TW202035366A - Polymers for use in electronic devices - Google Patents

Abstract

Disclosed is a polyamine having Formula I. In Formula I: Q¹ is H, R¹ , or R⁹ ; Q² is of H, R² , or R⁹ ; Q³ is R³ or R⁹ ; Q⁴ is R⁴ or R⁹ ; Q⁵ is R⁷ or R⁹ ; R¹ and R² are the same or different at each occurrence and are F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, siloxy, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, or unsubstituted or substituted aryloxy; R³ , R⁴ , R⁵ , R⁶ , and R⁷ are the same or different and are H, F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, siloxy, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, or unsubstituted or substituted aryloxy; R⁸ is alkyl, silyl, unsubstituted or substituted hydrocarbon aryl, or unsubstituted or substituted heteroaryl; R⁹ is the same or different at each occurrence and is NH₂ or ArNH₂ ; Ar is the same or different at each occurrence and is an unsubstituted or substituted C_6-18 hydrocarbon aryl; and a and b are the same or different and are an integer from 0-3. In Formula I, at least two of Q¹ through Q⁵ are R⁹ .

Description

Polymers used in electronic devices

This disclosure is about novel polymeric compounds. The present disclosure further relates to methods for preparing such polymeric compounds and electronic devices having at least one layer containing such materials.

Materials used for 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 required properties require innovation in materials with new and/or improved properties. Polyimines represent a class of polymeric compounds widely used in various electronic applications. They can serve as flexible substitutes for glass in electronic display devices, provided they have suitable properties. These materials can be used as components of liquid crystal displays ("LCD"), where their moderate electrical power consumption, light weight, and layer flatness are key characteristics for practical utility. Other uses in electronic display devices that preferentially set such parameters include device substrates, color filter substrates, cover films, touch screen panels, and so on.

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

Polyimide films generally have sufficient thermal stability, high glass transition temperature, and mechanical toughness to be worth considering for such applications. Moreover, when subjected to repeated deflection, polyimide usually does not produce haze, so compared to other transparent substrates such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN ), they are often preferred in flexible display applications.

Polyimide is generally a hard, highly aromatic material; 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 direction and the vertical direction of the film, resulting in optical retardation that may adversely affect display performance. New monomers with novel structural characteristics may lead to polyimides with improved properties for specific applications.

There is a continuing need for polymer materials suitable for electronic devices.

， 其中： Q¹ 選自由H、R¹ 、以及R⁹ 組成之群組； Q² 選自由H、R² 、以及R⁹ 組成之群組； Q³ 選自由R³ 以及R⁹ 組成之群組； Q⁴ 選自由R⁴ 以及R⁹ 組成之群組； Q⁵ 選自由R⁷ 以及R⁹ 組成之群組； R¹ 和R² 在每次出現時是相同或不同的，並且選自由以下各項組成之群組：F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、矽烷氧基、未取代或取代的烴芳基、未取代或取代的雜芳基、以及未取代或取代的芳氧基； R³ 、R⁴ 、R⁵ 、R⁶ 、以及R⁷ 係相同或不同的，並且選自由以下各項組成之群組：H、F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、矽烷氧基、未取代或取代的烴芳基、未取代或取代的雜芳基、以及未取代或取代的芳氧基； R⁸ 選自由以下各項組成之群組：烷基、矽基、未取代或取代的烴芳基、以及未取代或取代的雜芳基； R⁹ 在每次出現時是相同或不同的，並且選自由NH₂ 以及ArNH₂ 組成之群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C_6-18 烴芳基；以及 a和b是相同或不同的並且是從0~3的整數； 其前提係Q¹ 至Q⁵ 中的至少兩個係R⁹ 。A polyamine of formula I is provided:

, Where: Q ^{1 is} selected from the group consisting of H, R ¹ , and R ⁹ ; Q ^{2 is} selected from the group consisting of H, R ² , and R ⁹ ; Q ^{3 is} selected from the group consisting of R ³ and R ⁹ ; Q ^{4 is} selected from the group consisting of R ⁴ and R ⁹ ; Q ^{5 is} selected from the group consisting of R ⁷ and R ⁹ ; R ¹ and R ² are the same or different each time, and are selected from the following Item composition group: F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, silalkoxy, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl , And unsubstituted or substituted aryloxy; R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same or different, and are selected from the group consisting of: H, F, CN, alkane Group, fluoroalkyl group, alkoxy group, fluoroalkoxy group, silyl group, silalkoxy group, unsubstituted or substituted hydrocarbon aryl group, unsubstituted or substituted heteroaryl group, and unsubstituted or substituted aryloxy group; R ^{8 is} selected from the group consisting of: alkyl, silyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl; R ⁹ is the same or different in each occurrence, And is selected from the group consisting of NH ₂ and ArNH ₂ ; Ar is the same or different each time, and is an unsubstituted or substituted C _6-18 hydrocarbon aryl group; and a and b are the same or different, and It is an integer from 0 to 3; the premise is that at least two of Q ¹ to Q ⁵ are R ⁹ .

， 其中： R^a 在每次出現時是相同或不同的，並且表示一個或多個四羧酸組分殘基；以及 R^b 在每次出現時是相同或不同的，並且表示一個或多個芳香族二胺殘基； 其中10~100 mol%的R^b 係來自一種或多種具有式I之二胺的二胺殘基。Further provided is a polyamide acid having a repeating unit of formula II:

, Where: 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; wherein 10-100 mol% of R ^b is derived from one or more diamine residues with diamines of formula I.

Further provided is a composition comprising (a) a polyamide acid having a repeating unit of formula II and (b) a high-boiling aprotic solvent.

， 其中R^a 和R^b 如式II中所定義。Further provided is a polyimide, the repeating unit of which has the structure in formula III:

, Where R ^a and R ^b are as defined in formula II.

Further provided is a polyimide film, which comprises a polyimide having a repeating unit of formula III.

Further provided are one or more methods for preparing a polyimide film, wherein the polyimide has a repeating unit of formula III.

There is further provided a flexible substitute for glass in an electronic device, wherein the flexible substitute for glass is a polyimide film containing polyimide having a repeating unit of formula III.

There is further provided an electronic device having at least one layer, the at least one layer comprising a polyimide film, the polyimide film comprising a polyimide having a repeating unit of formula III.

There is further provided an organic electronic device, such as an OLED, wherein the organic electronic device contains a flexible substitute for glass as disclosed herein.

The foregoing general description and the following detailed description are only exemplary and illustrative, and do not limit the present invention as defined by the scope of the appended application.

A polyamine of formula I as described in detail below is provided.

Further provided is a polyamide acid having a repeating unit of formula II as described in detail below.

Further provided is a composition comprising (a) a polyamide acid having a repeating unit of formula II and (b) a high-boiling aprotic solvent.

There is further provided a polyimine as described in detail below, the repeating unit of the polyimine having the structure in formula III.

Further provided are one or more methods for preparing a polyimide film, wherein the polyimide has a repeating unit of formula III.

There is further provided a flexible substitute for glass in an electronic device, wherein the flexible substitute for glass is a polyimide film containing polyimide having a repeating unit of formula III.

There is further provided an electronic device having at least one layer, the at least one layer comprising a polyimide film, the polyimide film comprising a polyimide having a repeating unit of formula III.

There is further provided an organic electronic device, such as an OLED, wherein the organic electronic device contains a flexible substitute for glass as disclosed herein.

Many aspects and embodiments have been described above and are only exemplary and non-limiting. After reading this specification, skilled technicians should understand that other aspects and embodiments are possible without departing from the scope of the present invention.

From the following detailed description and from the scope of the patent application, other features and benefits of any one or more embodiments will be apparent. The detailed description first proposes definitions and clarifications of terms, followed by polyamines of formula I, polyamide acid, polyimine, methods for preparing polyimide films, electronic devices, and finally examples.

1. Definition and clarification of terms

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

As in "Definitions and Clarification of Terms" ^{used, R, R a, R b} , R ', R'' and any other system variables common name, and may be defined as those of formula in the same or different.

The term "alignment layer" is intended to refer to the organic polymer layer in a liquid crystal device (LCD), which is the result of rubbing against the LCD glass in a preferred direction during the LCD manufacturing process to bring the molecules closest to each other. The boards are aligned.

As used herein, the term "alkyl" includes branched and straight chain saturated aliphatic hydrocarbon groups. Unless otherwise indicated, the term is also intended to include cyclic groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl , Cyclohexyl, isohexyl, etc. The term "alkyl" further includes both substituted and unsubstituted hydrocarbyl groups. In some embodiments, alkyl groups 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. Heteroalkyl groups can have from 1-20 carbon atoms.

The term "aprotic" refers to a type of solvent that lacks acidic hydrogen atoms and therefore cannot act as a hydrogen donor. Common aprotic solvents include alkanes, carbon tetrachloride (CCl4), benzene, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) )Wait.

The term "aromatic compound" is intended to mean an organic compound containing at least one unsaturated cyclic group with 4n+2 unlocalized π electrons. The term is intended to cover both aromatic compounds and heteroaromatic compounds, the aromatic compound having only carbon and hydrogen atoms, one or more of the carbon atoms in the cyclic group in the heteroaromatic compound has been replaced by another Replacement of atoms such as nitrogen, oxygen, sulfur, etc.

The term "aryl" or "aryl group" refers to the moiety formed by removing one or more hydrogen ("H") or deuterium ("D") from an aromatic compound. The aryl group can be a single ring (monocyclic) or have multiple rings (bicyclic, or more) fused together or covalently connected. The "hydrocarbon aryl group" 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, the hydrocarbon aryl group has 6 to 60 ring carbon atoms; in some embodiments, 6 to 30 ring carbon atoms. In some embodiments, the heteroaryl group has from 4 to 50 ring carbon atoms; in some embodiments, 4 to 30 ring carbon atoms.

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

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

Unless otherwise indicated, all groups may be substituted or unsubstituted. Optionally substituted groups, such as but not limited to alkyl or aryl groups, 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, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy Group, aryloxy group, heteroaryloxy group, alkoxycarbonyl group, perfluoroalkyl group, perfluoroalkoxy group, arylalkyl group, silyl group, silalkoxy group, siloxane, thioalkoxy group,- S(O) ₂ -, -C(=O)-N(R')(R”), (R')(R”)N-alkyl, (R')(R”)N-alkoxy Alkyl, (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 bound, may form a ring system in certain embodiments. The substituent may also be a crosslinking group.

。The term "amine" is intended to refer to compounds containing a basic nitrogen atom with a lone pair of electrons, where the lone pair of electrons refers to a set of two valence electrons that are not shared with another atom. The term "amino group" refers to the functional group -NH ₂ , -NHR or -NR ₂ , where 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 an associated lone pair of electrons. The term "polyamine" is intended to refer to compounds containing two or more basic nitrogen atoms with associated lone pairs of electrons. The term "aromatic diamine" is intended to mean an aromatic compound having two amine groups. The term "aromatic polyamine" is intended to refer to aromatic compounds having two or more amine groups. The term "bent diamine" is intended to refer to diamines in which two basic nitrogen atoms and an associated lone pair of electrons are arranged asymmetrically around the center of symmetry of the corresponding compound or functional group, such as isobenzene Diamine:

.

