Polymers used in electronic devices

Abstract

A diamine having formula (I) is disclosed. In formula (I), Q is a group having a spiro atom; R 7 and R 8 It may be the same or different each time it appears, and is F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, or silyl, wherein the adjacent R 7 and / or R 8 Groups can link together to form an aromatic ring; c and d are the same or different each time they appear and are integers from 0 to 4; and m and q are the same or different and are integers from 0 to 6. #imgabs0#

Description

[0001] Benefit of prior application

[0002] This application claims the benefit of U.S. Provisional Application No. 62 / 688,059, filed on June 21, 2018, which is incorporated herein by reference in its entirety.

[0003] Background Information Technical Field

[0004] The present disclosure relates to novel polymeric compounds. The present disclosure further relates to methods for preparing such polymeric compounds and electronic devices having at least one layer comprising these materials. Background Art

[0005] Materials used in electronic applications generally have strict requirements in terms of their structural properties, optical properties, thermal properties, electronic properties and other properties. As the number of commercial electronic applications continues to increase, the breadth and specificity of the required properties require innovations in materials with new and / or improved properties. Polyimides represent a class of polymeric compounds that have been widely used in various electronic applications. They can serve as flexible substitutes for glass in electronic display devices, provided that they have suitable properties. These materials can be used as components of liquid crystal displays ("LCDs"), where their moderate electrical power consumption, light weight and layer flatness are key properties for practical utility. Other uses in electronic display devices that prioritize setting such parameters include device substrates, substrates for color filters, cover films, touch screen panels, etc.

[0006] Many of these components are also important in the construction and operation of organic electronic devices with organic light emitting diodes ("OLEDs"). OLEDs are promising for many display applications due to their high power conversion efficiency and applicability to a wide range of end uses. They are increasingly used in cell phones, tablet devices, handheld / laptop computers, and other commercial products. In addition to low power consumption, these applications require displays with high information content, full color, and fast video rate response times.

[0007] Polyimide films generally have sufficient thermal stability, high glass transition temperature, and mechanical toughness to be worthy of consideration for such applications. Moreover, polyimides generally do not develop haze when subjected to repeated flexing, so they are often preferred over other transparent substrates like polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) in flexible display applications.

[0008] However, the use of traditional amber polyimides in some display applications such as color filters and touch screen panels is hampered by the priority given to optical transparency. In addition, polyimides are generally hard, highly aromatic materials; and as the film / coating is formed, the polymer chains tend to be oriented in the plane of the film / coating. This results in a difference in refractive index (birefringence) between the parallel and perpendicular directions of the film, resulting in light delay that may adversely affect display performance. If additional uses for polyimides are sought in the display market, solutions are needed to maintain their desired properties while improving their optical transparency and reducing the amber color and birefringence that causes light delay.

[0009] There is therefore a continuing need for polymer materials suitable for use in electronic devices. Summary of the invention

[0010] A diamine having formula I is provided

[0011]

[0012] in:

[0013] Q is a group having a spiro atom;

[0014] R 7 and R 8 are the same or different at each occurrence and are selected from the group consisting of F, CN, alkyl, fluoroalkyl, hydrocarbon aryl, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, silyl, and siloxy, wherein adjacent R 7 and / or R 8 The groups can be linked together to form aromatic rings;

[0015] c and d are the same or different at each occurrence and are integers from 0 to 4; and

[0016] m and q are the same or different and are integers of 0-6.

[0017] Further provided is a polyamic acid having a repeating unit of formula II

[0018]

[0019] in:

[0020] R a is the same or different at each occurrence and represents one or more tetracarboxylic acid component residues; and

[0021] R b is the same or different at each occurrence and represents one or more aromatic diamine residues;

[0022] 10-100 mol% of Rb is a diamine residue from one or more diamines having formula I.

[0023] Further provided is a composition comprising (a) a polyamic acid having a repeating unit of Formula II and (b) a high boiling point aprotic solvent.

[0024] A polyimide is further provided, wherein the repeating unit of the polyimide has the structure of formula IV

[0025]

[0026] Where R a and R b As defined in Formula II.

[0027] Further provided is a polyimide film comprising a repeating unit having Formula IV.

[0028] Further provided are one or more methods for preparing a polyimide membrane, wherein the polyimide membrane has a repeating unit of Formula IV.

[0029] Further provided is a flexible replacement for glass in an electronic device, wherein the flexible replacement for glass is a polyimide film having a repeating unit of Formula IV.

[0030] Further provided is an electronic device having at least one layer comprising a polyimide film having a repeating unit of Formula IV.

[0031] Further provided is an organic electronic device, such as an OLED, wherein the organic electronic device contains a flexible replacement for glass as disclosed herein.

[0032] The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Embodiments are illustrated in the accompanying drawings to improve understanding of the concepts as presented herein.

[0034] Figure 1 Included is an illustration of one example of a polyimide film that can serve as a flexible alternative to glass.

[0035] Figure 2 Included is an illustration of an example of an electronic device including a flexible alternative to glass.

[0036] It should be understood by those skilled in the art that the objects in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the size of some objects in the drawings may be magnified relative to other objects to help improve the understanding of the embodiments. DETAILED DESCRIPTION

[0037] A diamine having formula I is provided as described in detail below.

[0038] Further provided is a polyamic acid having a repeating unit of formula II as described in detail below.

[0039] Further provided is a composition comprising (a) a polyamic acid having a repeating unit of Formula II and (b) a high boiling point aprotic solvent.

[0040] Further provided is a polyimide as described in detail below, the repeating unit of the polyimide having the structure of Formula IV.

[0041] Further provided are one or more methods for preparing a polyimide membrane, wherein the polyimide membrane has a repeating unit of Formula IV.

[0042] Further provided is a flexible replacement for glass in an electronic device, wherein the flexible replacement for glass is a polyimide film having a repeating unit of Formula IV.

[0043] Further provided is an electronic device having at least one layer comprising a polyimide film having a repeating unit of Formula IV.

[0044] Further provided is an organic electronic device, such as an OLED, wherein the organic electronic device contains a flexible replacement for glass as disclosed herein.

[0045] Many aspects and embodiments have been described above and are exemplary and non-limiting only. After reading this specification, skilled artisans will appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

[0046] Other features and benefits of any one or more embodiments will be apparent from the following detailed description and from the claims. The detailed description first presents definitions and clarifications of terms, followed by diamines of formula I, polyamic acids having a repeating unit structure of formula II, polyimides having a repeating unit structure of formula IV, methods for preparing polyimide films, electronic devices, and finally examples.

[0047] 1. Definition and clarification of terms

[0048] Before presenting details of the following embodiments, some terms are defined or clarified.

[0049] As used in the “Definition and Clarification of Terms”, R, R a , R b, R', R" and any other variables are generic names and may be the same as or different from those defined in the formula.

[0050] The term "alignment layer" is intended to refer to an organic polymer layer in a liquid crystal device (LCD) that aligns the molecules closest to each plate as a result of it being rubbed onto the LCD glass in a preferred direction during the LCD manufacturing process.

[0051] As used herein, the term "alkyl" includes branched and straight chain saturated aliphatic hydrocarbon groups. Unless otherwise specified, the term is also intended to include cyclic groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl, etc. The term "alkyl" further includes both substituted and unsubstituted hydrocarbon groups. In certain embodiments, the alkyl group can be mono-, di- and tri-substituted. An example of a substituted alkyl group is trifluoromethyl. Other substituted alkyl groups are formed by one or more of the substituents described herein. In certain embodiments, the alkyl group has 1 to 20 carbon atoms. In other embodiments, the group has 1 to 6 carbon atoms. The term is intended to include heteroalkyl groups. The heteroalkyl group can have 1-20 carbon atoms.

[0052] The term "aprotic" refers to a class of solvents that lack acidic hydrogen atoms and therefore cannot act as hydrogen donors. Common aprotic solvents include alkanes, carbon tetrachloride (CCl4), benzene, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), etc.

[0053] The term "aromatic compound" is intended to refer to an organic compound containing at least one unsaturated cyclic group having 4n+2 delocalized π electrons. The term is intended to encompass both aromatic compounds, which have only carbon and hydrogen atoms, and heteroaromatic compounds, in which one or more carbon atoms within the cyclic group has been replaced by another atom, such as nitrogen, oxygen, sulfur, etc.

[0054] The term "aryl" or "aryl group" refers to a moiety formed by removing one or more hydrogen ("H") or deuterium ("D") from an aromatic compound. An aryl group can be a single ring (monocyclic) or have multiple rings (bicyclic, or more) fused together or covalently linked. "Hydrocarbyl" has only carbon atoms in one or more aromatic rings. "Heteroaryl" has one or more heteroatoms in at least one aromatic ring. In some embodiments, a hydrocarbyl group has 6 to 60 ring carbon atoms; in some embodiments, 6 to 30 ring carbon atoms. In some embodiments, a heteroaryl group has 4-50 ring carbon atoms; in some embodiments, 4-30 ring carbon atoms.

[0055] The term "alkoxy" is intended to refer to the group -OR, where R is alkyl.

[0056] The term "aryloxy" is intended to refer to the group -OR, where R is aryl.

[0057] Unless otherwise indicated, all groups may be substituted or unsubstituted. Optionally substituted groups, such as but not limited to alkyl or aryl, may be substituted with one or more substituents which may be the same or different. Suitable substituents include alkyl, aryl, nitro, cyano, -N(R')(R ” ), halogen, hydroxy, carboxyl, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, silyloxy, siloxane, thioalkoxy, -S(O)2-, -C(=O)-N(R')(R"), (R')(R")N-alkyl, (R')(R")N-alkoxyalkyl, (R')(R")N-alkylaryloxyalkyl, -S(O) s -aryl (where s=0-2), or -S(O) s - heteroaryl (where s = 0-2). Each R' and R" is independently an optionally substituted alkyl, cycloalkyl or aryl group. R' and R", together with the nitrogen atom to which they are attached, may form a ring system in certain embodiments. The substituent may also be a crosslinking group.

[0058] The term "amine" is intended to refer to a compound containing a basic nitrogen atom with a lone pair of electrons. The term "amino" refers to the functional group -NH2, -NHR or -NR2, wherein R is the same or different at each occurrence and can be an alkyl group or an aryl group. The term "diamine" is intended to refer to a compound containing two basic nitrogen atoms with associated lone pairs of electrons. The term "aromatic diamine" is intended to refer to an aromatic compound with two amino groups. The term "bent diamine" is intended to refer to a diamine in which the two basic nitrogen atoms and the associated lone pairs of electrons are asymmetrically arranged around the symmetry center of the corresponding compound or functional group, such as m-phenylenediamine:

[0059]

[0060] The term "aromatic diamine residue" is intended to refer to a portion bonded to two amino groups in an aromatic diamine. The term "aromatic diisocyanate residue" is intended to refer to a portion bonded to two isocyanate groups in an aromatic diisocyanate compound. This is further described below.

[0061]

[0062] The terms "diamine residue" and "diisocyanate residue" are intended to refer to a moiety bonded to two amino groups or two isocyanate groups, respectively, wherein the moiety is aliphatic or aromatic.

[0063] The term "b*" is intended to refer to the b* axis representing the yellow / blue opposition color in the CIELab color space. Yellow is represented by a positive b* value, and blue is represented by a negative b* value. The b* value measured may be affected by solvents, particularly because solvent selection may affect the color measured on the material exposed to high temperature processing conditions. This may occur as a result of the inherent properties of the solvent and / or the properties associated with the low-level impurities contained in the various solvents. Specific solvents are usually pre-selected to achieve the b* value desired for a particular application.

[0064] The term "birefringence" is intended to refer to the difference in refractive index in different directions in a polymer film or coating. The term typically refers to the difference between the x-axis or y-axis (in-plane) and z-axis (out-of-plane) refractive index.

[0065] The term "charge transport" when referring to a layer, material, component, or structure is intended to mean that such layer, material, component, or structure facilitates the migration of such charge through the thickness of such layer, material, component, or structure with relative efficiency and small charge loss. Hole transport materials favor positive charges; electron transport materials favor negative charges. Although light-emitting materials may also have some charge transport properties, the term "charge transport layer, material, component, or structure" is not intended to include layers, materials, components, or structures whose primary function is to emit light.

[0066] The term "compound" is intended to mean an uncharged substance composed of molecules further comprising atoms, wherein the atoms cannot be separated from their corresponding molecules by physical means without breaking chemical bonds. The term is intended to include oligomers and polymers.

[0067] The term "coefficient of linear thermal expansion (CTE or α)" is intended to refer to a parameter that defines the amount a material expands or contracts with temperature. It is expressed as the change in length per degree Celsius and is usually expressed in units of μm / m / °C or ppm / °C.

[0068] α=(ΔL / L0) / ΔT

[0069] The measured CTE values ​​disclosed herein are generated via known methods during either the first or second heating scan.An understanding of the relative expansion / contraction characteristics of a material can be an important consideration in the manufacture and / or reliability of electronic devices.

