <Examples 8 to 10, Comparative Example 5>

[0377] In Example 1, the tetracarboxylic acid component and the diamine component were changed into the compound and the amount (molar ratio) shown in Table 3, and it reacted similarly to Example 1, and obtained the polyimide precursor solution.

[0378] 2-phenylimidazole as an imidazole compound was dissolved in 4 times the mass of N-methyl-2-pyrrolidone to obtain a uniform solution having a solid content concentration of 20 mass % of 2-phenylimidazole. The solution of the imidazole compound was mixed with the above-synthesized polyimide precursor solution in such a manner that the amount of the imidazole compound relative to 1 mol of the repeating unit of the polyimide precursor was the amount described in Table 3, and stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor composition.

[0379] Thereafter, a polyimide film was produced and film properties were evaluated in the same manner as in Example 7. However, in Comparative Example 5, since the viscosity stability of the obtained polyimide precursor composition was poor, it was difficult to form a uniform polyimide film on the substrate, and thus film properties could not be evaluated.

[0380] <Examples 12 to 25, Comparative Examples 9 and 10>

[0381] In Example 1, the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratio) shown in Table 4 or 5, and the reaction was carried out in the same manner as in Example 1 to obtain a polyimide precursor solution.

[0382] The imidazole compound was changed to a compound shown in Table 4 or 5, and the solution of the imidazole compound was mixed with the polyimide precursor solution synthesized above in an amount described in Table 4 or 5, and stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor composition.

[0383] Thereafter, a polyimide film was produced in the same manner as in Example 1 except that the maximum heating temperature for imidization was changed to 420° C. or 450° C. (as described in Table 4 or 5), and the film properties were evaluated. In Comparative Example 9, no imidazole compound was added.

[0384] This application summarizes the examples of condition (i) and condition (ii) specified in 1. of the invention series A as follows.

[0385] (i)1~6, 7~11, 15~18, 19~25, 28

[0386] (ii)8~10, 12~18, 19~25, 26, 27, 28

[0387] [Table 2]

[0388]

[0389] The unit of the amount of the imidazole compound is eq (the number of moles per 1 mole of the repeating unit).

[0390] [Table 3]

[0391]

[0392] The unit of the amount of the imidazole compound is eq (the number of moles per 1 mole of the repeating unit).

[0393] [Table 4]

[0394]

[0395] The unit of the amount of the imidazole compound is eq (the number of moles per 1 mole of the repeating unit).

[0396] [Table 5]

[0397]

[0398] The unit of the amount of the imidazole compound is eq (the number of moles per 1 mole of the repeating unit).

[0399] [Adhesion test after inorganic thin film formation]

[0400] On the polyimide film surface of the polyimide film / substrate laminate manufactured in the same manner as in the embodiment and the comparative example, SiOx and SiNx were formed into 400nm films in sequence by plasma CVD method. Afterwards, annealing treatment was performed at 430°C for 60 minutes in an annealing furnace. Take it out from the annealing furnace for visual observation, and observe the peeling between the polyimide film and the glass substrate, and between the polyimide film and the SiOx film. If no peeling is observed, it is evaluated as "○", and if any peeling is observed, it is evaluated as "×". The results are shown in Tables 2 to 5.

[0401] [Adhesion test 2 after inorganic thin film formation]

[0402] On the polyimide film surface of the polyimide film / substrate laminate manufactured in the same manner as in the embodiment and the comparative example, SiOx and SiNx were formed into 400nm films in sequence by plasma CVD method. Afterwards, annealing treatment was performed at 430°C for 8 hours in an annealing furnace. Take it out from the annealing furnace for visual observation, and observe the peeling between the polyimide film and the glass substrate, and between the polyimide film and the SiOx film. When peeling was not observed, it was evaluated as "○", and when peeling was observed in either case, it was evaluated as "×". The results are shown in Table 6.

[0403] [Table 6]

[0404]

[0405] The unit of the amount of the imidazole compound is eq (the number of moles per 1 mole of the repeating unit).

[0406] According to the above results, when the total of ODPA and s-BPDA in the tetracarboxylic acid component is more than 70 mol% and the ratio of ODPA is more than 50 mol%, the peel strength shows an extremely high value exceeding 400gffcm, and the increase of 450nm transmittance and the decrease of yellowness (YI) are significantly observed. In addition, it is also confirmed that the addition of imidazole compounds is effective for the increase of 450nm transmittance and the decrease of yellowness (YI). In addition, if the imidazole compound is added in an amount of more than 0.01 mole and less than 1 mole, the total of ODPA and s-BPDA in the tetracarboxylic acid component is more than 70 mol% (even if the ratio of ODPA is less than 50 mol%), the effect of high peel strength, high 450nm transmittance and low yellowness (YI) is confirmed.