The term "aromatic diamine residue" is intended to mean a moiety that is bonded to two amine groups in an aromatic diamine. The term "aromatic polyamine residue" is intended to mean a moiety bonded to two or more amine groups in the aromatic polyamine. The term "aromatic diisocyanate residue" is intended to mean a moiety bonded to two isocyanate groups in the aromatic diisocyanate compound. The term "aromatic polyisocyanate residue" is intended to mean a moiety bonded to two or more isocyanate groups in the aromatic polyisocyanate compound. This is explained further below.

The terms "diamine residue" and "diisocyanate residue" are intended to refer to the moiety bonded to two amine groups or two isocyanate groups, respectively, where the moiety is aliphatic or aromatic. The terms "polyamine residue" and "polyisocyanate residue" are intended to refer to the moiety bonded to two or more amine groups or two or more isocyanate groups, respectively, wherein the moiety is aliphatic or Aromatic.

The term "b*" is intended to refer to the b* axis representing the opposite color of yellow/blue in the CIELab color space. Yellow is represented by a positive b* value, and blue is represented by a negative b* value. The measured b* value may be affected by the solvent, especially because the choice of solvent can affect the color measured on materials exposed to high temperature processing conditions. This can occur as a result of the inherent properties of the solvent and/or the properties associated with the low levels of impurities contained in various solvents. Usually a specific solvent is selected in advance to achieve the b* value desired for a specific application.

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

When referring to a layer, material, member, or structure, the term "charge transport" is intended to mean that such layer, material, member, or structure promotes such charge to pass through such layer, material with relative efficiency and small charge loss , Component, or structure thickness migration. Hole transport materials are good for positive charges; electron transport materials are good for negative charges. Although the luminescent material may also have some charge transport properties, the term "charge transport layer, material, member, or structure" is not intended to include a layer, material, member, or structure whose main function is to emit light.

The term "compound" is intended to refer to an uncharged substance composed of molecules, which further includes atoms, where atoms cannot be separated from their corresponding molecules by physical means that do not break chemical bonds. The term is intended to include oligomers and polymers.

The term "coefficient of linear thermal expansion (CTE or α)" is intended to refer to a parameter that defines the amount of expansion or contraction of a material 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. α = (ΔL/L ₀ )/ΔT

The measured CTE value disclosed herein is generated by known methods during the first or second heating scan. An understanding of the relative expansion/contraction characteristics of materials can be an important consideration for the manufacturing and/or reliability of electronic devices.

The term "dopant" is intended to refer to the material in the layer that includes the host material, and one or more electronic characteristics or one or more wavelengths of the radiation emission, reception, or filtering of the layer in the absence of such material In contrast, the material changes one or more electronic properties or one or more target wavelengths of radiation emission, reception, or filtering of the layer.

When referring to a layer or material, the term "electroactive" is intended to mean a layer or material that electronically promotes the operation of the device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block charge, where the charge may be electrons or holes, or materials that emit radiation when receiving radiation or exhibit electron-hole pair concentration changes. Examples of inactive materials include, but are not limited to, planarization materials, insulating materials, and environmental barrier materials.

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 by, for example, ASTM method D882.

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

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 amorphous region of a semi-crystalline polymer, where the material suddenly changes from a hard, glassy or brittle state Become a flexible or elastic state. Under the microscope, the glass transition occurs when stationary polymer chains that are normally wound become free to rotate and can move past each other. Differential scanning calorimetry (DSC), thermomechanical analysis (TMA), or dynamic mechanical analysis (DMA) or other methods can be used to measure T _g .

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

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

The term "host material" is intended to refer to materials to which dopants are 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 higher concentration.

The term "isothermal weight loss" is intended to refer to material properties directly related to its thermal stability. It is usually measured at a constant target temperature via thermogravimetric analysis (TGA). Materials with high thermal stability generally exhibit a very low isothermal weight loss percentage within a desired period of time at the required use or processing temperature, and can therefore be used for applications at these temperatures without significant strength loss , Degassing and/or structural changes.

The term "laser particle counter test" refers to a method used to evaluate the particle content of polyamide and other polymer solutions, whereby a representative sample of the test solution is spin-coated on a 5" silicon wafer and soft-baked /Drying. 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.

The term "liquid composition" is intended to mean 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.

The term "substrate" is intended to refer to the foundation on which one or more layers are deposited in the formation of, for example, electronic devices. Non-limiting examples include glass, silicon, and the like.

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

The term "optical retardation (or R _TH )" is intended to refer to the difference between the average in-plane refractive index and the out-of-plane refractive index (ie, birefringence), and then this difference is multiplied by the thickness of the film or coating . The optical delay is typically measured for light of a given frequency and reported in nanometers.

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.

The term "particle content" is intended to refer to the number or count of insoluble particles present in the solution. The particle content measurement 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 evaluate this characteristic.

The term "photoactive" refers to the emission of light when activated by an applied voltage (as in light-emitting diodes or chemical cells), the emission of light after absorbing photons (as in down-conversion phosphor devices), Or a material or layer that responds to radiant energy and generates a signal (as in a photodetector or photovoltaic cell) with or without an applied bias.

The term "polyamide acid solution" refers to a solution of a polymer containing amide acid units that have intramolecular cyclization ability to form amide groups.

The term "polybasic acid anhydride" refers to a compound having two or more acid anhydride groups. The term "polybasic acid anhydride residue" is intended to mean a moiety that is bonded to two or more acid anhydride groups. This is explained further below.

The term "polyimine" refers to a condensation polymer obtained by reacting one or more polyfunctional carboxylic acid components with one or more primary polyamines or polyisocyanates. They contain the imine structure -CO-NR-CO- as linear or heterocyclic units along the main chain of the polymer backbone.

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

The term "soft bake" is intended to refer to a process commonly used in electronics manufacturing in which the coated material is heated to drive off the solvent and cure the film. The soft baking is usually carried out at a temperature between 90°C and 110°C on a hot plate or in an exhaust oven as a preparation step for the subsequent heat treatment of the coated layer or film.

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, such materials may include, but are not limited to, glass, polymer, metal, or ceramic materials, or combinations thereof. The substrate may or may not include electronic components, circuits, or conductive members.

The term "siloxane" refers to the group R ₃ SiOR ₂ Si-, where R is the same or different at each occurrence and is H, C _1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced by Si.

The term "silanoxy" refers to the group R ₃ SiO-, where R is the same or different at each occurrence and is H, C _1-20 alkyl, fluoroalkyl, or aryl.

The term "silyl" refers to the group R ₃ Si-, where R is the same or different at each occurrence and is H, C _1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced by Si.

The term "spin coating" is intended to refer to a process used to deposit a uniform thin film on a flat substrate. Generally, a small amount of coating material is applied on the center of the substrate, and the substrate is rotated at a low speed or not at all. The substrate is then rotated at a prescribed speed in order to spread the coating material uniformly by centrifugal force.

The term "spiro group" refers to a group having a bicyclic organic moiety in which the two rings have a common atom. The rings can be different or the same in nature, and can form part of other ring systems. The shared atom has two bonds in each ring and is called a spiro atom. In some embodiments, the spiro atom is selected from the group consisting of C and Si.

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

The term "tetracarboxylic acid component" is intended to refer to any one or more of the following: tetracarboxylic acid, tetracarboxylic acid monoanhydride, tetracarboxylic dianhydride, tetracarboxylic acid monoester, and tetracarboxylic acid diester.

The term "tetracarboxylic acid component residue" is intended to mean the moiety bonded to the four carboxyl groups in the tetracarboxylic acid component. This is explained further below.

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

， 這意味著取代基R可在一個或多個環上的任何可用位置處鍵合。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 look bluish. Especially for polymerization and/or curing processes that operate 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 the low levels of impurities contained in various solvents. Usually a specific solvent is selected in advance to achieve the desired YI value for a specific application. In a structure where the substituent bonds as shown below pass through one or more rings:

This means that the substituent R can be bonded at any available position on one or more rings.

。When used to refer to layers in a device, the phrase "adjacent" does not necessarily mean that one layer is next to another. On the other hand, the phrase "adjacent R groups" is used to refer to the R groups in the chemical formula that are next to each other (ie, the R groups on the atoms bonded by a bond). Exemplary adjacent R groups are shown below:

.

In this specification, unless otherwise clearly indicated or otherwise indicated by the context of use, the embodiments of the subject matter of the present invention are stated or described as comprising (comprising), including (including), containing (containing), having certain features or When an element is composed of, or consists of, certain features or elements, one or more features or elements other than those explicitly stated or described may also be present in the embodiment. The disclosed alternative embodiments of the subject matter of the present invention are described as mainly composed of certain features or elements, wherein the features or elements of the embodiments that will substantially change the operating principle or the distinguishing features of the embodiments do not exist here. Another alternative embodiment of the described subject matter of the invention is described as being composed of certain features or elements, and in this embodiment or in its non-essential variants, only the features or elements specifically stated or described exist.

In addition, unless expressly stated to the contrary, "or" refers to an inclusive "or" rather than 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).

Moreover, the term "a/an" is used to describe the elements and components described herein. This is done for convenience and to give a general meaning to the scope of the invention. This description should be construed to include one or at least one, and the singular form also includes the plural form, unless it clearly indicates otherwise.

The group numbers corresponding to the columns in the periodic table use the "New Notation" convention as seen in the CRC Handbook of Chemistry and Physics , 81st edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those with ordinary knowledge in the technical field. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. Unless specific paragraphs are cited, all publications, patent applications, patents, and other references mentioned herein are incorporated herein in their entirety by reference. In case of conflict, the specification, including definitions, shall prevail. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

To the extent not described herein, many details about specific materials, processing behaviors, 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.

2. Polyamines of formula I

， 其中： Q¹ 選自由H、R¹ 、以及R⁹ 組成之群組； Q² 選自由H、R² 、以及R⁹ 組成之群組； Q³ 選自由R³ 以及R⁹ 組成之群組； Q⁴ 選自由R⁴ 以及R⁹ 組成之群組； Q⁵ 選自由R⁷ 以及R⁹ 組成之群組； R¹ 和R² 在每次出現時是相同或不同的，並且選自由以下各項組成之群組：F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、矽烷氧基、未取代或取代的烴芳基、未取代或取代的雜芳基、以及未取代或取代的芳氧基； R³ 、R⁴ 、R⁵ 、R⁶ 、以及R⁷ 係相同或不同的，並且選自由以下各項組成之群組：H、F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、矽烷氧基、未取代或取代的烴芳基、未取代或取代的雜芳基、以及未取代或取代的芳氧基； R⁸ 選自由以下各項組成之群組：烷基、矽基、未取代或取代的烴芳基、以及未取代或取代的雜芳基； R⁹ 在每次出現時是相同或不同的，並且選自由NH₂ 以及ArNH₂ 組成之群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C_6-18 烴芳基；以及 a和b是相同或不同的並且是從0~3的整數； 其前提係Q¹ 至Q⁵ 中的至少兩個係R⁹ 。The polyamines described herein have Formula I:

, Where: Q ^{1 is} selected from the group consisting of H, R ¹ , and R ⁹ ; Q ^{2 is} selected from the group consisting of H, R ² , and R ⁹ ; Q ^{3 is} selected from the group consisting of R ³ and R ⁹ ; Q ^{4 is} selected from the group consisting of R ⁴ and R ⁹ ; Q ^{5 is} selected from the group consisting of R ⁷ and R ⁹ ; R ¹ and R ² are the same or different each time, and are selected from the following Item composition group: F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, silalkoxy, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl , And unsubstituted or substituted aryloxy; R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same or different, and are selected from the group consisting of: H, F, CN, alkane Group, fluoroalkyl group, alkoxy group, fluoroalkoxy group, silyl group, silalkoxy group, unsubstituted or substituted hydrocarbon aryl group, unsubstituted or substituted heteroaryl group, and unsubstituted or substituted aryloxy group; R ^{8 is} selected from the group consisting of: alkyl, silyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl; R ⁹ is the same or different in each occurrence, And is selected from the group consisting of NH ₂ and ArNH ₂ ; Ar is the same or different each time, and is an unsubstituted or substituted C _6-18 hydrocarbon aryl group; and a and b are the same or different, and It is an integer from 0 to 3; the premise is that at least two of Q ¹ to Q ⁵ are R ⁹ .