[0070] The term "dopant" is intended to refer to a material within a layer that includes a host material that changes one or more electronic properties or one or more target wavelengths of radiation emission, reception, or filtering of the layer as compared to the one or more electronic properties or one or more wavelengths of radiation emission, reception, or filtering of the layer in the absence of such material.

[0071] The term "electroactive" when referring to a layer or material is intended to mean a layer or material that electronically facilitates the operation of a device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block electric charge, where the charge may be electrons or holes, or materials that emit radiation or exhibit a change in the concentration of electron-hole pairs upon receiving radiation. Examples of inactive materials include, but are not limited to, planarizing materials, insulating materials, and environmental barrier materials.

[0072] The term "tensile elongation" or "tensile strain" is intended to refer to the percentage increase in length that occurs in a material before it breaks under an applied tensile stress. It can be measured, for example, by ASTM method D882.

[0073] The prefix "fluoro" is intended to indicate that one or more hydrogens in the group have been replaced by fluorine.

[0074] The term "glass transition temperature (or T g )” is intended to refer to the temperature at which a reversible change occurs in an amorphous polymer, or in the noncrystalline region of a semicrystalline polymer, in which the material suddenly changes from a hard, glassy, ​​or brittle state to a flexible or elastic state. Under a microscope, the glass transition occurs when normally coiled, stationary polymer chains become free to rotate and can move past each other. T can be measured using differential scanning calorimetry (DSC), thermomechanical analysis (TMA), or dynamic mechanical analysis (DMA), or other methods. g .

[0075] The prefix "hetero" indicates that one or more carbon atoms have been replaced by a different atom. In some embodiments, the heteroatom is O, N, S, or a combination thereof.

[0076] The term "high boiling point" is intended to mean a boiling point above 130°C.

[0077] The term "host material" is intended to refer to a material to which a dopant is added. The host material may or may not have one or more electronic properties or capabilities to emit, receive, or filter radiation. In some embodiments, the host material is present in a relatively high concentration.

[0078] The term "isothermal weight loss" is intended to refer to a material property that is directly related to its thermal stability. It is typically measured via thermogravimetric analysis (TGA) at a constant target temperature. Materials with high thermal stability typically exhibit very low isothermal weight loss percentages at the required use or processing temperature over a desired period of time, and can therefore be used in applications at these temperatures without significant strength loss, degassing, and / or structural changes.

[0079] The term "laser particle counter test" refers to a method for evaluating the particle content of polyamic acid and other polymer solutions whereby a representative sample of the test solution is spin coated onto a 5" silicon wafer and soft baked / dried. The particle content of the film thus prepared is evaluated by any number of standard measurement techniques. Such techniques include laser particle detection and other techniques known in the art.

[0080] The term "liquid composition" is intended to refer to a liquid medium in which a material is dissolved to form a solution, a liquid medium in which a material is dispersed to form a dispersion, or a liquid medium in which a material is suspended to form a suspension or emulsion.

[0081] The term "substrate" is intended to refer to a foundation upon which one or more layers are deposited, for example, in the formation of an electronic device. Non-limiting examples include glass, silicon, and the like.

[0082] The term "1% TGA weight loss" is intended to mean the temperature at which 1% of the original polymer weight is lost due to decomposition (excluding absorbed water).

[0083] The term “optical delay (or R TH )" is intended to refer to the difference between the average in-plane and out-of-plane refractive indices (ie, birefringence), which is then multiplied by the thickness of the film or coating. Optical retardation is typically measured for a given frequency of light, and the units are reported in nanometers.

[0084] The term "organic electronic device" or sometimes "electronic device" is intended herein to refer to a device that includes one or more organic semiconductor layers or one or more materials.

[0085] The term "particle content" is intended to refer to the number or count of insoluble particles present in a solution. Measurement of particle content can be performed on the solution itself or on finished materials (sheets, films, etc.) prepared from those films. Various optical methods can be used to assess this property.

[0086] The term "photoactive" refers to a material or layer that emits light when activated by an applied voltage (as in a light emitting diode or chemical cell), emits light after absorbing a photon (as in a down-converting phosphor device), or generates a signal in response to radiant energy with or without an applied bias (as in a photodetector or photovoltaic cell).

[0087] The term "polyamic acid solution" refers to a solution of a polymer containing an amic acid unit having intramolecular cyclization capability to form an imide group.

[0088] The term "polyimide" refers to a condensate obtained by reacting one or more difunctional carboxylic acid components with one or more primary diamines or diisocyanates. They contain the imide structure -CO-NR-CO- as a linear or heterocyclic unit along the main chain of the polymer backbone.

[0089] When referring to a material property or characteristic, the term "satisfactory" is intended to mean that the property or characteristic meets all requirements / needs of the material in use. For example, in the context of the polyimide films disclosed herein, an isothermal weight loss of less than 1% at 350° C. for 3 hours in nitrogen can be considered a non-limiting example of a "satisfactory" property.

[0090] The term "soft bake" is intended to refer to a process commonly used in electronics manufacturing where the applied material is heated to drive off solvents and cure the film. The soft bake is typically performed at a temperature of 90°C to 110°C on a hot plate or in an exhaust oven as a preparatory step for subsequent thermal treatment of the applied layer or film.

[0091] The term "substrate" refers to a base material that may be rigid or flexible and may include one or more layers of one or more materials, which may include, but are not limited to, glass, polymers, metals, or ceramic materials, or combinations thereof. The substrate may or may not include electronic components, circuits, or conductive members.

[0092] The term "siloxane" refers to a group R3SiOR2Si-, where R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced by Si.

[0093] The term "silyloxy" refers to the group R3SiO-, where R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl.

[0094] The term "silyl" refers to a group R3Si-, wherein R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced by Si.

[0095] The term "spin coating" is intended to refer to a process for depositing a uniform thin film onto a flat substrate. Generally, a small amount of coating material is applied to the center of a substrate that is spinning at a slow speed or not spinning at all. The substrate is then spun at a specified speed so that the coating material is spread evenly by centrifugal force.

[0096] The term "spiro group" refers to a group with a bicyclic organic moiety, wherein the two rings have a shared atom. These rings can be different or identical in nature, and can form parts of other ring systems. The shared atom has two bonds in each ring and is referred to as a spiro atom. In certain embodiments, the spiro atom is selected from the group consisting of C and Si.

[0097] The term "tensile modulus" is intended to refer to a measure of the stiffness of a solid material that defines the initial relationship between stress (force per unit area) and strain (proportional deformation) in a material such as a film. The unit commonly used is the gigapascal (GPa).

[0098] The term "tetracarboxylic acid component" is intended to refer to any one or more of a tetracarboxylic acid, a tetracarboxylic acid monoanhydride, a tetracarboxylic acid dianhydride, a tetracarboxylic acid monoester, and a tetracarboxylic acid diester.

[0099] The term "tetracarboxylic acid component residue" is intended to mean a portion bonded to four carboxyl groups in the tetracarboxylic acid component. This is further described below.

[0100]

[0101] The term "transmittance" refers to the percentage of light of a given wavelength impinging on a film that passes through the film so as to be detectable on the other side. Light transmittance measurements in the visible region (380 nm to 800 nm) are particularly useful for characterizing the film color features that are most important for understanding the in-use properties of the polyimide films disclosed herein.

[0102] The term "yellowness index (or YI)" refers to the magnitude of yellowness relative to a standard. A positive value of YI indicates the presence and magnitude of yellow. Materials with negative YI appear bluish. Particularly for polymerization and / or curing processes operating at high temperatures, it should also be noted that YI can be solvent dependent. For example, the magnitude of color introduced using DMAC as a solvent may be different from the magnitude of color introduced using NMP as a solvent. This can occur as a result of the inherent properties of the solvent and / or the properties associated with low levels of impurities contained in various solvents. Specific solvents are usually pre-selected to achieve the YI value desired for a specific application.

[0103] In structures in which a substituent bond passes through one or more rings as shown below,

[0104]

[0105] This means that the substituent R may be bonded at any available position on one or more rings.

[0106] When used to refer to layers in a device, the phrase "adjacent" does not necessarily mean that one layer is immediately adjacent to another layer. On the other hand, the phrase "adjacent R groups" is used to refer to R groups that are immediately adjacent to each other in a chemical formula (i.e., R groups on atoms that are bound by a bond). Exemplary adjacent R groups are shown below:

[0107]

[0108] In this specification, unless otherwise expressly indicated or indicated to the contrary by the context of use, where an embodiment of the inventive subject matter is stated or described as comprising, including, containing, having, consisting of, or composed of certain features or elements, one or more features or elements in addition to those explicitly stated or described may also be present in that embodiment. An alternative embodiment of the disclosed inventive subject matter is described as consisting essentially of certain features or elements, wherein features or elements of the embodiment that would substantially change the principle of operation or the distinguishing characteristics of the embodiment are absent therefrom. Another alternative embodiment of the described inventive subject matter is described as consisting of certain features or elements, in which embodiment or in insubstantial variations thereof, only the features or elements specifically stated or described are present.

[0109] In addition, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, condition A or B is satisfied by any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0110] Moreover, "a / an" is used to describe the elements and components described herein. This is done only for convenience and to give a general sense of the scope of the invention. The description should be interpreted as including one / a or at least one / a, and the singular also includes the plural unless it is obvious that it is otherwise intended.

[0111] The group numbers corresponding to the columns within the Periodic Table of the Elements use the "New Notation" convention as found in the CRC Handbook of Chemistry and Physics, 81st Edition (2000-2001).

[0112] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those of ordinary skill in the art to which the present invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or test of embodiments of the present invention, suitable methods and materials are described below. Unless citing a specific paragraph, all publications, patent applications, patents and other references mentioned herein are incorporated herein by reference in their entirety. In the event of a conflict, this specification, including definitions, shall prevail. In addition, materials, methods and examples are only illustrative and are not intended to be restrictive.

[0113] To the extent not described herein, many details regarding specific materials, processing activities, and circuits are conventional and can be found in textbooks and other sources in the field of organic light emitting diode displays, photodetectors, photovoltaics, and semiconductor components.

[0114] 2. Diamines having formula I

[0115] The diamines described herein have the formula I

[0116]

[0117] in:

[0118] Q is a group having a spiro atom;

[0119] R 7 and R 8 are the same or different at each occurrence and are selected from the group consisting of F, CN, alkyl, fluoroalkyl, hydrocarbon aryl, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, silyl, and siloxy, wherein adjacent R 7 and / or R 8 The groups can be linked together to form aromatic rings;

[0120] c and d are the same or different at each occurrence and are integers from 0 to 4; and

[0121] m and q are the same or different and are integers of 0-6.

[0122] In some embodiments of Formula I, Q has the formula Q1

[0123]

[0124] in:

[0125] R 1 -R 4 are the same or different and are selected from the group consisting of H, alkyl, alkoxy, hydrocarbon aryl, heteroaryl, aryloxy, silyl, and siloxy;

[0126] R 5 and R 6 is the same or different at each occurrence and is selected from the group consisting of F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, silyl, and siloxy;

[0127] a and b are the same or different and are integers from 0 to 3; and

[0128] *Indicates attachment point.

[0129] In some embodiments of Formula Q1, R 1 =R 2 =R 3 =R 4 .

[0130] In some embodiments of Formula Q1, R 1 ≠R 2 .

[0131] In some embodiments of Formula Q1, R 1 =R 3 And R 2 =R 4 .

[0132] In some embodiments of Formula Q1, R 1 =H.

[0133] In some embodiments of Formula Q1, R 1 It is C 1-10 Alkyl; in some embodiments, C 1-5 alkyl.

[0134] In some embodiments of Formula Q1, R 1 It is C 1-10 Alkoxy; in some embodiments, C 1-5 Alkoxy.

[0135] In some embodiments of Formula Q1, R 1 It is C 3-10 Silyl; in some embodiments, C 3-6 Silyl.

[0136] In some embodiments of Formula Q1, R 1 It is C 6-18 Hydrocarbon aromatic group.

[0137] For R in formula Q1 1 All the above-described embodiments are also applicable to R in formula Q1 2 , R 3 and R 4.

[0138] In some embodiments of formula Q1, a=0.

[0139] In some embodiments of formula Q1, a=1.

[0140] In some embodiments of Formula Q1, a=2.

[0141] In some embodiments of Formula Q1, a=3.

[0142] In some embodiments of Formula Q1, a>0.

[0143] In some embodiments of formula Q1, b=0.

[0144] In some embodiments of formula Q1, b=1.

[0145] In some embodiments of Formula Q1, b=2.

[0146] In some embodiments of Formula Q1, b=3.

[0147] In some embodiments of formula Q1, b>0.

[0148] In some embodiments of formula Q1, a>0 and at least one R 5 It's F.