[0407] [Example of adding silane compound]

[0408] <Examples 29 to 34, 40 to 43, Reference Example 13>

[0409] In the same manner as in Example 7, the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratios) shown in Table 7, and the reaction was carried out in the same manner as in Example 1 to obtain a polyimide precursor solution.

[0410] As a silane compound, the compound and amount shown in Table 7 (mass parts relative to a total of 100 mass parts of tetracarboxylic acid components and diamine components) were mixed with the above-synthesized polyimide precursor solution and stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor composition. Using the obtained polyimide precursor composition, the maximum heating temperature of imidization was set to 450° C., and a polyimide film was manufactured in the same manner as in Example 1, and the film properties were evaluated.

[0411] <Examples 35 to 39>

[0412] As in Example 8, in Example 1, the tetracarboxylic acid component and the diamine component are changed to the compounds and amounts (molar ratio) shown in Table 8, and the reaction is carried out in the same manner as in Example 1 to obtain a polyimide precursor solution, and then the solution of the imidazole compound is mixed with the polyimide precursor solution in such a manner that the amount of the imidazole compound is the amount described in Table 8. Regarding Examples 36 to 39, as silane compounds, the compounds and amounts shown in Table 8 (mass parts relative to a total of 100 mass parts of tetracarboxylic acid components and diamine components) are mixed with the above-synthesized polyimide precursor solution, and stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor composition. Using the obtained polyimide precursor composition, the maximum heating temperature of imidization is set to 450°C, and a polyimide film is manufactured in the same manner as in Example 1, and the film properties are evaluated. It should be noted that, for comparison, Example 35 does not add a silane compound, and the composition is the same as that of Examples 36 to 39, but Example 35 is an example of the present application.

[0413] <Examples 44 to 50>

[0414] As in Examples 7 and 8, in Example 1, the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratio) shown in Table 9, and the reaction was carried out in the same manner as in Example 1 to obtain a polyimide precursor solution. For Examples 47 and 48, the imidazole compound solution was mixed with the polyimide precursor solution in such a manner that the amount of the imidazole compound was the amount described in Table 9. For Examples 45, 46, 48 to 50, as silane compounds, the compounds and amounts shown in Table 9 (mass parts relative to a total of 100 mass parts of tetracarboxylic acid components and diamine components) were mixed with the above-synthesized polyimide precursor solution, and stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor composition. Using the obtained polyimide precursor composition, the maximum heating temperature of imidization was set to 450° C., and a polyimide film was manufactured in the same manner as in Example 1, and the film properties were evaluated. It should be noted that Examples 44 and 47 are examples in which no silane compound was added for comparison, and are examples of the present application.

[0415] <Examples 51 to 53>

[0416] As in Example 8, in Example 1, the tetracarboxylic acid component and the diamine component are changed to the compound and amount (molar ratio) shown in Table 10, and reacted in the same manner as in Example 1 to obtain a polyimide precursor solution, and then the solution of the imidazole compound is mixed with the polyimide precursor solution in such a manner that the amount of the imidazole compound is the amount recorded in Table 10. Regarding Examples 52 and 53, as silane compounds, the compound and amount shown in Table 10 (mass parts relative to a total of 100 mass parts of tetracarboxylic acid components and diamine components) are mixed with the above-synthesized polyimide precursor solution, stirred at room temperature for 3 hours, and a uniform and viscous polyimide precursor composition is obtained. Using the obtained polyimide precursor composition, the maximum heating temperature of imidization is set to 450°C, and a polyimide film is manufactured in the same manner as in Example 1, and the film properties are evaluated. It should be noted that Example 51 is an example in which a silane compound is not added for comparison, and is an embodiment of the present application.

[0417] For Examples 51 to 53, the peel strength test in the glass laminate and the residual stress in the silicon wafer laminate were performed in the same manner as in Example 1. Furthermore, the peeling between the polyimide film and the glass substrate and between the polyimide film and the SiOx film were observed in the same manner as in the above-mentioned [Adhesion Test 2 after Inorganic Thin Film Formation]. The measurement and evaluation results are shown in Table 10.

[0418] [Table 7]

[0419]

[0420] Content of the silane compound is parts by mass with respect to 100 parts by mass of the total of tetracarboxylic dianhydride and diamine.

[0421] [Table 8]

[0422]

[0423] The unit of the amount of the imidazole compound is eq (the number of moles per 1 mole of the repeating unit).

[0424] Content of the silane compound is parts by mass with respect to 100 parts by mass of the total of tetracarboxylic dianhydride and diamine.