In some embodiments of formula I, exactly two of Q ¹ to Q ⁵ are R ⁹ .

In some embodiments of Formula I, Q ¹ and Q ² are R ⁹ .

In some embodiments of Formula I, Q ³ and Q ⁴ are R ⁹ .

In some embodiments of Formula I, Q ¹ and Q ⁵ are R ⁹ .

In some embodiments of Formula I, Q ¹ is R ⁹ .

In some embodiments of Formula I, Q ¹ is H.

In some embodiments of Formula I, Q ¹ is F.

In some embodiments of Formula I, Q ¹ is CN.

In some embodiments of formula I, Q ¹ is a C _1-20 alkyl group; in some embodiments, it is a C _1-10 alkyl group.

In some embodiments of formula I, Q ¹ is a C _1-20 fluoroalkyl group; in some embodiments, it is a C _1-10 fluoroalkyl group.

In some embodiments of formula I, Q ¹ is a C _1-20 perfluoroalkyl group; in some embodiments, it is a C _1-10 perfluoroalkyl group.

In some embodiments of formula I, Q ¹ is a C _1-20 alkoxy; in some embodiments, it is a C _1-10 alkoxy.

In some embodiments of formula I, Q ¹ is a C _1-20 fluoroalkoxy; in some embodiments, it is a C _1-10 fluoroalkoxy.

In some embodiments of formula I, Q ¹ is a C _1-20 perfluoroalkoxy; in some embodiments, it is a C _1-10 perfluoroalkoxy.

In some embodiments of Formula I, Q ¹ is SiH ₃ .

In some embodiments of formula I, Q ¹ is C _1-12 silyl; in some embodiments, C _3-6 silyl.

In some embodiments of formula I, Q ¹ is a C _1-12 silyloxy group; in some embodiments, it is a C _3-6 silyloxy group.

In some embodiments of formula I, Q ¹ is an unsubstituted or substituted C _6-30 hydrocarbon aryl; in some embodiments, it is an unsubstituted or substituted C _6-18 hydrocarbon aryl; in some embodiments, it is Unsubstituted.

In some embodiments of formula I, Q ¹ is an unsubstituted or substituted C _3-30 heteroaryl; in some embodiments, it is an unsubstituted or substituted C _3-18 heteroaryl; in some embodiments, it is Unsubstituted.

In some embodiments of formula I, Q ¹ is an unsubstituted or substituted C _6-30 hydrocarbon aryloxy; in some embodiments, it is an unsubstituted or substituted C _6-18 hydrocarbon aryloxy; in some embodiments The middle line is not replaced.

In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, Alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and silalkoxy.

All the above-described embodiments of Q ¹ in formula I are equally applicable to Q ² , Q ³ , Q ⁴ , and Q ⁵ in formula I.

In some embodiments of Formula I, a=0.

In some embodiments of Formula I, a=1.

In some embodiments of Formula I, a=2.

In some embodiments of Formula I, a=3.

In some embodiments of Formula I, a>0.

In some embodiments of Formula I, a>0 and at least one R ¹ is F.

In some embodiments of Formula I, a>0 and at least one R ¹ is CN.

In some embodiments of formula I, a>0 and at least one R ¹ is a C _1-20 alkyl group; in some embodiments, it is a C _1-10 alkyl group.

In some embodiments of formula I, a>0 and at least one R ¹ is a C _1-20 fluoroalkyl group; in some embodiments, it is a C _1-10 fluoroalkyl group.

In some embodiments of formula I, a>0 and at least one R ¹ is a C _1-20 perfluoroalkyl group; in some embodiments, it is a C _1-10 perfluoroalkyl group.

In some embodiments of formula I, a>0 and at least one R ¹ is a C _1-20 alkoxy; in some embodiments, it is a C _1-10 alkoxy.

In some embodiments of formula I, a>0 and at least one R ¹ is a C _1-20 fluoroalkoxy; in some embodiments, it is a C _1-10 fluoroalkoxy.

In some embodiments of formula I, a>0 and at least one R ¹ is a C _1-20 perfluoroalkoxy; in some embodiments, it is a C _1-10 perfluoroalkoxy.

In some embodiments of Formula I, a>0 and at least one R ¹ is SiH ₃ .

In some embodiments of formula I, a>0 and at least one R ¹ is C _1-12 silyl; in some embodiments, C _3-6 silyl.

In some embodiments of formula I, a>0 and at least one R ¹ is a C _1-12 silyloxy group; in some embodiments, it is a C _3-6 silyloxy group.

In some embodiments of formula I, a>0 and at least one R ¹ is an unsubstituted or substituted C _6-30 hydrocarbon aryl group; in some embodiments, it is an unsubstituted or substituted C _6-18 hydrocarbon aryl group; In some embodiments it is unsubstituted.

In some embodiments of formula I, a>0 and at least one R ¹ is an unsubstituted or substituted C _3-30 heteroaryl group; in some embodiments, it is an unsubstituted or substituted C _3-18 heteroaryl group; In some embodiments it is unsubstituted.

In some embodiments of formula I, a>0 and at least one R ¹ is an unsubstituted or substituted C _6-30 hydrocarbon aryloxy; in some embodiments, it is an unsubstituted or substituted C _6-18 hydrocarbon aryloxy Group; in some embodiments unsubstituted.

In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, Alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and silalkoxy.

In some embodiments of Formula I, b=0.

In some embodiments of Formula I, b=1.

In some embodiments of Formula I, b=2.

In some embodiments of Formula I, b=3.

In some embodiments of Formula I, b>0.

In some embodiments of Formula I, b>0 and at least one R ² is F.

In some embodiments of Formula I, b>0 and at least one R ² is CN.

In some embodiments of formula I, b>0 and at least one R ² is a C _1-20 alkyl group; in some embodiments, it is a C _1-10 alkyl group.

In some embodiments of formula I, b>0 and at least one R ² is a C _1-20 fluoroalkyl group; in some embodiments, it is a C _1-10 fluoroalkyl group.

In some embodiments of formula I, b>0 and at least one R ² is a C _1-20 perfluoroalkyl group; in some embodiments, it is a C _1-10 perfluoroalkyl group.

In some embodiments of formula I, b>0 and at least one R ² is a C _1-20 alkoxy; in some embodiments, it is a C _1-10 alkoxy.

In some embodiments of formula I, b>0 and at least one R ² is C _1-20 fluoroalkoxy; in some embodiments, C _1-10 fluoroalkoxy.

In some embodiments of formula I, b>0 and at least one R ² is a C _1-20 perfluoroalkoxy; in some embodiments, it is a C _1-10 perfluoroalkoxy.

In some embodiments of Formula I, b>0 and at least one R ² is SiH ₃ .

In some embodiments of formula I, b>0 and at least one R ² is C _1-12 silyl; in some embodiments, C _3-6 silyl.

In some embodiments of formula I, b>0 and at least one R ² is a C _1-12 silanoxy group; in some embodiments, it is a C _3-6 silanoxy group.

In some embodiments of formula I, b>0 and at least one R ² is an unsubstituted or substituted C _6-30 hydrocarbon aryl group; in some embodiments, it is an unsubstituted or substituted C _6-18 hydrocarbon aryl group; In some embodiments it is unsubstituted.

In some embodiments of Formula I, b>0 and at least one R ² is an unsubstituted or substituted C _3-30 heteroaryl group; in some embodiments, it is an unsubstituted or substituted C _3-18 heteroaryl group; In some embodiments it is unsubstituted.

In some embodiments of formula I, b>0 and at least one R ² is an unsubstituted or substituted C _6-30 hydrocarbon aryloxy; in some embodiments, it is an unsubstituted or substituted C _6-18 hydrocarbon aryloxy Group; in some embodiments unsubstituted.

In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, Alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and silalkoxy.

In some embodiments of Formula I, R ⁵ = R ⁶ .

In some embodiments of Formula I, R ⁵ ≠ R ⁶ .

In some embodiments of Formula I, R ⁵ = R ⁶ =H.

In some embodiments of Formula I, R ⁵ is H.

In some embodiments of Formula I, R ⁵ is F.

In some embodiments of Formula I, R ⁵ is CN.

In some embodiments of Formula I, R ⁵ is C _1-20 alkyl; in some embodiments, C _1-10 alkyl.

In some embodiments of formula I, R ⁵ is C _1-20 fluoroalkyl; in some embodiments, C _1-10 fluoroalkyl.

In some embodiments of formula I, R ⁵ is a C _1-20 perfluoroalkyl group; in some embodiments, it is a C _1-10 perfluoroalkyl group.

In some embodiments of formula I, R ⁵ is C _1-20 alkoxy; in some embodiments, C _1-10 alkoxy.

In some embodiments of formula I, R ⁵ is C _1-20 fluoroalkoxy; in some embodiments, C _1-10 fluoroalkoxy.

In some embodiments of formula I, R ⁵ is C _1-20 perfluoroalkoxy; in some embodiments, C _1-10 perfluoroalkoxy.

In some embodiments of Formula I, R ⁵ is SiH ₃ .

In some embodiments of formula I, R ⁵ is C _1-12 silyl; in some embodiments, C _3-6 silyl.

In some embodiments of formula I, R ⁵ is a C _1-12 silyloxy group; in some embodiments, it is a C _3-6 silyloxy group.

In some embodiments of Formula I, R ⁵ is an unsubstituted or substituted C _6-30 hydrocarbon aryl group; in some embodiments, it is a C _6-18 hydrocarbon aryl group; in some embodiments, it is unsubstituted.

In some embodiments of Formula I, R ⁵ is an unsubstituted or substituted C _3-30 heteroaryl; in some embodiments, it is a C _3-18 heteroaryl; in some embodiments, it is unsubstituted.

In some embodiments of Formula I, R ⁵ is an unsubstituted or substituted C _6-30 hydrocarbon aryloxy group; in some embodiments, it is a C _6-18 hydrocarbon aryloxy group; in some embodiments, it is unsubstituted .

In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, Alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and silalkoxy.

All the above-described embodiments of R ⁵ in Formula I are equally applicable to R ⁶ in Formula I.

In some embodiments of formula I, R ⁸ is a C _1-20 alkyl group; in some embodiments, it is a C _1-10 alkyl group.

In some embodiments of formula I, R ⁸ is C _1-12 silyl; in some embodiments, C _3-6 silyl.

In some embodiments of Formula I, R ⁸ is an unsubstituted or substituted C _6-30 hydrocarbon aryl group; in some embodiments, it is a C _6-18 hydrocarbon aryl group; in some embodiments, it is unsubstituted.