[0149] In some embodiments of formula Q1, a>0 and at least one R 5 It is CN.

[0150] In some embodiments of formula Q1, a>0 and at least one R 5 It is C 1-10 Alkyl; in some embodiments, C 1-5 alkyl.

[0151] In some embodiments of formula Q1, a>0 and at least one R 5 It is C 1-10 Alkoxy; in some embodiments, C 1-5 Alkoxy.

[0152] In some embodiments of formula Q1, a>0 and at least one R 5 It is C 1-10 Fluoroalkyl; in some embodiments, C 1-5 Fluoroalkyl; in some embodiments, C 1-5 Perfluoroalkyl.

[0153] In some embodiments of formula Q1, a>0 and at least one R 5 It is C 3-10 Silyl; in some embodiments, C 3-6 Silyl.

[0154] In some embodiments of formula Q1, a>0 and at least one R 5 It is C 3-10 Siloxy; in some embodiments, C 3-6 Siloxy.

[0155] For R in formula Q1 5 All the above-described embodiments are also applicable to R in formula Q1 6 .

[0156] In some embodiments of Formula I, Q has the formula Q2

[0157]

[0158] in:

[0159] R 5 and R 6 is the same or different at each occurrence and is selected from the group consisting of F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, silyl, and siloxy;

[0160] a and b are the same or different and are integers from 0 to 3; and

[0161] *Indicates attachment point.

[0162] For R in formula Q1 5 , R 6 All of the above-described embodiments of a, b, and d are also applicable to R in formula Q2. 5 , R 6 , a, and b.

[0163] In some embodiments of Formula I, Q has the formula Q3

[0164]

[0165] in:

[0166] R 1 -R 4 are the same or different and are selected from the group consisting of H, alkyl, alkoxy, hydrocarbon aryl, heteroaryl, aryloxy, silyl, and siloxy;

[0167] R 5 and R 6 is the same or different at each occurrence and is selected from the group consisting of F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, silyl, and siloxy;

[0168] a and b are the same or different and are integers from 0 to 3; and

[0169] *Indicates attachment point.

[0170] For R in formula Q1 1 To R 6 All of the above-described embodiments of a, b, and d are also applicable to R in formula Q3. 1 To R 6 , a, and b.

[0171] In some embodiments of Formula I, m=0.

[0172] In some embodiments of Formula I, m=1.

[0173] In some embodiments of Formula I, m=2.

[0174] In some embodiments of Formula I, m=3.

[0175] In some embodiments of Formula I, m=4.

[0176] In some embodiments of Formula I, m=5.

[0177] In some embodiments of Formula I, m=6.

[0178] In some embodiments of Formula I, q=0.

[0179] In some embodiments of Formula I, q=1.

[0180] In some embodiments of Formula I, q=2.

[0181] In some embodiments of Formula I, q=3.

[0182] In some embodiments of Formula I, q=4.

[0183] In some embodiments of Formula I, q=5.

[0184] In some embodiments of Formula I, q=6.

[0185] In some embodiments of Formula I, m=q.

[0186] In some embodiments of Formula I, m≠q.

[0187] In some embodiments of Formula I, m=q=1.

[0188] In some embodiments of Formula I, c=0.

[0189] In some embodiments of Formula I, c=1.

[0190] In some embodiments of Formula I, c=2.

[0191] In some embodiments of Formula I, c=3.

[0192] In some embodiments of Formula I, c=4.

[0193] In some embodiments of Formula I, c>0.

[0194] In some embodiments of Formula I, d=0.

[0195] In some embodiments of Formula I, d=1.

[0196] In some embodiments of Formula I, d=2.

[0197] In some embodiments of Formula I, d=3.

[0198] In some embodiments of Formula I, d=4.

[0199] In some embodiments of Formula I, d>0.

[0200] In some embodiments of Formula I, c>0 and at least one R 7 It's F.

[0201] In some embodiments of Formula I, c>0 and at least one R 7 It is CN.

[0202] In some embodiments of Formula I, c>0 and at least one R 7 It is C 1-10 Alkyl; in some embodiments, C 1-5 alkyl.

[0203] In some embodiments of Formula I, c>0 and at least one R 7 It is C 1-10 Alkoxy; in some embodiments, C 1-5 Alkoxy.

[0204] In some embodiments of Formula I, c>0 and at least one R 7 It is C 1-10 Fluoroalkyl; in some embodiments, C 1-5 Fluoroalkyl; in some embodiments, C 1-5 Perfluoroalkyl.

[0205] In some embodiments of Formula I, c>0 and at least one R 7 It is C 3-10 Silyl; in some embodiments, C 3-6 Silyl.

[0206] In some embodiments of Formula I, c>0 and at least one R 7 It is C 3-10 Siloxy; in some embodiments, C 3-6 Siloxy.

[0207] For R in Formula I 7 All the above-described embodiments are also applicable to R in Formula I 8 .

[0208] In some embodiments of Formula I, the diamine has Formula Ia

[0209]

[0210] Where R 1 To R 6 , a, and b are as defined in Formula Q1.

[0211] In some embodiments of Formula I, the diamine has Formula Ib or Formula Ic

[0212]

[0213] Where R 1 To R 6 , a, and b are as defined in Formula Q1.

[0214] In some embodiments of Formula I, the diamine has Formula Id

[0215]

[0216] Where R 1 To R 6 , a, and b are as defined in Formula Q1; R 7 , R 8 , c and d are as defined in Formula I.

[0217] In some embodiments of Formula I, the diamine has Formula Ie or Formula If

[0218]

[0219] Where R 1 To R 6 , a, and b are as defined in Formula Q1; R 7 , R 8 , c and d are as defined in Formula I.

[0220] In some embodiments of Formula I, the diamine has the formula Ig

[0221]

[0222] Where R 5, R 6 , a, and b are as defined in Formula Q2.

[0223] In some embodiments of Formula I, the diamine has Formula Ih or Formula Ii

[0224]

[0225]

[0226] Where R 5 , R 6 , a, and b are as defined in Formula Q2.

[0227] In some embodiments of Formula I, the diamine has Formula Ij

[0228]

[0229] Where R 5 , R 6 , a, and b are as defined in Formula Q2; R 7 , R 8 , c and d are as defined in Formula I.

[0230] In some embodiments of Formula I, the diamine has Formula Ik or Formula Im

[0231]

[0232] Where R 5 , R 6 , a, and b are as defined in Formula Q2; R 7 , R 8 , c and d are as defined in Formula I.

[0233] In some embodiments of Formula I, the diamine has the formula In

[0234]

[0235] Where R 1 To R 6 , a, and b are as defined in Formula Q1.

[0236] In some embodiments of Formula I, the diamine has Formula Io or Formula Ip

[0237]

[0238] Where R 1 To R 6 , a, and b are as defined in Formula Q1.

[0239] In some embodiments of Formula I, the diamine has the formula Iq

[0240]

[0241] Where R 1 To R 6 , a, and b are as defined in Formula Q1; R 7 , R 8 , c and d are as defined in Formula I.

[0242] In some embodiments of Formula I, the diamine has Formula Ir or Formula Is

[0243]

[0244] Where R 1 To R 6 , a, and b are as defined in Formula Q1; R 7 , R 8 , c and d are as defined in Formula I.

[0245] The new compounds can be prepared using any technique that will produce a CC or CN bond. A variety of such techniques are known, such as Suzuki, Yamamoto, Stille, Negishi, and metal-catalyzed CN couplings and metal-catalyzed and oxidative direct arylations. Exemplary preparations are given in the Examples.

[0246] A synthetic scheme for compounds of Formula Ib is shown below.

[0247]

[0248]

[0249] In the above scheme: Tf represents trifluoromethanesulfonate; Tf2O represents trifluoromethanesulfonic anhydride; BOC represents tert-butoxycarbonyl.

[0250] Compound A can be prepared according to the procedure reported by Chen, W.-F.; Lin, H.-Y.; Dai, SA Org. Letters [Org. Chem. Commun.] 2004, 6, 2341.

[0251] One synthetic scheme for compounds of formula Id is shown below.

[0252]

[0253] Any of the above embodiments of Formula I may be combined with one or more of the other embodiments as long as they are not mutually exclusive. 1 It is C 1-3 Examples of alkyl groups may include those wherein R1 =R 2 =R 3 =R 4 Those skilled in the art will understand which embodiments are mutually exclusive and will therefore be readily able to determine the combinations of embodiments contemplated by the present application.

[0254] Some non-limiting examples of compounds having Formula I are shown below.

[0255] Compound 1

[0256]

[0257] Compound 2

[0258]

[0259] Compound 3

[0260]

[0261] Compound 4

[0262]

[0263] Compound 5

[0264]

[0265] Compound 6

[0266]

[0267] Compound 7

[0268]

[0269] Compound 8

[0270]

[0271] Compound 9

[0272]

[0273] Compound 10

[0274]

[0275] Compound 11

[0276]

[0277] Compound 12

[0278]

[0279] Compound 13

[0280]

[0281] Compound 14

[0282]

[0283] Compound 15

[0284]

[0285] Compound 16

[0286]

[0287] Compound 17

[0288]

[0289] 3. Polyamic acid having a repeating unit structure of formula II

[0290] The polyamic acid described herein has a repeating unit structure of formula II

[0291]

[0292] in:

[0293] R a is the same or different at each occurrence and represents one or more tetracarboxylic acid component residues; and

[0294] R b is the same or different at each occurrence and represents one or more aromatic diamine residues;

[0295] 10-100 mol% of R b is a residue from one or more diamines of formula I.

[0296] In some embodiments of Formula II, R a represents a single tetracarboxylic acid component residue.

[0297] In some embodiments of Formula II, R a represents two tetracarboxylic acid component residues.

[0298] In some embodiments of Formula II, R a represents three tetracarboxylic acid residues.

[0299] In some embodiments of Formula II, R a represents four tetracarboxylic acid residues.

[0300] In some embodiments of Formula II, R a represents one or more tetracarboxylic dianhydride residues.

[0301] Examples of suitable aromatic tetracarboxylic dianhydrides include, but are not limited to, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4'-hexafluoroisopropylidene diphthalic anhydride (6FDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-bisphenol-A dianhydride (BPADA), hydroquinone diphthalic anhydride (HQDEA), ethylene glycol bis(trimellitic anhydride) (TMEG-100), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (DTDA); 4,4'-bisphenol A dianhydride (BPADA), and the like, and combinations thereof. These aromatic dianhydrides may be optionally substituted with groups known in the art, including alkyl, aryl, nitro, cyano, -N(R')(R ” ), halogen, hydroxy, carboxyl, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, silyloxy, siloxane, thioalkoxy, -S(O)2-, -C(=O)-N(R')(R"), (R')(R")N-alkyl, (R')(R")N-alkoxyalkyl, (R')(R")N-alkylaryloxyalkyl, -S(O) s -Aryl (where s=0-2) or -S(O) s - heteroaryl (where s = 0-2). Each R' and R" is independently an optionally substituted alkyl, cycloalkyl or aryl group. R' and R", together with the nitrogen atom to which they are attached, may form a ring system in certain embodiments. The substituent may also be a crosslinking group.

[0302] In some embodiments of Formula II, R a represents one or more residues from tetracarboxylic dianhydride selected from the group consisting of PMDA, BPDA, 6FDA, and BTDA.

[0303] In some embodiments of Formula II, R a represents PMDA residues.

[0304] In some embodiments of Formula II, R a represents BPDA residues.

[0305] In some embodiments of Formula II, R arepresents 6FDA residues.

[0306] In some embodiments of Formula II, R a represents BTDA residues.

[0307] In some embodiments of Formula II, R a indicates PMDA residues and BPDA residues.

[0308] In some embodiments of Formula II, R a PMDA residues and 6FDA residues are indicated.

[0309] In some embodiments of Formula II, R a indicates PMDA residues and BTDA residues.

[0310] In some embodiments of Formula II, R a indicates BPDA residues and 6FDA residues.

[0311] In some embodiments of Formula II, R a represents BPDA residues and BTDA residues.

[0312] In some embodiments of Formula II, R a 6FDA residues and BTDA residues are indicated.

[0313] In some embodiments of Formula II, R a Represents PMDA residues, BPDA residues, and 6FDA residues.

[0314] In Formula II, 10-100 mol% of R b represents a diamine residue from one or more diamines having Formula I as shown above.

[0315] In some embodiments of Formula II, 10-100 mol% of R b represents a diamine residue from a diamine having Formula I as shown above.

[0316] In some embodiments of Formula II, 10-100 mol% of R b represents diamine residues from two different diamines, both of which have Formula I as shown above.

[0317] In some embodiments of Formula II, 10-100 mol% of R b represents diamine residues from three different diamines, all having Formula I as shown above.

[0318] In some embodiments of Formula II, 10-100 mol% of R brepresents diamine residues from four or more different diamines all having Formula I as shown above.