[0425] [Table 9]

[0426]

[0427] The unit of the amount of the imidazole compound is eq (the number of moles per 1 mole of the repeating unit).

[0428] Content of the silane compound is parts by mass with respect to 100 parts by mass of the total of tetracarboxylic dianhydride and diamine.

[0429] [Table 10]

[0430]

[0431] The unit of the amount of the imidazole compound is eq (the number of moles per 1 mole of the repeating unit).

[0432] Content of the silane compound is parts by mass with respect to 100 parts by mass of the total of tetracarboxylic dianhydride and diamine.

[0433] Referring to Table 7, compared with Example 7, in the examples to which silane compounds (KBM-103 and KBM-202SS) were added, the 450nm transmittance was further improved. In Reference Example 13, the 450nm transmittance was also improved, but the decrease in the 1% weight loss temperature was large and the heat resistance was poor. Referring to Table 8, even in the system to which the imidazole compound was added, the increase in the 450nm transmittance was confirmed by the addition of the silane compound.

[0434] The same tendency is observed in Tables 9 and 10.

[0435] Industrial Applicability

[0436] The present invention can be suitably used in the manufacture of flexible electronic devices, for example, flexible displays such as liquid crystal displays and organic EL displays, display devices such as electronic paper, and light receiving devices such as solar cells and CMOS.

Claims

1. A polyimide precursor composition comprising: a polyimide precursor having a repeating unit represented by the following general formula (I); and at least one imidazole compound as an optional component in an amount of less than 1 mol relative to 1 mol of the repeating unit of the polyimide precursor, [Chemistry 1] In the general formula I, X1 is a tetravalent aliphatic group or aromatic group, Y1 is a divalent aliphatic group or aromatic group, R1 and R2 are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, wherein: X1 satisfies (i), (i) contains 50 mol% or more of the structure represented by formula (1-1) and contains 70 mol% or more of the structure represented by formula (1-1) and the structure represented by formula (1-2) in total, [Chemistry 2] Y1 contains 70 mol% or more of the structure represented by formula (B), and does not contain a structure having a nitrogen-containing heterocyclic ring in an amount of 3 mol% to 8 mol%, [Chemistry 3] 2. A polyimide precursor composition for producing a polyimide film used as a flexible display substrate, the polyimide precursor composition comprising: a polyimide precursor having a repeating unit represented by the following general formula (I); and at least one imidazole compound as an optional component in an amount of less than 1 mol relative to 1 mol of the repeating unit of the polyimide precursor, [Chemistry 4] In the general formula I, X1 is a tetravalent aliphatic group or aromatic group, Y1 is a divalent aliphatic group or aromatic group, R1 and R2 are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, wherein: X1 satisfies (i), (i) contains 50 mol% or more of the structure represented by formula (1-1) and contains 70 mol% or more of the structure represented by formula (1-1) and the structure represented by formula (1-2) in total, [Chemistry 5] Y1 contains 70 mol % or more of the structure represented by formula (B), [Chemistry 6] 3. The polyimide precursor composition according to claim 1 or 2, characterized in that: 60 mol% or more of X1 is the structure represented by formula (1-1).

4. The polyimide precursor composition according to claim 1 or 2, wherein 80 mol% or more of Y1 is a structure represented by formula (B).

5. The polyimide precursor composition according to claim 1 or 2, wherein At least one imidazole compound is further contained in an amount of 0.01 mol or more and less than 1 mol per 1 mol of the repeating unit of the polyimide precursor.

6. The polyimide precursor composition according to claim 5, characterized in that The imidazole compound is at least one selected from the group consisting of 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1-phenylimidazole, imidazole, and benzimidazole. 7 . A polyimide film obtained from the polyimide precursor composition according to claim 1 .

8. A polyimide film / substrate laminate, characterized in that: It has: A polyimide film obtained from the polyimide precursor composition according to claim 1 or 2; and Base material.

9. The laminate according to claim 8, wherein The laminate further has an inorganic thin film layer on the polyimide film.

10. The laminate according to claim 8 or 9, wherein The substrate is a glass substrate.

11. A method for producing a polyimide film / substrate laminate, comprising the following steps: (a) a step of coating the polyimide precursor composition according to claim 1 or 2 on a substrate; and (b) A step of heat-treating the polyimide precursor on the substrate to laminate a polyimide film on the substrate.

12. The method for producing a laminate according to claim 11, wherein: After the step (b), the method further comprises: (c) forming an inorganic thin film layer on the polyimide film of the laminate.

13. A method for manufacturing a flexible electronic device, comprising the following steps: (d) a step of forming at least one layer selected from a conductor layer and a semiconductor layer on the inorganic thin film layer of the laminate produced according to claim 12; and (e) A step of peeling the substrate and the polyimide film.

Images