In some embodiments of formula I, R ⁸ is an unsubstituted or substituted C _3-30 heteroaryl; in some embodiments, it is a C _3-18 heteroaryl; in some embodiments, it is unsubstituted.

In some embodiments, any of the above hydrocarbon aryl and heteroaryl groups is further substituted with one or more substituents selected from the group consisting of: F, CN, alkyl, fluoroalkane Group, alkoxy group, fluoroalkoxy group, silyl group, and silyloxy group.

In some embodiments of Formula I, two R ⁹ groups are present and are the same.

In some embodiments of Formula I, there are two R ⁹ groups and are different.

In some embodiments of Formula I, there are three R ⁹ groups and all are the same. In some embodiments, two or three of the R ⁹ groups are different.

In some embodiments of Formula I, there are four R ⁹ groups and all are the same. In some embodiments, two, three, or four of the R ⁹ groups are different.

In some embodiments of Formula I, there are five R ⁹ groups and all are the same. In some embodiments, two, three, four, or five of the R ⁹ groups are different.

In some embodiments of Formula I, at least one R ⁹ is NH ₂ .

In some embodiments of Formula I, at least one R ⁹ is ArNH ₂ .

， 其中： R¹⁰ 和R¹¹ 在每次出現時是相同或不同的，並且選自由以下各項組成之群組：F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基，其中相鄰的R¹⁰ 和/或R¹¹ 基團可以連接在一起以形成稠環； p和q是相同或不同的並且是從0~4的整數； s係從0~3的整數；並且 *表示附接點。In some embodiments of formula I, at least one R ⁹ is ArNH ₂ , where Ar has formula a:

, Where: R ¹⁰ and R ¹¹ are the same or different each time they appear, and are selected from the group consisting of: F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, Unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and silalkoxy, where adjacent R ¹⁰ and/or R ¹¹ groups can be connected Together to form a fused ring; p and q are the same or different and are an integer from 0 to 4; s is an integer from 0 to 3; and * represents the point of attachment.

In some embodiments of Formula I, Ar is selected from the group consisting of phenyl, biphenyl, and naphthyl, which may be unsubstituted or substituted. In some embodiments, Ar has at least one substituent selected from the group consisting of F, alkyl, fluoroalkyl, alkoxy, and fluoroalkoxy.

， 其中R¹ 至R⁹ 、a、和b如式I中所定義。式I中的R¹ 至R⁹ 、a、和b的所有以上描述的實施例同樣適用於式IA中的R¹ 至R⁹ 、a、和b。In some embodiments of Formula I, the polyamine has Formula IA:

, Wherein R ¹ to R ⁹ , a, and b are as defined in Formula I. All the above-described embodiments of R ¹ to R ⁹ , a, and b in formula I are equally applicable to R ¹ to R ⁹ , a, and b in formula IA.

， 其中R¹ 、R² 、R⁵ 至R⁹ 、a、和b如式I中所定義。式I中的R¹ 、R² 、R⁵ 至R⁹ 、a、和b的所有以上描述的實施例同樣適用於式IB中的R¹ 、R² 、R⁵ 至R⁹ 、a、和b。In some embodiments of Formula I, the polyamine has Formula IB:

, Wherein R ¹ , R ² , R ⁵ to R ⁹ , a, and b are as defined in Formula I. Formula I is R ^1, R ^2, applies equally to formula IB wherein R Example all of R ⁵ to R ^9, a, and b of the above-described ^1, R ^2, R ⁵ to R ^9, a, and b .

， 其中R¹ 至R⁶ 、R⁸ 、R⁹ 、a、和b如式I中所定義。式I中的R¹ 至R⁶ 、R⁸ 、R⁹ 、a、和b的所有以上描述的實施例同樣適用於式IC中的R¹ 至R⁶ 、R⁸ 、R⁹ 、a、和b。In some embodiments of formula I, the polyamine has formula IC:

, Wherein R ¹ to R ⁶ , R ⁸ , R ⁹ , a, and b are as defined in Formula I. Formula I wherein R ¹ to ^{R 6, R 8, R 9} , all a, and b of the above-described embodiments apply equally to formula IC wherein R Embodiment ¹ through ^{R 6, R 8, R 9} , a, and b .

New compounds can be prepared using any technique that will create C-C or C-N bonds. Many such techniques are known, such as Suzuki, Yamamoto, Stille, Negishi and metal-catalyzed CN coupling and metal-catalyzed and oxidative direct arylation, and Diel Diels-Alder (Diels-Alder) cycloaddition reaction. Exemplary preparations are given in the examples.

。A synthesis scheme is shown below:

.

In the above scheme, "Bpin" stands for boron pinacolate.

Any of the above embodiments of Formula I can be combined with one or more of the other embodiments, as long as they are not mutually exclusive. For example, an embodiment in which Q ¹ and Q ² are R ⁷ can be combined with an embodiment in which at least one R ⁷ is NH ₂ , an embodiment in which a=0, and an embodiment in which b=0. Those with ordinary knowledge in the art will understand which embodiments are mutually exclusive and will therefore easily be able to determine the combination of embodiments considered in this application.

化合物2

化合物3

化合物4

化合物5

化合物6

Some non-limiting examples of compounds of formula I are shown below. Compound 1

Compound 2

Compound 3

Compound 4

Compound 5

Compound 6

3. Polyamide acid

The polyamide acid described herein is a reaction product of one or more polybasic acid anhydrides and one or more polyamines, wherein 10-100 mol% of the one or more polyamines have formula I.

In some embodiments of polyamic acid, a polyamine of formula I is reacted.

In some embodiments of polyamides, two different polyamines of formula I are reacted.

In some embodiments of polyamides, three different polyamines of formula I are reacted.

In some embodiments of polyamic acid, four different polyamines of formula I are reacted.

In some embodiments of polyamide acid, 20-100 mol% of the one or more polyamines have 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%.

In some embodiments of polyamide acids, at least one additional polyamine is reacted with one or more polyamines of formula I.

In some embodiments of polyamides, an additional polyamine reacts with one or more polyamines of formula I.

In some embodiments of polyamides, two additional polyamines are reacted with one or more polyamines of formula I.

In some embodiments of polyamides, three additional polyamines are reacted with one or more polyamines of formula I.

In some embodiments of polyamides, four additional polyamines are reacted with one or more polyamines of formula I.

， 其中： R^a 在每次出現時是相同或不同的，並且表示一個或多個四羧酸殘基；以及 R^b 在每次出現時是相同或不同的，並且表示一個或多個二胺殘基； 其中10~100 mol%的R^b 係來自一種或多種具有式I之二胺的殘基。In some embodiments of polyamide acid, polyamide acid has a repeating unit structure of formula II:

, Where: R ^a is the same or different at each occurrence and represents one or more tetracarboxylic acid residues; and R ^b is the same or different at each occurrence and represents one or more diamines Residues: 10-100 mol% of R ^b is derived from one or more residues of diamines of formula I.

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

In some embodiments of Formula II, R ^a represents two different tetracarboxylic acid component residue.

In some embodiments of Formula II, R ^a represents three different tetracarboxylic acid residue.

In some embodiments of Formula II, R ^a represents four different tetracarboxylic acid residue.

In some embodiments of Formula II, R ^a represents one or more tetracarboxylic dianhydride residue.

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 phthalic acid polybasic anhydride (6FDA), 3,3',4,4'-benzophenone tetracarboxylic acid Anhydride (BTDA), 3,3',4,4'-diphenyl tetracarboxylic dianhydride (DSDA), 4,4'-bisphenol-A dianhydride (BPADA), hydroquinone diphthalic anhydride ( HQDEA), ethylene glycol bis(trimellitic anhydride) (TMEG-100), 4-(2,5-di-side oxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2- Dicarboxylic acid anhydride (DTDA); 4,4'-bisphenol A dianhydride (BPADA), etc. and combinations thereof. The aromatic dianhydrides can be optionally substituted with groups known in the art, and these groups include alkyl, aryl, nitro, cyano, -N(R')(R ^" ), halogen, and hydroxyl. , 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 optionally substituted alkyl, cycloalkyl or aryl Group. R'and R", together with the nitrogen atom to which they are bound, may form a ring system in certain embodiments. The substituent may also be a crosslinking group.

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

In some embodiments of Formula II, R ^a represents a residue of PMDA.

In some embodiments of Formula II, R ^a represents a residue of BPDA.

In some embodiments of Formula II, R ^a represents a residue of 6FDA.

In some embodiments of Formula II, R ^a represents a residue BTDA.

In some embodiments of Formula II, R ^a represents a residue of PMDA and BPDA residues.

In some embodiments of Formula II, R ^a represents a residue of PMDA and 6FDA residues.

In some embodiments of Formula II, R ^a represents a residue of PMDA and BTDA residues.

In some embodiments of Formula II, R ^a represents a residue BPDA and 6FDA residues.

In some embodiments of Formula II, R ^a represents a residue of BPDA and BTDA residues.

In some embodiments of Formula II, R ^a represents a residue, and BTDA 6FDA residues.

In some embodiments of Formula II, R ^a represents a residue PMDA, BPDA residues, and residues 6FDA.

In formula II, 10-100 mol% of R ^b represents one or more diamine residues having the diamine of formula I as shown above.

In some embodiments of formula II, 10-100 mol% of R ^b represents a diamine residue having a diamine of formula I as shown above.

In some embodiments of Formula II, 10-100 mol% of R ^b represents a diamine residue from two different diamines, both of which have the diamine of Formula I as shown above.

In some embodiments of formula II, 10-100 mol% of R ^b represents a diamine residue from three different diamines, all having the diamine of formula I as shown above.

In some embodiments of formula II, 10-100 mol% of R ^b represents four or more different diamine residues, all having the diamine of formula I as shown above.

In some embodiments of formula II, 20-100 mol% of R ^b is derived from one or more residues of diamines of 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%.

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

In some embodiments of Formula II, R ^b represents one or more diamine residues having a diamine of Formula I and at least one additional diamine residue.

In some embodiments of Formula II, R ^b represents a diamine residue derived from one or more diamines of Formula I and an additional diamine residue.

In some embodiments of Formula II, R ^b represents one or more diamine residues having the diamine of Formula I and two additional diamine residues.

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

In some embodiments of Formula II, the one or more additional diamine residues are derived from one or more additional aromatic diamine residues.

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) pyridine (FDA), o-tolidine (TSN), 2,3,5,6-tetramethyl-1,4-phenylene Diamine (TMPD), 2,4-Diamino-1,3,5-Trimethylbenzene (DAM), 3,3',5,5'-Tetramethylbenzidine (3355TMB), 2,2' -Bis(trifluoromethyl)benzidine (22TFMB or TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-methylene bis Aniline (MDA), 4,4'-[1,3-phenylene bis(1-methyl-ethylene)] bisaniline (Bis-M), 4,4'-[1,4-phenylene Bis (1-methyl-ethylene)] bisaniline (Bis-P), 4,4'-oxydiphenylamine (4,4'-ODA), m-phenylene diamine (MPD), 3 ,4'-oxydiphenylamine (3,4'-ODA), 3,3'-diaminodiphenyl sulfide (3,3'-DDS), 4,4'-diaminodiphenyl sulfide (4 ,4'-DDS), 4,4'-diaminodiphenyl sulfide (ASD), 2,2-bis[4-(4-aminophenoxy)phenyl] sulfide (BAPS), 2 ,2-Bis[4-(3-aminophenoxy)-phenyl] sulfide (m-BAPS), 1,4'-bis(4-aminophenoxy)benzene (TPE-Q), 1 ,3'-bis(4-aminophenoxy)benzene (TPE-R), 1,3'-bis(4-aminophenoxy)benzene (APB-133), 4,4'-bis (4-Aminophenoxy)biphenyl (BAPB), 4,4'-diaminophenylaniline (DABA), methylene bis(anthranilic acid) (MBAA), 1,3' -Bis(4-aminophenoxy)-2,2-dimethylpropane (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'-bis Amino diphenylmethane (TMMDA), etc. and combinations thereof.