[0319] In some embodiments of Formula II, 20-100 mol% of R b is a residue from one or more diamines having Formula I; in some embodiments, 30-100 mol %; in some embodiments, 40-100 mol %; in some embodiments, 50-100 mol %; in some embodiments, 60-100 mol %; in some embodiments, 70-100 mol %; in some embodiments, 80-100 mol %; in some embodiments, 90-100 mol %; in some embodiments, 100%.

[0320] Any of the above embodiments of Formula I in Formula II may be combined with one or more of the other embodiments, as long as they are not mutually exclusive.

[0321] In some embodiments of Formula II, R b represents a diamine residue from one or more diamines having Formula I and at least one additional diamine residue.

[0322] In some embodiments of Formula II, R b represents a diamine residue from one or more diamines having Formula I and one additional diamine residue.

[0323] In some embodiments of Formula II, R b represents a diamine residue from one or more diamines having Formula I and two additional diamine residues.

[0324] In some embodiments of Formula II, R b represents a diamine residue from one or more diamines having Formula I and three additional diamine residues.

[0325] In some embodiments, the additional aromatic diamine is selected from the group consisting of p-phenylenediamine (PPD), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 3,3'-dimethyl-4,4'-diaminobiphenyl (o-tolidine), 3,3'-dihydroxy-4,4'-diaminobiphenyl (HAB), 9,9'-bis(4-aminophenyl)fluorene (FDA), o-tolidine sulfone (TSN), 2,3,5,6-tetramethyl-1,4-phenylenediamine (TMPD), 2,4-diamino-1,3,5-trimethylbenzidine (DAM), 3,3',5,5'-tetramethylbenzidine (3355TMB), 2,2'-bis(trifluoromethyl)fluorene (3355TMB), ) benzidine (22TFMB or TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-methylenedianiline (MDA), 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]dianiline (Bis-M), 4,4'-[1,4-phenylenebis(1-methyl-ethylidene)]dianiline (Bis-P), 4,4'-oxydianiline (4,4'-ODA), metaphenylenediamine (MPD), 3,4'-oxydianiline (3,4'-ODA), 3,3'-diaminodiphenyl sulfone (3,3'-DDS), 4,4'-diaminodiphenyl sulfone (4,4'-DDS), 4, 4'-Diaminodiphenyl sulfide (ASD), 2,2-bis[4-(4-amino-phenoxy)phenyl]sulfone (BAPS), 2,2-bis[4-(3-aminophenoxy)-phenyl]sulfone (m-BAPS), 1,4'-bis(4-aminophenoxy)benzene (TPE-Q), 1,3'-bis(4-aminophenoxy)benzene (TPE-R), 1,3'-bis(4-amino-phenoxy)benzene (APB-133), 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), 4,4'-diaminobenzanilide (DABA), methylenebis(anthranilic acid) (MBAA), 1,3'-bis(4-aminophenoxy)-2,2-dimethylbenzene hexafluoropropane (DANPG), 1,5-bis(4-aminophenoxy)pentane (DA5MG), 2,2'-bis[4-(4-aminophenoxyphenyl)]hexafluoropropane (HFBAPP), 2,2-bis(4-aminophenyl)hexafluoropropane (Bis-A-AF), 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (Bis-AP-AF), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane (Bis-AT-AF), 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl (6BFBAPB), 3,3'5,5'-tetramethyl-4,4'-diaminodiphenylmethane (TMMDA), and the like, and combinations thereof.

[0326] In some embodiments of Formula II, R brepresents diamine residues from one or more diamines having Formula I and diamine residues from at least one additional diamine, wherein the additional diamine is selected from the group consisting of PPD, 4,4'-ODA, 3,4'-ODA, TFMB, Bis-A-AF, Bis-AT-AF, and Bis-P.

[0327] In some embodiments of Formula II, the moiety derived from the monoanhydride monomer is present as a capping group.

[0328] In some embodiments, the monoanhydride monomers are selected from the group consisting of phthalic anhydride and the like and derivatives thereof.

[0329] In some embodiments, these monoanhydrides are present in an amount up to 5 mol % of the total tetracarboxylic acid composition.

[0330] In some embodiments of Formula II, the moiety derived from the monoamine monomer is present as a capping group.

[0331] In some embodiments, the monoamine monomers are selected from the group consisting of aniline and the like and derivatives thereof.

[0332] In some embodiments, these monoamines are present in amounts up to 5 mol % of the total amine composition.

[0333] In some embodiments, the polyamic acid has a weight average molecular weight (M) greater than 100,000 based on gel permeation chromatography with polystyrene standards. W ).

[0334] In some embodiments, the polyamic acid has a weight average molecular weight (M) greater than 150,000 based on gel permeation chromatography with polystyrene standards. W ).

[0335] In some embodiments, the polyamic acid has a molecular weight (M) greater than 200,000 based on gel permeation chromatography with polystyrene standards. W ).

[0336] In some embodiments, the polyamic acid has a weight average molecular weight (M) greater than 250,000 based on gel permeation chromatography with polystyrene standards. W ).

[0337] In some embodiments, the polyamic acid has a weight average molecular weight (M) greater than 300,000 based on gel permeation chromatography with polystyrene standards. W ).

[0338] In some embodiments, the polyamic acid has a weight average molecular weight (MW) of 100,000 to 400,000 based on gel permeation chromatography with polystyrene standards.W ).

[0339] In some embodiments, the polyamic acid has a weight average molecular weight (MW) of 200,000 to 400,000 based on gel permeation chromatography with polystyrene standards. W ).

[0340] In some embodiments, the polyamic acid has a weight average molecular weight (MW) of 250,000 to 350,000 based on gel permeation chromatography with polystyrene standards. W ).

[0341] In some embodiments, the polyamic acid has a weight average molecular weight (MW) of 200,000 to 300,000 based on gel permeation chromatography with polystyrene standards. W ).

[0342] Any of the above embodiments of the polyamic acid may be combined with one or more of the other embodiments as long as they are not mutually exclusive.

[0343] The overall polyamic acid composition can be named via symbols commonly used in the art. For example, a polyamic acid having a tetracarboxylic acid component of 100% ODPA and a diamine component of 90 mol % Bis-P and 10 mol % TFMB can be represented as:

[0344] ODPA / / Bis-P / 22TFMB 100 / / 90 / 10.

[0345] Also provided is a liquid composition comprising (a) a polyamic acid having a repeating unit of formula II and (b) a high boiling point aprotic solvent. The liquid composition is also referred to herein as a "polyamic acid solution".

[0346] In some embodiments, the high boiling point aprotic solvent has a boiling point of 150°C or higher.

[0347] In some embodiments, the high boiling point aprotic solvent has a boiling point of 175°C or higher.

[0348] In some embodiments, the high boiling point aprotic solvent has a boiling point of 200°C or higher.

[0349] In some embodiments, the high boiling point aprotic solvent is a polar solvent. In some embodiments, the solvent has a dielectric constant greater than 20.

[0350] Some examples of high boiling point aprotic solvents include, but are not limited to, N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), γ-butyrolactone, dibutyl carbitol, butyl carbitol acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like, and combinations thereof.

[0351] In some embodiments of the liquid composition, the solvent is selected from the group consisting of NMP, DMAc, and DMF.

[0352] In some embodiments of the liquid composition, the solvent is NMP.

[0353] In some embodiments of liquid compositions, the solvent is DMAc.

[0354] In some embodiments of liquid compositions, the solvent is DMF.

[0355] In some embodiments of liquid compositions, the solvent is gamma-butyrolactone.

[0356] In some embodiments of the liquid composition, the solvent is dibutyl carbitol.

[0357] In some embodiments of the liquid composition, the solvent is butyl carbitol acetate.

[0358] In some embodiments of the liquid composition, the solvent is diethylene glycol monoethyl ether acetate.

[0359] In some embodiments of liquid compositions, the solvent is propylene glycol monoethyl ether acetate.

[0360] In some embodiments, more than one of the above noted high boiling point aprotic solvents is used in the liquid composition.

[0361] In some embodiments, additional co-solvents are used in the liquid compositions.

[0362] In some embodiments, the liquid composition is <1 wt% polyamic acid in >99 wt% high boiling aprotic solvent.

[0363] In some embodiments, the liquid composition is 1 wt% to 5 wt% polyamic acid in 95 wt% to 99 wt% high boiling point aprotic solvent.

[0364] In some embodiments, the liquid composition is 5 wt%-10 wt% polyamic acid in 90 wt%-95 wt% high boiling point aprotic solvent.

[0365] In some embodiments, the liquid composition is 10 wt% to 15 wt% polyamic acid in 85 wt% to 90 wt% high boiling point aprotic solvent.

[0366] In some embodiments, the liquid composition is 15 wt%-20 wt% polyamic acid in 80 wt%-85 wt% high boiling point aprotic solvent.

[0367] In some embodiments, the liquid composition is 20 wt% to 25 wt% polyamic acid in 75 wt% to 80 wt% high boiling point aprotic solvent.

[0368] In some embodiments, the liquid composition is 25 wt%-30 wt% polyamic acid in 70 wt%-75 wt% high boiling point aprotic solvent.

[0369] In some embodiments, the liquid composition is 30 wt% to 35 wt% polyamic acid in 65 wt% to 70 wt% high boiling point aprotic solvent.

[0370] In some embodiments, the liquid composition is 35 wt%-40 wt% polyamic acid in 60 wt%-65 wt% high boiling point aprotic solvent.

[0371] In some embodiments, the liquid composition is 40 wt% to 45 wt% polyamic acid in 55 wt% to 60 wt% high boiling point aprotic solvent.

[0372] In some embodiments, the liquid composition is 45 wt%-50 wt% polyamic acid in 50 wt%-55 wt% high boiling point aprotic solvent.

[0373] In some embodiments, the liquid composition is 50 wt % polyamic acid in 50 wt % high boiling point aprotic solvent.

[0374] The polyamic acid solution may optionally further contain any of a number of additives. Such additives may be antioxidants, heat stabilizers, adhesion promoters, coupling agents (such as silanes), inorganic fillers or various reinforcing agents, as long as they do not adversely affect the desired polyimide properties.

[0375] Polyamic acid solutions can be prepared using various available methods for introducing the components (i.e., monomers and solvents). Some methods for producing polyamic acid solutions include:

[0376] (a) A method in which a diamine component and a dianhydride component are mixed together in advance and then the mixture is added portionwise to a solvent while stirring.

[0377] (b) A method in which a solvent is added to a stirred mixture of the diamine and dianhydride components. (The opposite of (a) above)

[0378] (c) A method in which a diamine is dissolved separately in a solvent, and then a dianhydride is added thereto in a proportion that allows the reaction rate to be controlled.

[0379] (d) A method in which a dianhydride component is separately dissolved in a solvent, and then an amine component is added thereto in a ratio that allows control of the reaction rate.

[0380] (e) A method in which a diamine component and a dianhydride component are separately dissolved in solvents and then these solutions are mixed in a reactor.

[0381] (f) A method in which a polyamic acid having an excess amine component and another polyamic acid having an excess dianhydride component are preformed and then reacted with each other in a reactor, particularly in such a manner as to produce a non-random or block copolymer.

[0382] (g) A method in which a specific part of the amine component and the dianhydride component is first reacted, and then the remaining diamine component is reacted, or vice versa.

[0383] (h) A method wherein the components are added partly or as a whole to part or all of the solvent in any order, further wherein part or all of any component may be added as a solution in part or all of the solvent.

[0384] (i) A method in which one of the dianhydride components is first reacted with one of the diamine components to obtain a first polyamic acid. The other dianhydride component is then reacted with the other amine component to obtain a second polyamic acid. The polyamic acids are then combined in any of a variety of ways prior to film formation.

[0385] Generally speaking, the polyamic acid solution can be obtained by any of the polyamic acid solution preparation methods disclosed above.

[0386] The polyamic acid solution can then be filtered one or more times to reduce the particle content. The polyimide film produced by this filtered solution can show a reduced number of defects and thus produce excellent performance in electronic applications disclosed herein. The evaluation of filtration efficiency can be performed by a laser particle counter test, wherein a representative sample of the polyamic acid solution is cast onto a 5 "silicon wafer. After soft baking / drying, the particle content of the film is evaluated by any number of laser particle counting techniques on commercially available and known instruments in the art.

[0387] In some embodiments, a polyamic acid solution is prepared and filtered to produce a particle content of less than 40 particles as measured by a laser particle counter test.

[0388] In some embodiments, a polyamic acid solution is prepared and filtered to produce a particle content of less than 30 particles as measured by a laser particle counter test.

[0389] In some embodiments, a polyamic acid solution is prepared and filtered to produce a particle content of less than 20 particles as measured by a laser particle counter test.

[0390] In some embodiments, a polyamic acid solution is prepared and filtered to produce a particle content of less than 10 particles as measured by a laser particle counter test.