In some embodiments of formula II, R ^b represents a diamine residue derived from one or more diamines of formula I and a diamine residue derived from at least one additional diamine, wherein the additional diamine is selected from Groups consisting of: PPD, 4,4'-ODA, 3,4'-ODA, TFMB, Bis-A-AF, Bis-AT-AF, and Bis-P.

In some embodiments of Formula II, the moiety derived from the mono-anhydride monomer is present as a capping group.

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

In some embodiments, the monoanhydrides are present in amounts up to 5 mol% of the total tetracarboxylic acid composition.

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

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

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

In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight greater than 100,000 (M _W).

In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight greater than 150,000 (M _W).

In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight greater than 200,000 (M _W).

In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight greater than 250,000 (M _W).

In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight greater than 300,000 (M _W).

In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight (M _W) of between 100,000 and 400,000.

In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight (M _W) of between 200,000 and 400,000.

In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight (M _W) of between 250,000 and 350,000.

In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight (M _W) of between 200,000 and 300,000.

Any of the above embodiments of polyamide may be combined with one or more of the other embodiments, as long as they are not mutually exclusive.

The overall polyamide composition can be named via symbols commonly used in the art. For example, a polyamide with a tetracarboxylic acid component of 100% ODPA and a diamine component of 90 mol% of Bis-P and 10 mol% of TFMB can be expressed as: ODPA//Bis-P/TFMB 100//90/10.

A liquid composition is also provided, which comprises (a) a polyamide acid having a repeating unit of formula II and (b) a high-boiling aprotic solvent. This liquid composition is also referred to herein as "polyamide acid solution".

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

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

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

In some embodiments, the high-boiling aprotic solvent is a polar solvent. In some embodiments, the solvent has a dielectric constant greater than 20.

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

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

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

In some embodiments of the liquid composition, the solvent is DMAc.

In some embodiments of the liquid composition, the solvent is DMF.

In some embodiments of the liquid composition, the solvent is gamma-butyrolactone.

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

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

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

In some embodiments of the liquid composition, the solvent is propylene glycol monoethyl ether acetate.

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

In some embodiments, additional co-solvents are used in the liquid composition.

In some embodiments, the liquid composition is> 1% by weight of polyamide acid in> 99% by weight of high-boiling aprotic solvent.

In some embodiments, the liquid composition is 1% to 5% by weight of polyamide acid in 95% to 99% by weight of high boiling point aprotic solvent.

In some embodiments, the liquid composition is 5% to 10% by weight of polyamic acid in 90% to 95% by weight of high boiling point aprotic solvent.

In some embodiments, the liquid composition is 10% to 15% by weight of polyamic acid in 85% to 90% by weight of a high boiling point aprotic solvent.

In some embodiments, the liquid composition is 15 wt% to 20 wt% polyamic acid in 80 wt% to 85% by weight high boiling point aprotic solvent.

In some embodiments, the liquid composition is 20% to 25% by weight of polyamic acid in 75% to 80% by weight of a high boiling point aprotic solvent.

In some embodiments, the liquid composition is 25% to 30% by weight of polyamic acid in 70% to 75% by weight of high-boiling aprotic solvent.

In some embodiments, the liquid composition is 30% to 35% by weight of polyamic acid in 65% to 70% by weight of a high boiling point aprotic solvent.

In some embodiments, the liquid composition is 35% to 40% by weight of polyamic acid in 60% to 65% by weight of high-boiling aprotic solvent.

In some embodiments, the liquid composition is 40% to 45% by weight of polyamic acid in 55% to 60% by weight of high boiling point aprotic solvent.

In some embodiments, the liquid composition is 45% to 50% by weight of polyamic acid in 50% to 55% by weight of high boiling point aprotic solvent.

In some embodiments, the liquid composition is 50% by weight of polyamide acid in 50% by weight of high-boiling aprotic solvent.

The polyamide acid solution may further contain any of many additives as necessary. Such additives may be: antioxidants, heat stabilizers, adhesion promoters, coupling agents (such as silane), inorganic fillers or various reinforcing agents, as long as they do not deleteriously affect the desired polyimide properties.

The polyamide acid solution can be prepared using various available methods for introducing components (ie, monomer and solvent). Some methods of producing polyamide acid solutions include: (a) A method in which the polyamine component and the polybasic acid anhydride component are mixed together in advance, and then the mixture is added to the solvent in batches while stirring. (b) A method in which a solvent is added to a stirred mixture of polyamine and polyanhydride components. (Contrary to (a) above) (c) A method in which a polyamine is separately dissolved in a solvent, and then a polybasic acid anhydride is added thereto in a ratio that allows control of the reaction rate. (d) A method in which the polybasic acid anhydride component is separately dissolved in a solvent, and then the amine component is added thereto in a ratio that allows control of the reaction rate. (e) A method in which the polyamine component and the polybasic acid anhydride component are separately dissolved in a solvent and then the solutions are mixed in a reactor. (f) A method in which a polyamide acid having an excess of polyamine components and another polyamide acid having an excess of polybasic anhydride components are formed in advance, and then they are allowed to react with each other in a reactor, especially to produce Such ways of non-random or block copolymers react with each other. (g) A method in which a specific portion of the polyamine component and the polybasic acid anhydride component are first reacted, and then the remaining polyamine component is reacted, or vice versa. (h) A method in which these components are added partly or wholly to part or all of the solvent in any order, and part or all of any components can be added as a solution in part or all of the solvent. (i) A method in which one of the polybasic acid anhydride components and one of the polyamine components are first reacted to obtain the first polyamide acid. Then another polyacid anhydride component is reacted with another polyamine component to obtain a second polyamide acid. The polyamides are then combined in any of a variety of ways before film formation.

Generally speaking, the polyamic acid solution can be obtained by any of the methods for preparing the polyamic acid solution disclosed above.

The polyamide solution can then be filtered one or more times in order to reduce the particle content. The polyimide film produced from such a filtered solution can show a reduced number of defects, and thereby produce excellent performance in the electronic applications disclosed herein. The filtration efficiency can be evaluated by the laser particle counter test, in which a representative sample of the polyamide acid solution is poured on a 5" silicon wafer. After soft drying/drying, by any number of lasers The particle counting technique evaluates the particle content of the film on a commercially available instrument known in the art.

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

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

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

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

In some embodiments, a polyamide acid solution is prepared and filtered to produce a particle content between 2 particles and 8 particles, as measured by a laser particle counter test.

In some embodiments, a polyamide acid solution is prepared and filtered to produce a particle content between 4 particles and 6 particles, as measured by a laser particle counter test.

An exemplary preparation of the polyamide acid solution is given in the examples.

4. Polyimide

Provided is a polyimide obtained by the imidization of the above-mentioned polyimide. "Imidation" refers to the intramolecular cyclization of an amido acid group to form an amido group. In some embodiments, thermal imidization is used. In some embodiments, chemical imidization is used. In some embodiments, a combination of thermal imidization and chemical imidization is used.

， 其中： R^a 在每次出現時是相同或不同的，並且表示一個或多個四羧酸組分殘基；以及 R^b 在每次出現時是相同或不同的，並且表示一個或多個芳香族二胺殘基； 其中10~100 mol%的R^b 係來自一種或多種具有式I之二胺的殘基。In some embodiments, the polyimide has a repeating unit structure of formula III:

, Where: 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; wherein 10-100 mol% of R ^b is derived from one or more residues of diamines of formula I.

All Formula II R ^a and R ^b are the same applies to the above embodiment of Formula III R ^a and R ^b are described.

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

Polyimine can be made from any suitable polyimine precursor (such as polyimide, polyimide, polyisoimide, and polyimide).

A polyimide film is also provided, wherein the polyimide has a repeating unit structure of formula III as described above.

The polyimide film can be made by coating a polyimide precursor on a substrate and then imidizing it. This can be achieved by thermal conversion methods or chemical conversion methods.

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 a polyimide.

In some embodiments, the polyimide film including the polyimide having the repeating unit of Formula III has both a high glass transition temperature and a low coefficient of thermal expansion (CTE).

In some embodiments of the polyimide film, for the polyimide film cured at a temperature exceeding 325°C, the glass transition temperature ( _Tg ) is greater than 300°C; in some embodiments, the system It is greater than 350°C; in some embodiments, it is greater than 375°C.

In some embodiments of the polyimide film, for the first measurement, the in-plane coefficient of thermal expansion (CTE) is less than 50 ppm/°C between 50°C and 200°C; in some embodiments, the system Less than 35 ppm/°C; in some embodiments, less than 20 ppm/°C; in some embodiments, less than 15 ppm/°C.

In some embodiments of the polyimide film, for the second measurement, the in-plane coefficient of thermal expansion (CTE) between 50°C and 200°C is less than 50 ppm/°C; in some embodiments, the system Less than 40 ppm/°C.

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

In some embodiments of the polyimide film, the tensile modulus is between 1.5 GPa and 15.0 GPa; in some embodiments, it is between 1.5 GPa and 10.0 GPa; in some embodiments, the tensile modulus is between 1.5 GPa and 10.0 GPa; Between 1.5 GPa and 7.5 GPa; in some embodiments, between 1.5 GPa and 5.0 GPa.

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

In some embodiments of the polyimide film, the birefringence is less than 1.0; in some embodiments, the birefringence is less than 0.1; in some embodiments, the birefringence is less than 0.05.

In some embodiments of the polyimide film, the optical retardation is less than 500 at 550 nm; in some embodiments, it is less than 400; in some embodiments, it is less than 350.

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

In some embodiments of the polyimide film, b* is less than 7.5; in some embodiments, b* is less than 5.0.

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

In some embodiments of the polyimide film, the transmittance at 450 nm is greater than 50%; in some embodiments, it is greater than 80%.

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

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

Any of the above embodiments of the polyimide film can be combined with one or more of the other embodiments, as long as they are not mutually exclusive.

5. Method for preparing polyimide film

Generally speaking, polyimide membranes can be prepared from polyimine precursors by chemical or thermal conversion. In some embodiments, the films are prepared from corresponding polyamic acid solutions by chemical or thermal conversion methods. The polyimide film disclosed herein (especially when used as a flexible substitute for glass in electronic devices) is prepared by a thermal conversion method.

Generally speaking, polyimide membranes can be prepared from corresponding polyimide solutions by chemical or thermal conversion methods. The polyimide film disclosed herein (especially when used as a flexible substitute for glass in electronic devices) is prepared by thermal conversion or modified thermal conversion methods and chemical conversion methods.