[0391] In some embodiments, a polyamic acid solution is prepared and filtered to produce a particle content of 2 particles to 8 particles as measured by a laser particle counter test.

[0392] In some embodiments, a polyamic acid solution is prepared and filtered to produce a particle content of 4 particles to 6 particles as measured by a laser particle counter test.

[0393] An exemplary preparation of a polyamic acid solution is given in the Examples.

[0394] 4. Polyimide having a repeating unit structure of formula IV

[0395] A polyimide having a repeating unit structure of formula IV is provided

[0396]

[0397] in

[0398] R a is the same or different at each occurrence and represents one or more tetracarboxylic acid component residues; and

[0399] R b is the same or different at each occurrence and represents one or more aromatic diamine residues;

[0400] 10-100 mol% of R b is a residue from one or more diamines of formula I.

[0401] For R in Formula II a and R b All the above-described embodiments are also applicable to R in Formula IV a and R b .

[0402] Any of the above embodiments of Formula I in Formula IV may be combined with one or more of the other embodiments, as long as they are not mutually exclusive.

[0403] The polyimide may be made from any suitable polyimide precursor such as polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid salt.

[0404] Also provided is a polyimide film, wherein the polyimide has a repeating unit structure of Formula IV as described above.

[0405] The polyimide film can be made by coating a polyimide precursor onto a substrate and then imidizing it. This can be achieved by a thermal conversion method or a chemical conversion method.

[0406] Furthermore, if the polyimide is soluble in a suitable coating solvent, it can be provided as an already imidized polymer dissolved in a suitable coating solvent and coated as the polyimide.

[0407] In some embodiments, polyimide films having repeating units of Formula IV have both high glass transition temperature and low optical retardation.

[0408] In some embodiments of the polyimide film, for the polyimide film cured at a temperature exceeding 350° C., the glass transition temperature (T g ) is greater than 300°C; in some embodiments, greater than 370°C; in some embodiments, greater than 380°C.

[0409] In some embodiments of the polyimide film, the optical retardation is less than 120 at 550 nm; in some embodiments, less than 100; in some embodiments, less than 90.

[0410] In some embodiments of the polyimide film, for the first measurement, the in-plane coefficient of thermal expansion (CTE) is less than 45 ppm / °C at 50°C to 200°C; in some embodiments, less than 30 ppm / °C; in some embodiments, less than 20 ppm / °C; in some embodiments, less than 15 ppm / °C.

[0411] In some embodiments of the polyimide film, for the second measurement, the in-plane coefficient of thermal expansion (CTE) is less than 75 ppm / °C at 50°C to 200°C; in some embodiments, less than 65 ppm / °C.

[0412] In some embodiments of the polyimide film, the 1% TGA weight loss temperature is greater than 350°C; in some embodiments, greater than 400°C; in some embodiments, greater than 450°C.

[0413] In some embodiments of the polyimide film, the tensile modulus is 1.5 GPa to 15.0 GPa; in some embodiments, 1.5 GPa to 10.0 GPa; in some embodiments, 1.5 GPa to 7.5 GPa; in some embodiments, 1.5 GPa to 5.0 GPa.

[0414] In some embodiments of the polyimide film, the elongation at break is greater than 10%.

[0415] In some embodiments of the polyimide film, the haze is less than 1.0%; in some embodiments, less than 0.5%.

[0416] In some embodiments of the polyimide films, b* is less than 7.5; in some embodiments, less than 5.0.

[0417] In some embodiments of the polyimide film, the YI is less than 12; in some embodiments, less than 10.

[0418] In some embodiments of the polyimide film, the transmittance at 400 nm is greater than 40%; in some embodiments, greater than 50%.

[0419] In some embodiments of the polyimide film, the transmittance at 430 nm is greater than 60%; in some embodiments, greater than 70%.

[0420] In some embodiments of the polyimide film, the transmittance at 450 nm is greater than 70%; in some embodiments, greater than 80%.

[0421] In some embodiments of the polyimide film, the transmittance at 550 nm is greater than 70%; in some embodiments, greater than 80%.

[0422] In some embodiments of the polyimide film, the transmittance at 750 nm is greater than 70%; in some embodiments, greater than 80%.

[0423] Any of the above-described embodiments of the polyimide film may be combined with one or more of the other embodiments, as long as they are not mutually exclusive.

[0424] 5. Method for preparing polyimide film

[0425] In general, polyimide films can be prepared from polyimide precursors by chemical or thermal conversion. In certain embodiments, these films are prepared from corresponding polyamic acid solutions by chemical or thermal conversion methods. Polyimide films disclosed herein (particularly when used as a flexible substitute for glass in electronic devices) are prepared by thermal conversion methods.

[0426] In general, polyimide films can be prepared from the corresponding polyamic acid solutions by chemical or thermal conversion methods. The polyimide films disclosed herein, especially when used as flexible replacements for glass in electronic devices, are prepared by thermal conversion or modified thermal and chemical conversion methods.

[0427] Chemical conversion methods are described in U.S. Patent Nos. 5,166,308 and 5,298,331, which are incorporated herein by reference in their entirety. In such methods, conversion chemicals are added to a polyamic acid solution. Conversion chemicals found to be useful in the present invention include, but are not limited to: (i) one or more dehydrating agents, such as aliphatic anhydrides (acetic anhydride, etc.) and anhydrides; and (ii) one or more catalysts, such as aliphatic tertiary amines (triethylamine, etc.), tertiary amines (dimethylaniline, etc.) and heterocyclic tertiary amines (pyridine, picoline, isoquinoline, etc.). Anhydride dehydration materials are typically used in a slightly molar excess of the amount of amic acid groups present in the polyamic acid solution. The amount of acetic anhydride used is typically about 2.0-3.0 moles per equivalent of polyamic acid. In general, a considerable amount of tertiary amine catalyst is used.

[0428] Thermal conversion methods may or may not employ conversion chemicals (i.e., catalysts) to convert polyamic acid casting solutions into polyimide. If conversion chemicals are used, the method can be considered as an improved thermal conversion method. In two types of thermal conversion methods, only thermal energy is used to heat the film to not only dry the film of the solvent but also to carry out imidization. Thermal conversion methods with or without conversion catalysts are usually used to prepare polyimide films disclosed herein.

[0429] The specific method parameters are pre-selected in view of the fact that it is not just the film composition that produces the properties of interest. On the contrary, the curing temperature and the temperature ramp-up curve also play an important role in achieving the most desirable properties of the intended use disclosed herein. The polyamic acid should be imidized at or above the maximum temperature of any subsequent processing step (e.g., depositing one or more inorganic or other layers required to produce a functional display), but at a temperature lower than the temperature at which significant thermal degradation / discoloration of the polyimide occurs. It should also be noted that an inert atmosphere is generally preferred, particularly when imidization is performed using a higher processing temperature.

[0430] For the polyamic acid / polyimide disclosed herein, when subsequent processing temperatures exceeding 300°C are required, temperatures of 300°C to 320°C are typically employed. Selection of an appropriate curing temperature allows for a fully cured polyimide that achieves an optimal balance of thermal and mechanical properties. Due to this very high temperature, an inert atmosphere is required. Typically, an in-furnace oxygen level of <100 ppm should be employed. Very low oxygen levels enable the use of the highest curing temperatures without significant degradation / discoloration of the polymer. Catalysts that accelerate the imidization process are effective at achieving higher levels of imidization at curing temperatures of about 200°C to 300°C. If the flexible device is cured at a temperature below the T of the polyimide, the curing temperature will be reduced. g If the material is prepared at a higher curing temperature, this method can be optionally used.

[0431] The amount of time for each possible curing step is also an important process consideration. Generally speaking, the time for the highest temperature cure should be kept to a minimum. For example, for a 320°C cure, the cure time can be as long as about 1 hour under an inert atmosphere; but at higher cure temperatures, this time should be shortened to avoid thermal degradation. Generally speaking, higher temperatures indicate shorter times. Those skilled in the art will recognize the balance between temperature and time in order to optimize the properties of the polyimide for a particular end use.

[0432] In some embodiments, the polyamic acid solution is converted into a polyimide film via a thermal conversion process.

[0433] In some embodiments of the thermal conversion method, the polyamic acid solution is coated onto the substrate such that the soft-baked thickness of the resulting film is less than 50 μm.

[0434] In some embodiments of the thermal conversion method, the polyamic acid solution is coated onto the substrate such that the soft-baked thickness of the resulting film is less than 40 μm.

[0435] In some embodiments of the thermal conversion method, the polyamic acid solution is coated onto the substrate such that the soft-baked thickness of the resulting film is less than 30 μm.

[0436] In some embodiments of the thermal conversion method, the polyamic acid solution is coated onto the substrate such that the soft-baked thickness of the resulting film is less than 20 μm.

[0437] In some embodiments of the thermal conversion method, the polyamic acid solution is coated onto the substrate such that the soft-baked thickness of the resulting film is 10 μm to 20 μm.

[0438] In some embodiments of the thermal conversion method, the polyamic acid solution is coated onto the substrate such that the soft-baked thickness of the resulting film is 15 μm to 20 μm.

[0439] In some embodiments of the thermal conversion process, the polyamic acid solution is coated onto the substrate such that the soft-baked thickness of the resulting film is 18 μm.

[0440] In some embodiments of the thermal conversion method, the polyamic acid solution is coated onto the substrate such that the soft-baked thickness of the resulting film is less than 10 μm.

[0441] In some embodiments of the thermal conversion method, the coated substrate is soft-baked in proximity mode on a hot plate, where nitrogen gas is used to hold the coated substrate just above the hot plate.

[0442] In some embodiments of the thermal conversion method, the coated substrate is soft-baked on a hot plate in full contact mode, where the coated substrate is in direct contact with the hot plate surface.

[0443] In some embodiments of the thermal conversion method, the coated substrate is soft-baked on a hot plate using a combination of proximity mode and full contact mode.

[0444] In some embodiments of the thermal conversion method, the coated substrate is soft-baked using a hot plate set at 80°C.

[0445] In some embodiments of the thermal conversion method, the coated substrate is soft-baked using a hot plate set at 90°C.

[0446] In some embodiments of the thermal conversion method, the coated substrate is soft-baked using a hot plate set at 100°C.

[0447] In some embodiments of the thermal conversion process, the coated substrate is soft-baked using a hot plate set at 110°C.

[0448] In some embodiments of the thermal conversion method, the coated substrate is soft-baked using a hot plate set at 120°C.

[0449] In some embodiments of the thermal conversion process, the coated substrate is soft-baked using a hot plate set at 130°C.

[0450] In some embodiments of the thermal conversion process, the coated substrate is soft-baked using a hot plate set at 140°C.

[0451] In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time exceeding 10 minutes.

[0452] In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 10 minutes.

[0453] In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 8 minutes.

[0454] In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 6 minutes.

[0455] In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of 4 minutes.

[0456] In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 4 minutes.

[0457] In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 2 minutes.

[0458] In some embodiments of the thermal conversion method, the soft baked coated substrate is then cured at 2 preselected temperatures for 2 preselected time intervals, where these time intervals may be the same or different.

[0459] In some embodiments of the thermal conversion method, the soft baked coated substrate is then cured at 3 preselected temperatures for 3 preselected time intervals, where each of these time intervals may be the same or different.

[0460] In some embodiments of the thermal conversion method, the soft baked coated substrate is then cured at four preselected temperatures for four preselected time intervals, where each of these time intervals may be the same or different.

[0461] In some embodiments of the thermal conversion method, the soft baked coated substrate is then cured at 5 preselected temperatures for 5 preselected time intervals, where each of these time intervals may be the same or different.

[0462] In some embodiments of the thermal conversion method, the soft baked coated substrate is then cured at 6 preselected temperatures for 6 preselected time intervals, where each of these time intervals may be the same or different.

[0463] In some embodiments of the thermal conversion method, the soft baked coated substrate is then cured at 7 preselected temperatures for 7 preselected time intervals, where each of these time intervals may be the same or different.

[0464] In some embodiments of the thermal conversion method, the soft baked coated substrate is then cured at 8 preselected temperatures for 8 preselected time intervals, where each of these time intervals may be the same or different.

[0465] In some embodiments of the thermal conversion method, the soft baked coated substrate is then cured at 9 preselected temperatures for 9 preselected time intervals, where each of these time intervals may be the same or different.

[0466] In some embodiments of the thermal conversion method, the soft baked coated substrate is then cured at 10 preselected temperatures for 10 preselected time intervals, where each of these time intervals may be the same or different.

[0467] In some embodiments of the thermal conversion method, the preselected temperature is greater than 80°C.

[0468] In some embodiments of the thermal conversion method, the preselected temperature is equal to 100°C.

[0469] In some embodiments of the thermal conversion method, the preselected temperature is greater than 100°C.

[0470] In some embodiments of the thermal conversion method, the preselected temperature is equal to 150°C.

[0471] In some embodiments of the thermal conversion method, the preselected temperature is greater than 150°C.

[0472] In some embodiments of the thermal conversion method, the preselected temperature is equal to 200°C.

[0473] In some embodiments of the thermal conversion method, the preselected temperature is greater than 200°C.

[0474] In some embodiments of the thermal conversion method, the preselected temperature is equal to 250°C.

[0475] In some embodiments of the thermal conversion method, the preselected temperature is greater than 250°C.

[0476] In some embodiments of the thermal conversion method, the preselected temperature is equal to 300°C.

[0477] In some embodiments of the thermal conversion method, the preselected temperature is greater than 300°C.

[0478] In some embodiments of the thermal conversion method, the preselected temperature is equal to 350°C.

[0479] In some embodiments of the thermal conversion method, the preselected temperature is greater than 350°C.

[0480] In some embodiments of the thermal conversion method, the preselected temperature is equal to 400°C.

[0481] In some embodiments of the thermal conversion method, the preselected temperature is greater than 400°C.

[0482] In some embodiments of the thermal conversion method, the preselected temperature is equal to 450°C.

[0483] In some embodiments of the thermal conversion method, the preselected temperature is greater than 450°C.

[0484] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 2 minutes.

[0485] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 5 minutes.

[0486] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 10 minutes.

[0487] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 15 minutes.

[0488] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 20 minutes.

[0489] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 25 minutes.

[0490] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 30 minutes.

[0491] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 35 minutes.

[0492] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 40 minutes.

[0493] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 45 minutes.

[0494] In some of the thermal conversion methods, one or more of the preselected time intervals is 50 minutes.

[0495] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 55 minutes.

[0496] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 60 minutes.

[0497] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is greater than 60 minutes.

[0498] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is from 2 minutes to 60 minutes.

[0499] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is from 2 minutes to 90 minutes.

[0500] In some embodiments of the thermal conversion method, one or more of the preselected time intervals is from 2 minutes to 120 minutes.

[0501] In some embodiments of the thermal conversion method, the method for preparing a polyimide film includes the following steps in sequence: coating the polyamic acid solution described above onto a substrate; soft baking the coated substrate; treating the soft baked coated substrate at multiple preselected temperatures for multiple preselected time intervals, whereby the polyimide film exhibits properties that meet those electronic applications as disclosed herein.

[0502] In some embodiments of the thermal conversion method, the method for preparing a polyimide film consists of the following steps in sequence: coating the polyamic acid solution described above onto a substrate; soft baking the coated substrate; treating the soft baked coated substrate at multiple preselected temperatures for multiple preselected time intervals, whereby the polyimide film exhibits properties that meet those electronic applications as disclosed herein.

[0503] In some embodiments of the thermal conversion method, the method for preparing a polyimide film consists essentially of the following steps in sequence: coating the polyamic acid solution described above onto a substrate; soft-baking the coated substrate; treating the soft-baked coated substrate at multiple preselected temperatures for multiple preselected time intervals, whereby the polyimide film exhibits properties that meet those electronic applications as disclosed herein.

[0504] Typically, the polyamic acid solution / polyimide disclosed herein is coated / cured onto a supporting glass substrate to aid processing during the rest of the display manufacturing process. At a certain point in the process determined by the display manufacturer, the polyimide coating is removed from the supporting glass substrate by a mechanical or laser stripping process. These processes separate the polyimide as a film with a deposited display layer from the glass and achieve a flexible form. Typically, the polyimide film with the deposited layer is then bonded to a thicker but still flexible plastic film to provide support for the subsequent manufacture of the display.

[0505] Also provided are improved thermal conversion processes wherein the conversion catalyst generally allows the imidization reaction to proceed at lower temperatures than would be possible in the absence of such conversion catalyst.

[0506] In some embodiments, the polyamic acid solution is converted into a polyimide film via a modified thermal conversion process.

[0507] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains a conversion catalyst.

[0508] In some embodiments of the improved thermal conversion process, the polyamic acid solution further contains a conversion catalyst selected from the group consisting of tertiary amines.

[0509] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains a conversion catalyst selected from the group consisting of tributylamine, dimethylethanolamine, isoquinoline, 1,2-dimethylimidazole, N-methylimidazole, 2-methylimidazole, 2-ethyl-4-imidazole, 3,5-lutidine, 3,4-lutidine, 2,5-lutidine, 5-methylbenzimidazole, and the like.

[0510] In some embodiments of the improved thermal conversion process, the conversion catalyst is present at 5 wt % or less of the polyamic acid solution.

[0511] In some embodiments of the improved thermal conversion process, the conversion catalyst is present at 3 wt % or less of the polyamic acid solution.

[0512] In some embodiments of the improved thermal conversion process, the conversion catalyst is present at 1 wt % or less of the polyamic acid solution.

[0513] In some embodiments of the improved thermal conversion process, the conversion catalyst is present at 1 wt % of the polyamic acid solution.

[0514] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains tributylamine as a conversion catalyst.

[0515] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains dimethylethanolamine as a conversion catalyst.

[0516] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains isoquinoline as a conversion catalyst.

[0517] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 1,2-dimethylimidazole as a conversion catalyst.

[0518] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 3,5-lutidine as a conversion catalyst.

[0519] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 5-methylbenzimidazole as a conversion catalyst.

[0520] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains N-methylimidazole as a conversion catalyst.

[0521] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 2-methylimidazole as a conversion catalyst.

[0522] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 2-ethyl-4-imidazole as a conversion catalyst.

[0523] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 3,4-lutidine as a conversion catalyst.

[0524] In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 2,5-lutidine as a conversion catalyst.

[0525] In some embodiments of the improved thermal conversion process, the polyamic acid solution is coated onto a substrate such that the soft-baked thickness of the resulting film is less than 50 μm.

[0526] In some embodiments of the improved thermal conversion process, the polyamic acid solution is coated onto a substrate such that the soft-baked thickness of the resulting film is less than 40 μm.

[0527] In some embodiments of the improved thermal conversion process, the polyamic acid solution is coated onto a substrate such that the soft-baked thickness of the resulting film is less than 30 μm.

[0528] In some embodiments of the improved thermal conversion process, the polyamic acid solution is coated onto a substrate such that the soft-baked thickness of the resulting film is less than 20 μm.

[0529] In some embodiments of the improved thermal conversion process, the polyamic acid solution is coated onto the substrate such that the soft-baked thickness of the resulting film is 10 μm to 20 μm.

[0530] In some embodiments of the improved thermal conversion process, the polyamic acid solution is coated onto the substrate such that the soft-baked thickness of the resulting film is 15 μm to 20 μm.

[0531] In some embodiments of the improved thermal conversion process, the polyamic acid solution is coated onto the substrate such that the soft-baked thickness of the resulting film is 18 μm.

[0532] In some embodiments of the improved thermal conversion process, the polyamic acid solution is coated onto a substrate such that the soft-baked thickness of the resulting film is less than 10 μm.

[0533] In some embodiments of the improved thermal conversion method, the coated substrate is soft-baked in proximity mode on a hot plate, where nitrogen gas is used to hold the coated substrate just above the hot plate.

[0534] In some embodiments of the improved thermal conversion method, the coated substrate is soft-baked on a hot plate in full contact mode, wherein the coated substrate is in direct contact with the hot plate surface.

[0535] In some embodiments of the improved thermal conversion method, the coated substrate is soft-baked on a hot plate using a combination of proximity mode and full contact mode.

[0536] In some embodiments of the improved thermal conversion process, the coated substrate is soft-baked using a hot plate set at 80°C.

[0537] In some embodiments of the improved thermal conversion process, the coated substrate is soft-baked using a hot plate set at 90°C.

[0538] In some embodiments of the improved thermal conversion process, the coated substrate is soft-baked using a hot plate set at 100°C.

[0539] In some embodiments of the improved thermal conversion process, the coated substrate is soft-baked using a hot plate set at 110°C.

[0540] In some embodiments of the improved thermal conversion process, the coated substrate is soft-baked using a hot plate set at 120°C.

[0541] In some embodiments of the improved thermal conversion process, the coated substrate was soft-baked using a hot plate set at 130°C.

[0542] In some embodiments of the improved thermal conversion process, the coated substrate was soft-baked using a hot plate set at 140°C.

[0543] In some embodiments of the improved thermal conversion process, the coated substrate is soft baked for a total time exceeding 10 minutes.

[0544] In some embodiments of the improved thermal conversion process, the coated substrate is soft baked for a total time of less than 10 minutes.

[0545] In some embodiments of the improved thermal conversion process, the coated substrate is soft baked for a total time of less than 8 minutes.

[0546] In some embodiments of the improved thermal conversion process, the coated substrate is soft baked for a total time of less than 6 minutes.

[0547] In some embodiments of the improved thermal conversion process, the coated substrate is soft baked for a total time of 4 minutes.

[0548] In some embodiments of the improved thermal conversion process, the coated substrate is soft baked for a total time of less than 4 minutes.

[0549] In some embodiments of the improved thermal conversion process, the coated substrate is soft baked for a total time of less than 2 minutes.

[0550] In some embodiments of the improved thermal conversion process, the soft baked coated substrate is then cured at 2 preselected temperatures for 2 preselected time intervals, where these time intervals may be the same or different.

[0551] In some embodiments of the improved thermal conversion process, the soft baked coated substrate is then cured at 3 preselected temperatures for 3 preselected time intervals, where each of these time intervals may be the same or different.

[0552] In some embodiments of the improved thermal conversion process, the soft baked coated substrate is then cured at four preselected temperatures for four preselected time intervals, where each of these time intervals may be the same or different.

[0553] In some embodiments of the improved thermal conversion process, the soft baked coated substrate is then cured at 5 preselected temperatures for 5 preselected time intervals, where each of these time intervals may be the same or different.

[0554] In some embodiments of the improved thermal conversion process, the soft baked coated substrate is then cured at 6 preselected temperatures for 6 preselected time intervals, where each of these time intervals may be the same or different.

[0555] In some embodiments of the improved thermal conversion process, the soft baked coated substrate is then cured at 7 preselected temperatures for 7 preselected time intervals, where each of these time intervals may be the same or different.

[0556] In some embodiments of the improved thermal conversion process, the soft baked coated substrate is then cured at 8 preselected temperatures for 8 preselected time intervals, where each of these time intervals may be the same or different.

[0557] In some embodiments of the improved thermal conversion process, the soft baked coated substrate is then cured at 9 preselected temperatures for 9 preselected time intervals, where each of these time intervals may be the same or different.

[0558] In some embodiments of the improved thermal conversion process, the soft baked coated substrate is then cured at 10 preselected temperatures for 10 preselected time intervals, where each of these time intervals may be the same or different.

[0559] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 80°C.

[0560] In some embodiments of the improved thermal conversion process, the preselected temperature is equal to 100°C.

[0561] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 100°C.

[0562] In some embodiments of the improved thermal conversion process, the preselected temperature is equal to 150°C.

[0563] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 150°C.

[0564] In some embodiments of the improved thermal conversion process, the preselected temperature is equal to 200°C.

[0565] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 200°C.

[0566] In some embodiments of the improved thermal conversion process, the preselected temperature is equal to 220°C.

[0567] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 220°C.

[0568] In some embodiments of the improved thermal conversion process, the preselected temperature is equal to 230°C.

[0569] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 230°C.

[0570] In some embodiments of the improved thermal conversion process, the preselected temperature is equal to 240°C.

[0571] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 240°C.

[0572] In some embodiments of the improved thermal conversion process, the preselected temperature is equal to 250°C.

[0573] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 250°C.

[0574] In some embodiments of the improved thermal conversion process, the preselected temperature is equal to 260°C.

[0575] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 260°C.

[0576] In some embodiments of the improved thermal conversion process, the preselected temperature is equal to 270°C.

[0577] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 270°C.

[0578] In some embodiments of the improved thermal conversion process, the preselected temperature is equal to 280°C.

[0579] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 280°C.

[0580] In some embodiments of the improved thermal conversion process, the preselected temperature is equal to 290°C.

[0581] In some embodiments of the improved thermal conversion process, the preselected temperature is greater than 290°C.

[0582] In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 300°C.

[0583] In some embodiments of the improved thermal conversion method, the preselected temperature is less than 300°C.

[0584] In some embodiments of the improved thermal conversion process, the preselected temperature is less than 290°C.

[0585] In some embodiments of the improved thermal conversion process, the preselected temperature is less than 280°C.

[0586] In some embodiments of the improved thermal conversion process, the preselected temperature is less than 270°C.

[0587] In some embodiments of the improved thermal conversion process, the preselected temperature is less than 260°C.

[0588] In some embodiments of the improved thermal conversion process, the preselected temperature is less than 250°C.

[0589] In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 2 minutes.

[0590] In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 5 minutes.

[0591] In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 10 minutes.

[0592] In some embodiments of the improved conversion method, one or more of the preselected time intervals is 15 minutes.