Chemical transformation methods are described in US 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 the polyamide 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 acid anhydrides; and (ii) one or more catalysts, such as aliphatic tertiary amines (Triethylamine, etc.), tertiary amines (dimethylaniline, etc.) and heterocyclic tertiary amines (pyridine, picoline, isoquinoilne, etc.). Anhydride dehydration materials are typically used in a slight molar excess of the amount of amide groups present in the polyamide acid solution. The amount of acetic anhydride used is typically about 2.0 to 3.0 moles per equivalent of polyamide acid. Generally, a considerable amount of tertiary amine catalyst is used.

The thermal conversion method may or may not use conversion chemicals (ie, catalysts) to convert the polyamide acid casting solution to polyimide. If conversion chemicals are used, the method can be considered an improved thermal conversion method. In the 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 perform the imidization reaction. The thermal conversion method with or without a conversion catalyst is generally used to prepare the polyimide membrane disclosed herein.

Considering that it is not only the film composition that produces the characteristics of interest, the specific method parameters are pre-selected. On the contrary, curing temperature and temperature ramping curves also play an important role in achieving the most desirable characteristics of the intended use disclosed herein. Polyamide acid should be at or above the maximum temperature of any subsequent processing steps (such as the deposition of one or more inorganic or other layers required for functional displays), but below the maximum temperature of the polyimide It is imidized at the temperature at which significant thermal degradation/discoloration occurs. It should also be noted that an inert atmosphere is generally preferred, especially when higher processing temperatures are used for the imidization.

For the polyamide/polyimide disclosed herein, when a subsequent processing temperature exceeding 300°C is required, a temperature of 300°C to 320°C is typically used. Choosing an appropriate curing temperature allows obtaining a fully cured polyimide that achieves the best balance of thermal and mechanical properties. Due to this very high temperature, an inert atmosphere is required. Typically, furnace oxygen levels >100 ppm should be used. The very low oxygen level enables the highest curing temperature to be used without significant degradation/discoloration of the polymer. The catalyst that accelerates the imidization process effectively achieves a higher level of imidization at a curing temperature between about 200°C and 300°C. If the flexible device is prepared at a higher curing temperature lower than the T _g of the polyimide, this method can be used as needed.

The amount of time for each possible curing step is also an important process consideration. In general, the time for curing at the highest temperature should be kept to a minimum. For example, for curing at 320°C, the curing time can be as long as one hour in an inert atmosphere; but at higher curing temperatures, this time should be shortened to avoid thermal degradation. Generally speaking, a higher temperature indicates a shorter time. Those with ordinary knowledge in the art will recognize the balance between temperature and time in order to optimize the properties of polyimides for specific end uses.

In some embodiments, the polyimide solution is converted into a polyimide film via a thermal conversion method.

In some embodiments of the thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is less than 50 µm.

In some embodiments of the thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is less than 40 µm.

In some embodiments of the thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is less than 30 µm.

In some embodiments of the thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is less than 20 µm.

In some embodiments of the thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is between 10 µm and 20 µm.

In some embodiments of the thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is between 15 µm and 20 µm.

In some embodiments of the thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is 18 µm.

In some embodiments of the thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is less than 10 µm.

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

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

In some embodiments of the thermal conversion method, a combination of proximity mode and full contact mode is used to soft bake the coated substrate on a hot plate.

In some embodiments of the thermal conversion method, a hot plate set at 80°C is used to soft bake the coated substrate.

In some embodiments of the thermal conversion method, a hot plate set at 90°C is used to soft bake the coated substrate.

In some embodiments of the thermal conversion method, a hot plate set at 100°C is used to soft bake the coated substrate.

In some embodiments of the thermal conversion method, a hot plate set at 110°C is used to soft bake the coated substrate.

In some embodiments of the thermal conversion method, a hot plate set at 120°C is used to soft bake the coated substrate.

In some embodiments of the thermal conversion method, a hot plate set at 130°C is used to soft bake the coated substrate.

In some embodiments of the thermal conversion method, a hot plate set at 140°C is used to soft bake the coated substrate.

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

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

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

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

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

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

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

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 2 pre-selected temperatures for 2 pre-selected time intervals, where the time intervals can be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 3 pre-selected temperatures for 3 pre-selected time intervals, where each of the time intervals can be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 4 pre-selected temperatures for 4 pre-selected time intervals, where each of the time intervals can be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 5 pre-selected temperatures for 5 pre-selected time intervals, where each of the time intervals can be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 6 pre-selected temperatures for 6 pre-selected time intervals, where each of the time intervals can be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 7 pre-selected temperatures for 7 pre-selected time intervals, where each of the time intervals can be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 8 pre-selected temperatures for 8 pre-selected time intervals, where each of the time intervals can be the same or different of.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 9 pre-selected temperatures for 9 pre-selected time intervals, where each of the time intervals can be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 10 pre-selected temperatures for 10 pre-selected time intervals, where each of the time intervals can be the same or different.

In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 80°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 100°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 100°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 150°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 150°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 200°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 200°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 250°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 250°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 300°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 300°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 350°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 350°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 400°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 400°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 450°C.

In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 450°C.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 2 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 5 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 10 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 15 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 20 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 25 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 30 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 35 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 40 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 45 minutes.

In some of the thermal conversion methods, one or more of the pre-selected time intervals are 50 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 55 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are 60 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are greater than 60 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are between 2 minutes and 60 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are between 2 minutes and 90 minutes.

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals are between 2 minutes and 120 minutes.

In some embodiments of the thermal conversion method, the method for preparing the polyimide film sequentially includes the following steps: coating the polyimide acid solution described above on a substrate; soft baking the coated substrate; The soft-baked coated substrate is treated at a plurality of pre-selected temperatures for a plurality of pre-selected time intervals, whereby the polyimide film exhibits characteristics that meet the requirements for electronic applications such as those disclosed herein.

In some embodiments of the thermal conversion method, the method for preparing the polyimide film consists of the following steps in order: coating the polyimide acid solution described above on a substrate; soft baking the coated substrate The soft-baked coated substrate is treated for a plurality of pre-selected time intervals at a plurality of pre-selected temperatures, whereby the polyimide film exhibits characteristics that satisfy those electronic applications as disclosed herein .

In some embodiments of the thermal conversion method, the method for preparing the polyimide film mainly consists of the following steps in order: coating the polyimide acid solution described above on the substrate; soft baking the coated Substrate; the soft-baked coated substrate is treated at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory performance for electronic applications such as those disclosed herein characteristic.

Typically, the polyimide solution/polyimide disclosed herein is coated/cured on the supporting glass substrate to facilitate processing during the rest of the display manufacturing process. At some point in the process determined by the display manufacturer, the polyimide coating is removed from the supporting glass substrate by a mechanical or laser lift-off process. These processes separate the polyimide as the film with the deposited display layer from the glass and realize a flexible form. Usually, the polyimide film with the deposited layer is then glued to a thicker but still flexible plastic film to provide support for the subsequent production of the display.

An improved thermal conversion method is also provided, in which the conversion catalyst generally causes the imidization reaction to proceed at a lower temperature than is possible in the absence of such a conversion catalyst.

In some embodiments, the polyimide solution is converted into a polyimide film via a modified thermal conversion method.

In some embodiments of the improved thermal conversion method, the polyamide acid solution further contains a conversion catalyst.

In some embodiments of the improved thermal conversion method, the polyamide acid solution further contains a conversion catalyst selected from the group consisting of tertiary amines.

In some embodiments of the improved thermal conversion method, the polyamide 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-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine Base pyridine, 5-methylbenzimidazole, etc.

In some embodiments of the improved thermal conversion method, the conversion catalyst is present at 5 wt% or less of the polyamide acid solution.

In some embodiments of the improved thermal conversion method, the conversion catalyst is present at 3% by weight or less of the polyamide acid solution.

In some embodiments of the improved thermal conversion method, the conversion catalyst is present at 1% by weight or less of the polyamide acid solution.

In some embodiments of the improved thermal conversion method, the conversion catalyst is present at 1% by weight of the polyamide acid solution.

In some embodiments of the improved thermal conversion method, the polyamide acid solution further contains tributylamine as a conversion catalyst.

In some embodiments of the improved thermal conversion method, the polyamide acid solution further contains dimethylethanolamine as a conversion catalyst.

In some embodiments of the improved thermal conversion method, the polyamide acid solution further contains isoquinoline as a conversion catalyst.

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

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

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

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

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

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

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

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

In some embodiments of the improved thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is less than 50 µm.

In some embodiments of the improved thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is less than 40 µm.

In some embodiments of the improved thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is less than 30 µm.

In some embodiments of the improved thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is less than 20 µm.

In some embodiments of the improved thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is between 10 µm and 20 µm.

In some embodiments of the improved thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is between 15 µm and 20 µm.

In some embodiments of the improved thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is 18 µm.

In some embodiments of the improved thermal conversion method, the polyamide acid solution is coated on the substrate so that the soft bake thickness of the resulting film is less than 10 µm.

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

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

In some embodiments of the improved thermal conversion method, a combination of proximity mode and full contact mode is used to soft bake the coated substrate on a hot plate.

In some embodiments of the improved thermal conversion method, a hot plate set at 80°C is used to soft bake the coated substrate.

In some embodiments of the improved thermal conversion method, a hot plate set at 90°C is used to soft bake the coated substrate.

In some embodiments of the improved thermal conversion method, a hot plate set at 100°C is used to soft bake the coated substrate.

In some embodiments of the improved thermal conversion method, a hot plate set at 110°C is used to soft bake the coated substrate.

In some embodiments of the improved thermal conversion method, a hot plate set at 120°C is used to soft bake the coated substrate.

In some embodiments of the improved thermal conversion method, a hot plate set at 130°C is used to soft bake the coated substrate.

In some embodiments of the improved thermal conversion method, a hot plate set at 140°C is used to soft bake the coated substrate.

In some embodiments of the improved thermal conversion method, the coated substrate is soft baked for a total time of more than 10 minutes.

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

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

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

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

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

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

In some embodiments of the improved thermal conversion method, the soft-baked coated substrate is then cured at 2 pre-selected temperatures for 2 pre-selected time intervals, where the time intervals can be the same or different .

In some embodiments of the improved thermal conversion method, the soft-baked coated substrate is then cured at 3 pre-selected temperatures for 3 pre-selected time intervals, where each of the time intervals can be Same or different.

In some embodiments of the improved thermal conversion method, the soft-baked coated substrate is then cured at 4 pre-selected temperatures for 4 pre-selected time intervals, where each of the time intervals can be Same or different.

In some embodiments of the improved thermal conversion method, the soft-baked coated substrate is then cured at 5 pre-selected temperatures for 5 pre-selected time intervals, where each of the time intervals can be Same or different.

In some embodiments of the improved thermal conversion method, the soft-baked coated substrate is then cured at 6 pre-selected temperatures for 6 pre-selected time intervals, where each of the time intervals can be Same or different.

In some embodiments of the improved thermal conversion method, the soft-baked coated substrate is then cured at 7 pre-selected temperatures for 7 pre-selected time intervals, where each of the time intervals can be Same or different.

In some embodiments of the improved thermal conversion method, the soft-baked coated substrate is then cured at 8 pre-selected temperatures for 8 pre-selected time intervals, where each of the time intervals can be Same or different.