[0593] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is 20 minutes.

[0594] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is 25 minutes.

[0595] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is 30 minutes.

[0596] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is 35 minutes.

[0597] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is 40 minutes.

[0598] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is 45 minutes.

[0599] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is 50 minutes.

[0600] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is 55 minutes.

[0601] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is 60 minutes.

[0602] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is greater than 60 minutes.

[0603] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is from 2 minutes to 60 minutes.

[0604] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is from 2 minutes to 90 minutes.

[0605] In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals is from 2 minutes to 120 minutes.

[0606] In some embodiments of the improved thermal conversion method, the method for preparing a polyimide film includes the following steps in sequence: coating the polyamic acid solution containing the conversion chemical described above onto a substrate; soft baking the coated substrate; treating the soft baked coated substrate at multiple preselected temperatures for multiple preselected time intervals, whereby the polyimide film exhibits properties that meet those electronic applications as disclosed herein.

[0607] In some embodiments of the improved thermal conversion process, the method for preparing a polyimide film consists of the following steps in sequence: coating the polyamic acid solution containing the conversion chemical described above onto a substrate; soft baking the coated substrate; treating the soft baked coated substrate at multiple preselected temperatures for multiple preselected time intervals, whereby the polyimide film exhibits properties satisfactory for use in electronic applications such as those disclosed herein.

[0608] In some embodiments of the improved thermal conversion process, the method for preparing a polyimide film consists essentially of the following steps in sequence: coating the polyamic acid solution containing the conversion chemical described above onto a substrate; soft baking the coated substrate; treating the soft baked coated substrate at multiple preselected temperatures for multiple preselected time intervals, whereby the polyimide film exhibits properties satisfactory for use in electronic applications such as those disclosed herein.

[0609] 6. Electronic devices

[0610] The polyimide films disclosed herein can be applied to multiple layers in electronic display devices (such as OLED and LCD displays). Non-limiting examples of such layers include substrates for devices, touch panels, substrates for color filters, cover films, etc. The characteristic requirements of specific materials for each application are unique and can be solved by one or more appropriate compositions and one or more processing conditions of the polyimide films disclosed herein.

[0611] In some embodiments, a flexible replacement for glass in electronic devices is a polyimide film having a repeating unit of Formula IV as described in detail above.

[0612] Organic electronic devices that may benefit from having one or more layers comprising at least one compound as described herein include, but are not limited to: (1) devices that convert electrical energy into radiation (e.g., light emitting diodes, light emitting diode displays, lighting devices, light sources, or diode lasers), (2) devices that detect signals by electronic means (e.g., photodetectors, photoconductive cells, photoresistors, photorelays, phototransistors, phototubes, IR detectors, biosensors), (3) devices that convert radiation into electrical energy (e.g., photovoltaic devices or solar cells), (4) devices that convert light of one wavelength into light of a longer wavelength (e.g., down-converting phosphor devices); and (5) devices that include one or more electronic components that include one or more organic semiconductor layers (e.g., transistors or diodes). Other uses of the compositions according to the present invention include coating materials for memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolyte capacitors, energy storage devices (such as rechargeable batteries), and electromagnetic shielding applications.

[0613] Figure 1 An illustration of a polyimide film that can serve as a flexible substitute for glass as described herein is shown in FIG. Flexible film 100 can have properties as described in embodiments of the present disclosure. In some embodiments, a polyimide film that can serve as a flexible substitute for glass is included in an electronic device. Figure 2 The case where the electronic device 200 is an organic electronic device is described. The device 200 has a substrate 100, an anode layer 110 and a second electrical contact layer, a cathode layer 130, and a photoactive layer 120 between them. Additional layers may optionally be present. Adjacent to the anode may be a hole injection layer (not shown), sometimes referred to as a buffer layer. Adjacent to the hole injection layer may be a hole transport layer (not shown) containing a hole transport material. Adjacent to the cathode may be an electron transport layer (not shown) containing an electron transport material. As an option, the device may use one or more additional hole injection layers or hole transport layers (not shown) adjacent to the anode 110 and / or one or more additional electron injection layers or electron transport layers (not shown) adjacent to the cathode 130. The layers between 110 and 130 are individually and collectively referred to as organic active layers. Additional layers that may or may not exist include color filters, touch panels, and / or cover sheets. One or more of these layers (in addition to the substrate 100) may also be made of a polyimide film disclosed herein.

[0614] Here we will refer to Figure 2 These different layers are discussed further below. However, the discussion is equally applicable to other configurations.

[0615] In some embodiments, the different layers have the following thickness ranges: substrate 100, 5-100 microns, anode In some embodiments, a hole injection layer (not shown), In some embodiments, a hole transport layer (not shown), In some embodiments, Photoactive layer 120, In some embodiments, an electron transport layer (not shown), In some embodiments, Cathode 130, In some embodiments, The desired ratio of layer thicknesses will depend on the exact nature of the materials used.

[0616] In some embodiments, organic electronic devices (OLEDs) contain flexible replacements for glass as disclosed herein.

[0617] In some embodiments, the organic electronic device comprises a substrate, an anode, a cathode, and a photoactive layer therebetween, and further comprises one or more additional organic active layers. In some embodiments, the additional organic active layer is a hole transport layer. In some embodiments, the additional organic active layer is an electron transport layer. In some embodiments, the additional organic layer is both a hole transport layer and an electron transport layer.

[0618] Anode 110 is an electrode that is particularly effective for injecting positive charge carriers. It can be made of, for example, a material containing a metal, a mixed metal, an alloy, a metal oxide or a mixed metal oxide, or it can be a conductive polymer, and mixtures thereof. Suitable metals include Group 11 metals, metals in Groups 4, 5 and 6, and transition metals in Groups 8-10. If the anode is to be light-transmitting, mixed metal oxides of Groups 12, 13 and 14 metals, such as indium tin oxide, are generally used. The anode may also contain an organic material such as polyaniline, as described in "Flexible light-emitting diodes made from soluble conducting polymer", Nature, Vol. 357, pp. 477-479 (June 11, 1992). At least one of the anode and cathode should be at least partially transparent to allow the generated light to be observed.

[0619] The optional hole injection layer may include a hole injection material. The term "hole injection layer" or "hole injection material" is intended to refer to a conductive or semiconductive material and may have one or more functions in an organic electronic device, including but not limited to planarization of the underlying layer, charge transport and / or charge injection characteristics, removal of impurities such as oxygen or metal ions, and other aspects that are beneficial to or improve the performance of the organic electronic device. The hole injection material may be a polymer, oligomer or small molecule, and may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture or other composition.

[0620] Hole injection layer can be formed with polymeric materials, such as polyaniline (PANI) or polyethylene dioxythiophene (PEDOT), and these polymeric materials are doped with protonic acid usually. Protonic acid can be, for example, poly (styrene sulfonic acid), poly (2-acrylamide-2-methyl-1-propane sulfonic acid) etc. Hole injection layer 120 can include charge transfer compounds etc., such as copper phthalocyanine and tetrathiafulvalene-tetracyano-p-benzoquinone dimethane system (TTF-TCNQ). In certain embodiments, hole injection layer 120 is made of a dispersion of a conductive polymer and a polymer acid that forms a colloid. Such materials have been described in, for example, U.S. Patent Applications 2004-0102577, 2004-0127637 and 2005-0205860 announced.

[0621] Other layers may include hole transport materials. Examples of hole transport materials for hole transport layers have been summarized, for example, in Y. Wang's Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition, Vol. 18, pp. 837-860, 1996. Both hole transport small molecules and polymers can be used. Commonly used hole transport molecules include, but are not limited to: 4,4',4"-tris(N,N-diphenyl-amino)-triphenylamine (TDATA); 4,4',4"-tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA); N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine (TPD); 4,4'-bis( carbazole-9-yl)biphenyl (CBP); 1,3-bis(carbazole-9-yl)benzene (mCP); 1,1-bis[(di-4-methylphenylamino)phenyl]cyclohexane (TAPC); N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl)biphenyl]-4,4'-diamine (ETPD); tetrakis-(3-methylphenyl)-N,N, N',N'-2,5-phenylenediamine (PDA); α-phenyl-4-N,N-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehyde diphenylhydrazone (DEH); triphenylamine (TPA); bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP); 1-phenyl-3-[p-(diethylamino)phenylphenyl]-5-[p-(diphenylamino)phenyl]-

[0013] Common hole transport polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophene), polyaniline, and polypyrrole. It is also possible to obtain hole transport polymers by incorporating hole transport molecules such as those described above into polymers such as polystyrene and polycarbonate. In some cases, triarylamine polymers are used, especially triarylamine-fluorene copolymers. In some cases, the polymers and copolymers are crosslinkable. Examples of crosslinkable hole transport polymers can be found, for example, in published US patent application 2005-0184287 and published PCT application WO2005 / 052027. In some embodiments, the hole transport layer is doped with a p-type dopant, such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10-tetracarboxy-3,4,9,10-dianhydride.

[0622] Depending on the application of the device, the photoactive layer 120 can be a light-emitting layer that is activated by an applied voltage (such as in a light-emitting diode or a light-emitting electrochemical cell), a material layer that absorbs light and emits light with a longer wavelength (such as in a down-converting phosphor device), or a material layer that responds to radiant energy and generates a signal with or without an applied bias (such as in a photodetector or photovoltaic device).

[0623] In some embodiments, the photoactive layer comprises a compound comprising an emissive compound as a photoactive material. In some embodiments, the photoactive layer further comprises a host material. Examples of host materials include, but are not limited to Phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, carbazole, indolocarbazole, furan, benzofuran, dibenzofuran, benzodifuran and metal quinolate complexes. In some embodiments, the host material is deuterated.

[0624] In some embodiments, the photoactive layer comprises (a) an electroluminescent dopant capable of having an emission maximum between 380 and 750 nm, (b) a first host compound, and (c) a second host compound. Suitable second host compounds are described above.

[0625] In some embodiments, the photoactive layer includes only (a) a dopant capable of electroluminescence having an emission maximum between 380 and 750 nm, (b) a first host compound, and (c) a second host compound, wherein there are no additional materials present that would substantially change the operating principle or distinguishing characteristics of the layer.

[0626] In some embodiments, the first host is present at a higher concentration based on weight in the photoactive layer than the second host.

[0627] In some embodiments, the weight ratio of the first host to the second host in the photoactive layer is 10: 1 to 1: 10. In some embodiments, the weight ratio is 6: 1 to 1: 6; in some embodiments, 5: 1 to 1: 2; in some embodiments, 3: 1 to 1: 1.

[0628] In some embodiments, the weight ratio of dopant to total host is 1:99 to 20:80; in some embodiments, 5:95 to 15:85.

[0629] In some embodiments, the photoactive layer includes (a) a red-light-emitting dopant, (b) a first host compound, and (c) a second host compound.

[0630] In some embodiments, the photoactive layer includes (a) a green light-emitting dopant, (b) a first host compound, and (c) a second host compound.

[0631] In some embodiments, the photoactive layer includes (a) a yellow light-emitting dopant, (b) a first host compound, and (c) a second host compound.

[0632] The optional layer may simultaneously function to facilitate electron transport and also act as a confinement layer to prevent exciton quenching at the layer interface. Preferably, the layer facilitates electron mobility and reduces exciton quenching.

[0633] In some embodiments, such layers include other electron transport materials. Examples of electron transport materials that can be used in the optional electron transport layer include metal chelated oxinoid compounds, including metal quinolate derivatives such as tris (8-hydroxyquinolinate) aluminum (AlQ), bis (2-methyl-8-hydroxyquinolinate) (p-phenylphenolate) aluminum (BAlq), tetrakis (8-hydroxyquinolinate) hafnium (HfQ) and tetrakis (8-hydroxyquinolinate) zirconium (ZrQ); and azole compounds such as 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (PBD), 3-(4-biphenyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (TAZ) and 1,3,5-tris(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivatives such as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthroline such as 4,7-diphenyl-1,10-phenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); triazine; fullerene; and mixtures thereof. In some embodiments, the electron transport material is selected from the group consisting of metal quinolate and phenanthroline derivatives. In some embodiments, the electron transport layer further comprises an n-type dopant. N-type dopant materials are well known. N-type dopants include, but are not limited to, Group 1 and Group 2 metals; Group 1 and Group 2 metal salts such as LiF, CsF, and Cs2CO3; Group 1 and Group 2 metal organic compounds such as lithium quinolate; and molecular n-type dopants such as leuco dyes, metal complexes such as W2(hpp)4 (wherein hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido-[1,2-a]-pyrimidine) and cobaltocene, tetrathia tetracene, bis(ethylenedithio)tetrathiafulvalene, heterocyclic groups or divalent groups, and dimers, oligomers, polymers, dispiro compounds, and polycyclic compounds of heterocyclic groups or divalent groups.