In some embodiments of the improved thermal conversion method, the soft-baked coated substrate is then cured at 9 pre-selected temperatures for 9 pre-selected time intervals, where each of the time intervals can be Same or different.

In some embodiments of the improved thermal conversion method, the soft-baked coated substrate is then cured at 10 pre-selected temperatures for 10 pre-selected time intervals, where each of the time intervals can be Same or different.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 80°C.

In some embodiments of the modified thermal conversion method, the pre-selected temperature is equal to 100°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 100°C.

In some embodiments of the modified thermal conversion method, the pre-selected temperature is equal to 150°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 150°C.

In some embodiments of the modified thermal conversion method, the pre-selected temperature is equal to 200°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 200°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 220°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 220°C.

In some embodiments of the modified thermal conversion method, the pre-selected temperature is equal to 230°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 230°C.

In some embodiments of the modified thermal conversion method, the pre-selected temperature is equal to 240°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 240°C.

In some embodiments of the modified thermal conversion method, the pre-selected temperature is equal to 250°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 250°C.

In some embodiments of the modified thermal conversion method, the pre-selected temperature is equal to 260°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 260°C.

In some embodiments of the modified thermal conversion method, the pre-selected temperature is equal to 270°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 270°C.

In some embodiments of the modified thermal conversion method, the pre-selected temperature is equal to 280°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 280°C.

In some embodiments of the modified thermal conversion method, the pre-selected temperature is equal to 290°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 290°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 300°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 300°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 290°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 280°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 270°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 260°C.

In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 250°C.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 2 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 5 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 10 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 15 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 20 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 25 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 30 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 35 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 40 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 45 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 50 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 55 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are 60 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is greater than 60 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are between 2 minutes and 60 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are between 2 minutes and 90 minutes.

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals are between 2 minutes and 120 minutes.

In some embodiments of the improved thermal conversion method, the method for preparing a polyimide film sequentially includes the following steps: coating the polyimide solution containing the conversion chemical described above on the substrate; soft baking The coated substrate; the soft-baked coated substrate is treated at a plurality of pre-selected temperatures for a plurality of pre-selected time intervals, whereby the polyimide film appears to be satisfactory for use as disclosed herein Characteristics of those electronic applications.

In some embodiments of the improved thermal conversion method, the method for preparing the polyimide film consists of the following steps in sequence: coating the polyimide solution containing the conversion chemical described above on the substrate; Baking the coated substrate; treating the soft-baked coated substrate at a plurality of pre-selected temperatures for a plurality of pre-selected time intervals, whereby the polyimide film appears to be satisfactory for use as described herein The characteristics of those electronic applications revealed.

In some embodiments of the improved thermal conversion method, the method for preparing the polyimide film mainly consists of the following steps in order: coating the polyimide solution containing the conversion chemical described above on the substrate; Soft-baking the coated substrate; treating the soft-baked coated substrate at a plurality of pre-selected temperatures for a plurality of pre-selected time intervals, whereby the polyimide film appears to be satisfactory for use as The characteristics of those electronic applications disclosed in this article.

6. Electronic device

The polyimide film 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 device substrates, touch panels, substrates of color filters, cover films, and the like. 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 film disclosed herein.

In some embodiments, a flexible substitute for glass in an electronic device includes a polyimide film of polyimide having a repeating unit of formula III as described in detail above.

In some embodiments, there is provided an organic electronic device having at least one layer comprising a polyimide film having a repeating unit of formula III as described in detail above.

Organic electronic devices that can benefit from having one or more layers including at least one compound as described herein include, but are not limited to: (1) devices that convert electrical energy into radiation (such as light-emitting diodes, light-emitting diodes) Displays, lighting devices, light sources, or diode lasers), (2) Devices that detect signals by electronic methods (such as photodetectors, photoconductive cells, photoresistors, photocontrol relays, phototransistors, phototubes, IR detectors, biosensors), (3) devices that convert radiation into electrical energy (such as photovoltaic devices or solar cells), (4) devices that convert one wavelength of light into longer wavelengths (such as the following Frequency conversion phosphor device); and (5) a device including one or more electronic components, the one or more electronic components including one or more organic semiconductor layers (for example, transistors or diodes). Other uses of the composition according to the present invention include coating materials for memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolytic capacitors, energy storage devices (such as rechargeable batteries), and electromagnetic Mask application.

An illustration of a polyimide film that can serve as a flexible alternative to glass as described herein is shown in FIG. The flexible film 100 may have characteristics as described in the embodiments of the present disclosure. In some embodiments, a polyimide film that can serve as a flexible substitute for glass is included in the electronic device. FIG. 2 illustrates the situation when the electronic device 200 is an organic electronic device. 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. There may be additional layers as needed. Adjacent to the anode may be a hole injection layer (not shown), sometimes called 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) immediately adjacent to the anode 110 and/or one or more additional electron injection layers or electron transport layers immediately adjacent to the cathode 130 Layer (not shown). The layers between 110 and 130 are individually and collectively referred to as organic active layers. Additional layers that may or may not be present include color filters, touch panels, and/or shields. One or more of these layers (except for the substrate 100) can also be made of the polyimide film disclosed herein.

These different layers will be discussed further with reference to FIG. 2. However, the discussion is equally applicable to other configurations.

In some embodiments, the different layers have the following thickness ranges: substrate 100, 5-100 microns, anode 110, 500-5000 Å, in some embodiments, 1000-2000 Å; hole injection layer (not shown) , 50~2000 Å, in some embodiments, 200~1000 Å; hole transport layer (not shown), 50~3000 Å, in some embodiments, 200~2000 Å; optical active layer 120, 10~ 2000 Å, in some embodiments, 100~1000 Å; electron transport layer (not shown), 50~2000 Å, in some embodiments, 100~1000 Å; cathode 130, 200~10000 Å, in some embodiments In the example, 300~5000 Å. The desired ratio of layer thicknesses will depend on the exact nature of the materials used.

In some embodiments, an organic electronic device (OLED) contains a flexible substitute for glass as disclosed herein.

In some embodiments, an organic electronic device is provided, wherein the device substrate includes the polyimide film disclosed herein. In some embodiments, the device is an organic light emitting diode (OLED).

In some embodiments, the organic electronic device includes a substrate, an anode, a cathode, and a photoactive layer therebetween, and further includes 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 active layer is both a hole transport layer and an electron transport layer.

The anode 110 is an electrode particularly effective for injecting positive charge carriers. It may be made of, for example, a material containing a metal, mixed metal, alloy, metal oxide, or mixed metal oxide, or it may be a conductive polymer, and a mixture 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 transparent, mixed metal oxides of metals of groups 12, 13 and 14 are generally used, such as indium tin oxide. The anode may also contain organic materials such as polyaniline, as described in "Flexible light-emitting diodes made from soluble conducting polymer", Nature [Nature], Vol. 357, No. 477 ~ Page 479 (June 11, 1992). At least one of the anode and cathode should be at least partially transparent to allow the light generated to be observed.

The hole injection layer may include a hole injection material as needed. The term "hole injection layer" or "hole injection material" is intended to be a conductive or semiconducting material, and may have one or more functions in organic electronic devices, including but not limited to the 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 facilitate or improve the performance of organic electronic devices. The hole injection material can be a polymer, oligomer or small molecule, and can be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture or other composition.

The hole injection layer can be formed of polymer materials, such as polyaniline (PANI) or polyethylene dioxythiophene (PEDOT), which are usually doped with protic acid. The protic acid may be, for example, poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), and the like. The hole injection layer 120 may include a charge transfer compound or the like, such as copper phthalocyanine and tetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ). In some embodiments, the hole injection layer 120 is made of a dispersion of a conductive polymer and a colloidal polymer acid. Such materials have been described in, for example, published US patent applications 2004-0102577, 2004-0127637, and 2005-0205860.

Other layers may contain hole transport materials. Examples of hole transport materials used in the hole transport layer have been summarized in, for example, Y. Wang's Kirk-Othmer Encyclopedia of Chemical Technology [Kirk Othmer Encyclopedia of Chemical Technology], Fourth Edition, Volume 18, No. 837 ~860 pages, in 1996. Both small hole transport 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- Benzene (mCP); 1,1-bis[(Di-4-tolylamino)phenyl]cyclohexane (TAPC); N,N'-bis(4-methylphenyl)-N, N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl)biphenyl]-4,4'-diamine (ETPD); Tetra-(3- Methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA); α-phenyl-4-N,N-diphenylaminostyrene (TPS); -(Diethylamino) benzaldehyde diphenylhydrazone (DEH); triphenylamine (TPA); bis[4-(N,N-diethylamino)-2-methylphenyl](4-methyl Phenyl)methane (MPMP); 1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline ( PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB); N,N,N',N'-tetra(4-methylphenyl)- (1,1'-biphenyl)-4,4'-diamine (TTB); N,N'-bis(naphthalene-1-yl)-N,N'-bis-(phenyl)benzidine ( α-NPB); and porphyrin compounds, such as copper phthalocyanine. Commonly used hole transport polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl)polysiloxane, poly(dioxythiophene), polyaniline, and polypyrrole. It is also possible to obtain hole-transporting polymers by incorporating hole-transporting molecules such as those described above into polymers such as polystyrene and polycarbonate. In some cases, triarylamine polymers are used, especially triarylamine-stilbene copolymers. In some cases, the polymers and copolymers are crosslinkable. Examples of crosslinkable hole transport polymers can be found in, for example, published U.S. patent application 2005-0184287 and published PCT application WO 2005/052027. In some embodiments, the hole transport layer is doped with p-type dopants, such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10-tetracarboxy-3,4,9,10 -Dianhydride.

Depending on the application of the device, the photoactive layer 120 may be a light-emitting layer 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-conversion phosphor device), or a layer of material that reacts to radiant energy and generates a signal with or without an applied bias (such as in a photodetector or photovoltaic device).

In some embodiments, the photoactive layer includes a compound that includes an emissive compound as a photoactive material. In some embodiments, the light active layer further includes a host material. Examples of host materials include, but are not limited to, phenanthrene, triphenanthrene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoline, phenylpyridine, carbazole, indolocarbazole, furan, benzene Difuran, dibenzofuran, benzodifuran and metal quinoline complexes. In some embodiments, the host material is deuterated.

In some embodiments, the photoactive layer includes (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.

In some embodiments, the photoactive layer only includes (a) an electroluminescent dopant capable of having an emission maximum between 380 and 750 nm, (b) a first host compound, and (c) a second The host compound, in which there is no additional material that will substantially change the operating principle or distinguishing characteristics of the layer.

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

In some embodiments, the weight ratio of the first body to the second body in the light active layer is in the range of 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, the weight ratio is in the range of 3:1 to 1:1.

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

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

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

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

An optional layer can simultaneously play a role in promoting electron transport and also serve as a confinement layer to prevent the quenching of excitons at the layer interface. Preferably, this layer promotes electron mobility and reduces exciton quenching.