[0634] An optional electron injection layer may be deposited over the electron transport layer. Examples of electron injection materials include, but are not limited to, organometallic compounds containing Li, LiF, Li2O, lithium quinolate; organometallic compounds containing Cs, CsF, Cs2O, and Cs2CO3. This layer may react with the underlying electron transport layer, the overlying cathode, or both. When an electron injection layer is present, the amount of material deposited is typically In some embodiments

[0635] The cathode 130 is an electrode that is particularly effective for injecting electrons or negative charge carriers. The cathode can be any metal or nonmetal having a work function lower than that of the anode. The material for the cathode can be selected from the alkali metals of Group 1 (e.g., Li, Cs), Group 2 (alkaline earth) metals, Group 12 metals, including rare earth elements and lanthanides, and actinides. Materials such as aluminum, indium, calcium, barium, samarium, and magnesium, and combinations thereof, can be used.

[0636] It is known to have other layers in organic electronic devices. For example, multiple layers (not shown) may be present between the anode 110 and the hole injection layer (not shown) to control the amount of positive charge injected and / or provide band gap matching of the layers, or to serve as a protective layer. Layers known in the art, such as ultra-thin layers of copper phthalocyanine, silicon oxynitride, fluorocarbons, silanes, or metals (such as Pt) may be used. Alternatively, some or all of the anode layer 110, active layer 120, or cathode layer 130 may be surface treated to increase the charge carrier transport efficiency. The choice of materials for each component layer is preferably determined by balancing the positive and negative charges in the emitter layer to provide a device with high electroluminescent efficiency.

[0637] It should be understood that each functional layer may be composed of more than one layer.

[0638] The device layer can generally be formed by any deposition technique or combination of techniques, including vapor deposition, liquid deposition and thermal transfer. Substrates such as glass, plastic and metal can be used. Conventional vapor deposition techniques such as thermal evaporation, chemical vapor deposition, etc. can be used. The organic layer can be applied from a solution or dispersion in a suitable solvent using conventional coating or printing techniques, including but not limited to coating, dip coating, roll-to-roll technology, inkjet printing, continuous nozzle printing, screen printing, gravure printing, etc.

[0639] For liquid deposition methods, one skilled in the art can readily determine the appropriate solvent for a particular compound or related class of compounds. For some applications, it is desirable that these compounds be dissolved in a non-aqueous solvent. Such non-aqueous solvents can be relatively polar, such as C1 to C 20 Alcohols, ethers and acid esters, or can be relatively non-polar, such as C1 to C 12Alkanes or aromatic compounds such as toluene, xylene, trifluorotoluene, etc. Other suitable liquids for making liquid compositions (as solutions or dispersions as described herein) comprising the novel compounds include, but are not limited to, chlorinated hydrocarbons (such as dichloromethane, chloroform, chlorobenzene), aromatic hydrocarbons (such as substituted and unsubstituted toluene and xylene, including trifluorotoluene), polar solvents (such as tetrahydrofuran (THP), N-methylpyrrolidone), esters (such as ethyl acetate), alcohols (isopropanol), ketones (cyclopentanone), and mixtures thereof. Suitable solvents for electroluminescent materials have been described, for example, in published PCT application WO2007 / 145979.

[0640] In some embodiments, the device is made by liquid depositing a hole injection layer, a hole transport layer, and a photoactive layer, and by vapor depositing an anode, an electron transport layer, an electron injection layer, and a cathode onto a flexible substrate.

[0641] It should be understood that the efficiency of the device can be improved by optimizing other layers in the device. For example, more efficient cathodes such as Ca, Ba or LiF can be used. Shaped substrates and novel hole transport materials that result in reduced operating voltage or increased quantum efficiency are also applicable. Additional layers can also be added to customize the energy levels of the various layers and promote electroluminescence.

[0642] In some embodiments, the device has the following structures in order: substrate, anode, hole injection layer, hole transport layer, photoactive layer, electron transport layer, electron injection layer, cathode.

[0643] Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. In addition, materials, methods and examples are only illustrative and are not intended to be limiting. All disclosures, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety.

[0644] Examples

[0645] The concepts described herein will be further illustrated in the following examples, which do not limit the scope of the invention described in the claims.

[0646] Example 1

[0647] This example illustrates the synthesis of a compound having Formula I (Compound 6).

[0648] (a)

[0649]

[0650] In a 200mL round-bottom flask equipped with a magnetic stirrer and a condenser attached to a nitrogen line, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirodi[indene]-6,6'-diylbis(trifluoromethanesulfonate) (2.00g, 3.49mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (2.66g, 10.49mmol) and potassium acetate (1.37g, 13.97mmol) are added to anhydrous dioxane (40mL). The mixture is bubbled with nitrogen for 20min. Then, Pd(dppf)2Cl2 (0.285g, 0.35mmol) is added, and bubbled for another 10min. The mixture is stirred and heated at 70°C under nitrogen for 9 hours. TLC analysis (DCM / hexane, 1 / 3) shows that all starting trifluoromethanesulfonates have been consumed.Mixture is cooled to room temperature, and is concentrated to dryness.Add DCM (100mL) and water (100mL), and extract mixture with additional DCM (100mL x 2).Organic layers are merged, through Na2SO4 dry and filter to remove insoluble material and color by Florisil.Solution is concentrated to dryness and gained solid is stirred in hexane for 10min and filtered at about 45 ℃, to obtain 2,2 '-(3,3,3 ',3 '-tetramethyl-2,2 ',3,3 '-tetrahydrochysene-1,1 '-spirodi[indene]-6,6 '-diyl) bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (1.26g, 68% yield) in white solid.NMR analysis shows that material is consistent with structure.

[0651] (b)

[0652]

[0653] In a 500 mL three-necked round bottom flask equipped with a magnetic stirrer and a condenser attached to a nitrogen line, 2,2'-(3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (10.0 g, 18.9 mmol), N-Boc 4 bromo-2-fluoroaniline (13.67 g, 47.3 mmol, Boc = butoxycarbonyl), and cesium carbonate (18.5 g, 56.8 mmol) were added to a mixture of dimethoxyethane (250 mL), ethanol (125 mL), and water (40 mL). The mixture was bubbled with nitrogen while the system was under a continuous nitrogen flow for 20 min. The product of 4-nitro-1-yl pyridine-2 ... The sample was dry loaded onto a 330 g silica gel column (hexane: DCM 0%-50%), the fractions were detected by TLC and UPLC, the fractions were concentrated and the hexane slurry was filtered to give di-tert-butyl ((3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diyl)bis(2-fluoro-4,1-phenylene))dicarbamate (7.95 g, 60% yield). NMR analysis indicated that the material was consistent with the structure.

[0654] (c)

[0655]

[0656] In a 250 mL RBF, di-tert-butyl ((3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diyl)bis(2-fluoro-4,1-phenylene))dicarbamate (7.95 g, 11.44 mmol) was dissolved in CH2Cl2 (90 mL). Trifluoroacetic acid (8.76 mL) was added and stirred overnight under nitrogen. After 17 hours, UPLC showed the desired m / z and retention time changes. The mixture was washed with saturated sodium bicarbonate solution until the pH was slightly alkaline (pH about 8). The organic layer was dried over Na2SO4, filtered, and concentrated. Acetonitrile was added to produce a slurry, filtered, and the solid was dried in vacuo. Compound 6 was an off-white solid (3.71 g, 65% yield), and NMR was consistent with the desired product. It was used as is in the polymerization.

[0657] Example 2

[0658] This example illustrates the preparation of a polyamic acid having formula II. The polyamic acid has the following composition:

[0659] BPDA / PMDA / 6FDA / / TFMB / Compound 6 70 / 10 / 20 / / 75 / 25

[0660] In the 250mL reaction flask equipped with nitrogen inlet and outlet, mechanical stirrer and thermocouple, 7.21gTFMB (0.0225 mole), 3.71g compound 6 (0.0075 mole) and 84.2g 1-methyl-2-pyrrolidone (NMP) are packed into.Mixture is stirred about 30 minutes at room temperature under nitrogen.Afterwards, 6.18g BPDA (0.021 mole) is slowly added in batches to the stirring solution of diamines, and 0.46g PMDA (0.0021 mole) and 2.67g 6FDA (0.006mol) are added in batches subsequently.Control the adding rate of dianhydride, to keep the maximum reaction temperature<30 ℃.After dianhydride adds and completes, and use the NMP of additional 9.35g to wash any remaining dianhydride powder from the wall of container and reaction flask.And gained mixture is stirred 8 days. Separately, prepare 5% solution of PMDA in NMP, and add with a small amount (about 0.650g) to increase the molecular weight of polymer and the viscosity of polymer solution over time.Use Brookfield cone and plate viscometer to monitor solution viscosity by taking out a small sample from reaction flask for testing.Add a total of 3.58g of this final solution (0.182g, 0.000825 mole of PMDA).React overnight at room temperature to allow polymer balance under gentle stirring.The final viscosity of polymer solution is 13,210cps at 25°C.

[0661] Example 3

[0662] This example illustrates the preparation of a polyimide membrane, wherein the polyimide has Formula IV.

[0663] The polyamic acid solution from Example 2 was filtered through a microfilter, spin-coated onto a clean silicon wafer, soft-baked on a hot plate at 90°C, and placed in an oven. The oven was purged with nitrogen and heated in stages to a maximum curing temperature of 375°C. The wafer was removed from the oven, soaked in water and manually layered to produce a polyimide film sample. The properties of the film are given below:

[0664]

[0665] It should be noted that not all of the activities described above in the general description or examples are required, that a portion of a specific activity may not be required, and that one or more other activities may be performed in addition to those described. Furthermore, the order in which the activities are listed is not necessarily the order in which they are performed.

[0666] In the foregoing description, the concepts have been described with reference to specific embodiments. However, it will be appreciated by those skilled in the art that various modifications and changes may be made without departing from the scope of the invention as set forth in the following claims. Therefore, the description and drawings should be regarded as illustrative rather than restrictive, and all such modifications are intended to be included within the scope of the invention.

[0667] Benefits, other advantages, and solutions to problems have been described above with respect to specific embodiments. However, benefits, advantages, solutions to problems, and any one or more features that may cause any benefit, advantage, or solution to occur or make it more obvious are not to be construed as key, necessary, or essential features of any or all claims.

[0668] It is to be understood that, for the sake of clarity, some features described herein in the context of a separate embodiment may also be provided in a single embodiment in combination. On the contrary, for the sake of brevity, each feature described in the context of a single embodiment may also be provided individually or in any sub-combination. The use of numerical values ​​in each range specified herein is expressed as approximations, just as the minimum and maximum values ​​in the range are both preceded by the word "about". In this way, slight changes above and below the range may be used to achieve results substantially the same as the values ​​in these ranges. Moreover, the disclosure of these ranges is intended to be a continuous range of each value included between the minimum and maximum mean values, including fractional values ​​that can be generated when some components of a value are mixed with components of different values. In addition, when disclosing wider and narrower ranges, within the expectations of the present invention, the minimum value from one range is matched with the maximum value from another range, and vice versa.

Claims

1. A diamine having formula I in: Q is the formula Q1 in: R 1 -R 4 are the same or different and are selected from the group consisting of: H and alkyl; R 5 and R 6 are the same or different at each occurrence and are selected from the group consisting of: alkyl; a and b are the same or different and are integers from 0 to 3; and * indicates attachment point; R 7 and R 8 It is F; c and d are the same or different at each occurrence and are an integer of 1, 2, 3 or 4; and m and q are each an integer 1.

2. A polyamic acid having a repeating unit of formula II in: R a is the same or different at each occurrence and represents one or more tetracarboxylic acid component residues; and R b is the same or different at each occurrence and represents one or more aromatic diamine residues; 10-100 mol% of R b From one or more The residue of a diamine having formula I according to claim 1.

3. A liquid composition comprising (a) the polyamic acid according to claim 2, and (b) a high boiling point aprotic solvent.

4. A polyimide having a repeating unit structure of formula IV in R a is the same or different at each occurrence and represents one or more tetracarboxylic acid component residues; and R b is the same or different at each occurrence and represents one or more aromatic diamine residues; 10-100 mol% of R b is a diamine residue from one or more diamines of formula I according to claim 1.

5. A method for preparing a polyimide film according to claim 4, the method comprising the following steps in sequence: applying a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components in a high boiling point aprotic solvent to a substrate; soft baking the coated substrate; The soft-baked coated substrate is treated at a plurality of pre-selected temperatures at a plurality of pre-selected time intervals.

6. A flexible replacement for glass in electronic devices, wherein the flexible replacement for glass comprises a film of the polyimide having Formula IV according to claim 4.

7. An electronic device comprising the flexible glass substitute according to claim 6.

8. The electronic device according to claim 7, wherein: The flexible alternative to glass is used in a device component selected from the group consisting of: a device substrate, a substrate for a color filter, a cover film, and a touch screen panel.

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