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 quinolinate derivatives such as tris(8-quinolinolato) aluminum (AlQ), double (2-Methyl-8-quinolinolato)(p-phenylphenolate) aluminum (BAlq), tetrakis-(8-hydroxyquinolinolato)hafnium (HfQ) and tetrakis-(8-hydroxyquinolinolato) Zirconium (ZrQ); and azole compounds, such as 2-(4-biphenyl)-5-(4-tertiary butylphenyl)-1,3,4-oxadiazole (PBD), 3-( 4-biphenyl)-4-phenyl-5-(4-tertiary butylphenyl)-1,2,4-triazole (TAZ) and 1,3,5-tris(phenyl-2- Benzimidazole)benzene (TPBI); Quinoline derivatives, such as 2,3-bis(4-fluorophenyl)quinoline; Phenoline, such as 4,7-diphenyl-1,10-phenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); three 𠯤; fullerene; and mixtures thereof. In some embodiments, the electron transport material is selected from the group consisting of: metal quinoline salts and phenanthroline derivatives. In some embodiments, the electron transport layer further includes 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 Cs ₂ CO ₃ ; 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 W ₂ (hpp) ₄ (where hpp = 1,3,4,6,7,8-hexahydro-2H- Pyrimido-[1,2-a]-pyrimidine) and cobalt diocene, tetrathiatetracene, bis(ethylenedithio)tetrathiafulvalene, heterocyclic group or divalent group, and Dimers, oligomers, polymers, dispiro compounds and polycyclic compounds of heterocyclic groups or divalent groups.

An optional electron injection layer can be deposited on the electron transport layer. Examples of electron injection materials include, but are not limited to, Li-containing organometallic compounds, LiF, Li ₂ O, lithium quinolate; Cs-containing organometallic compounds, CsF, Cs ₂ O, and Cs ₂ CO ₃ . This layer can 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 usually in the range of 1-100 Å, and in some embodiments 1-10 Å.

The cathode 130 is an electrode particularly effective for injecting electrons or negative charge carriers. The cathode can be any metal or non-metal with a lower work function than the anode. The material used for the cathode may be selected from the group 1 alkali metals (for example, 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 can be used.

It is known to have other layers in organic electronic devices. For example, there may be multiple layers (not shown) 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 serve as a protective layer . Layers known in the art, such as copper phthalocyanine, silicon oxynitride, fluorocarbon, silane, or ultra-thin layers of metals (such as Pt), can be used. Alternatively, some or all of the anode layer 110, the active layer 120, or the cathode layer 130 may be surface-treated to increase charge carrier transport efficiency. It is preferable to balance the positive and negative charges in the emitter layer to determine the selection of the material of each component layer to provide a device with high electroluminescence efficiency.

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

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

For the liquid deposition method, a person with ordinary knowledge in the art can easily determine the appropriate solvent for a specific compound or related class of compounds. For some applications, it is desirable that these compounds are dissolved in non-aqueous solvents. Such non-aqueous solvents may be relatively polar, such as C ₁ to C ₂₀ alcohols, ethers and acid esters, or may be relatively non-polar, such as C ₁ to C ₁₂ alkanes or aromatic compounds such as toluene, xylene, tri Fluorotoluene and so on. Other suitable liquids for the manufacture of liquid compositions including new compounds (as solutions or dispersions as described herein) include, but are not limited to, chlorinated hydrocarbons (such as dichloromethane, chloroform, chlorobenzene), aromatic hydrocarbons (such as substituted Unsubstituted 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 their mixtures. Suitable solvents for electroluminescent materials have been described in, for example, published PCT application WO 2007/145979.

In some embodiments, the device is prepared by liquid deposition of a hole injection layer, a hole transport layer, and a photoactive layer, and by vapor deposition of an anode, an electron transport layer, an electron injection layer, and a cathode on a flexible substrate. production.

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. Molded substrates and new hole transport materials that cause a decrease in operating voltage or increase quantum efficiency are also applicable. Additional layers can also be added to customize the energy level of each layer and promote electroluminescence.

In some embodiments, the device has the following structures in order: substrate, anode, hole injection layer, hole transport layer, light active layer, electron transport layer, electron injection layer, cathode.

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, the materials, methods, and examples are illustrative only and not intended to be limiting. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety.

Instance

The concepts described herein will be further illustrated in the following examples, which do not limit the scope of the present invention described in the scope of the patent application.

Example 1

This example illustrates the preparation of a diamine of formula I (compound 4).

(a) 2,6-bis(4-amino-2-trifluoromethylphenyl)anthracene (3) .

2,6-Bis-Bpin anthracene 1 (14.5 g, 33.71 mmol), 4-bromo-3-(trifluoromethyl)aniline 2 (24.27 g, 101.13 mmol), Pd(PPh ₃ ) ₄ (3.9 g, A mixture of 3.37 mmol) and potassium carbonate (23.29 g, 169 mmol) in toluene (400 ml), ethanol (200 ml) and water (80 ml) is degassed and heated at 85°C while stirring under a nitrogen atmosphere 3 days. The product 3 (9.7 g) precipitated from the reaction mixture was collected by hot filtration. The filtrate was cooled, and the precipitate was collected by filtration to produce 3.2 g of product with lower purity. ¹ H-NMR (DMSO-d ₆ , 500 MHz): 5.69 (s, 4H), 6.88 (dd, 2H, J1 = 2 Hz, J2 = 8 Hz), 7.03 (d, 2H, J = 2 Hz), 7.18 (d, 2H, J = 8 Hz), 7.40 (d, 2H, J = 9 Hz), 7.92 (s, 2H), 8.05 (d, 2H, J = 9 Hz), 8.58 (s, 2H).

(b) 6,14-bis(4-amino-2-trifluoromethylphenyl)-3a,4,9,9a-tetrahydro-2-phenyl-4,9[1',2'] -Benzo-1H-benzo[f]isoindole-1,3(2H)-dione (Compound 4).

A mixture of product 3 (7.637 g, 15.38 mmol) and N-phenylmaleimide (7.96 g, 45.97 mmol) in 1,2-dichlorobenzene (100 ml) at 150°C in a nitrogen atmosphere Heat for 1.5 hours. After that, an additional amount of maleimide (4.6 g) was added, and the mixture was heated at the same temperature for 1 hour. The reaction mixture was cooled, the solvent was evaporated using a rotary evaporator, and the residue was subjected to chromatographic purification on a silica gel column using a gradient elution with dichloromethane and a dichloromethane-acetone mixture. The product-containing fractions were collected and the eluent was evaporated to yield 6.41 g of diamine compound 4, which can be further purified by crystallization from a mixture of dichloromethane and hexane. ¹ H-NMR (DMSO-d ₆ , 500 MHz): 3.41 (dd, 1H, J1 = 4 Hz, J2 = 9 Hz), 3.47 (dd, 1H, J1 = 4 Hz, J2 = 9 Hz), 4.91 ( t, 2H, J = 4 Hz), 5.62 (s, 4H), 6.53-6.55 (m, 2H), 6.78 (td, 2H, J1 = 2Hz, J2 = 8 Hz), 6.89 (d, 1H, J = 8 Hz), 6.95 (dd, 2H, J1 = 2 Hz, J2 = 8 Hz), 7.02 (d, 1H, J = 8 Hz), 7.06 (d, 1H, J = 8 Hz), 7.10 (d, 1H , J = 8 Hz), 7.18 (s, 1H), 7.30 (d, 1H, J = 8 Hz), 7.32-7.33 (m, 3H), 7.41 (s, 1H), 7.49 (d, 1H, J = 8 Hz). ¹³ C-NMR (DMSO-d ₆ , 125 MHz, restricted configuration isomers): 176.35, 176.25, 148.83, 148.78, 141.7, 140.7, 139.4, 139.2, 138.9, 138.3, 133.64, 133.6, 132.3, 129.13, 128.9 , 127.9, 127.7, 127.5, 127.4, 127.11, 127.0, 126.0, 125.5, 124.7, 124.2, 123.8, 123.7, 117.0, 110.87, 110.83, 55.4, 47.22, 47.17, 45.0. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz, restricted configuration isomers): 55.27, 55.35.

Example 2

This example illustrates the preparation of a liquid composition comprising polyamic acid of formula II.

Make diamine compound 4 (4.5 g, 6.72 mmol), BPDA (2.768 g, 9.408 mmol), PMDA (0.293 g, 1.344 mmol), TFMB (2.152 g, 6.72 mmol) and N-methylpyrrolidone (62 g ) React at ambient temperature, then add PMDA (45 mg) in batches. The NMP was partially distilled out to a final 21 wt% polymer content and 27390 cP viscosity. GPC: Mn = 96941, Mw = 203561, Mp = 195824, Mz = 324327, PDI = 2.10.

Example 3

This example illustrates the preparation of a polyimide film, where the polyimide has formula III.

The polyamide acid solution from Example 2 was filtered through a micro filter, spin-coated onto a clean silicon wafer, soft-baked on a hot plate at 90°C, and placed in an oven. The furnace was purged with nitrogen and heated to a maximum temperature of 320°C. The wafer was taken out of the furnace, immersed in water and layered manually to produce a polyimide film sample.

Polyimide film with 8.62 µm thickness has the following characteristics: Haze: 0.19% T _g : 327°C CTE (first measurement): 34.1 ppm/°C Birefringence (633 nm): 0.042 Stretching mode Quantity: 4.77 GPa Tensile strength: 198.7 MPa Elongation at break: 24.6% 1% TGA loss: 415°C Optical delay: 369

It should be noted that not all of the activities described in the general description or examples above are necessary, some specific activities may not be necessary, and in addition to those described, one or more other activities may be carried out. activity. In addition, the order of the listed activities need not be the order in which they are performed.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, those with ordinary knowledge in the technical field can make various modifications and changes without departing from the scope of the present invention specified in the scope of the following patent applications. Therefore, the specification and the accompanying drawings should be regarded as exemplary rather than restrictive, and all such modifications are intended to be included in the scope of the present invention.

The benefits, other advantages, and solutions to problems have been described above with respect to specific embodiments. However, benefits, advantages, solutions to problems, and one or more of any features that may cause any benefit, advantage, or solution to appear or make it more obvious will not be construed as the key to any or all of the patented scope Essential, essential or basic characteristics.

It is to be understood that, for the sake of clarity, certain features described herein in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, for the sake of brevity, various features 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 an approximate value, just as the minimum and maximum values in the range are preceded by the word "about". In this way, slight changes above and below the stated ranges can be used to achieve substantially the same results as values in these ranges. Moreover, the disclosure of these ranges is intended as a continuous range including each value between the minimum and maximum average values, including fractional values that can be produced when some components of a value are mixed with components of different values. In addition, when a wider and narrower range is disclosed, it is within the expectations of the present invention to match the minimum value from one range with the maximum value from another range, and vice versa.

no

Embodiments are shown in the accompanying drawings to improve the understanding of the concepts as set forth herein.

Figure 1 includes a diagram of an example of a polyimide film that can serve as a flexible substitute for glass.

Figure 2 includes an illustration of an example of an electronic device including a flexible substitute for glass.

A skilled technician should understand that the object system in the figure is shown for simplicity and clarity, and is not necessarily drawn to scale. For example, the size of some objects in the figure may be enlarged relative to other objects to help improve the understanding of the embodiments.

Claims (9)

A polyamine of formula I:

, Where: Q ^{1 is} selected from the group consisting of H, R ¹ , and R ⁹ ; Q ^{2 is} selected from the group consisting of H, R ² , and R ⁹ ; Q ^{3 is} selected from the group consisting of R ³ and R ⁹ ; Q ^{4 is} selected from the group consisting of R ⁴ and R ⁹ ; Q ^{5 is} selected from the group consisting of R ⁷ and R ⁹ ; R ¹ and R ² are the same or different each time, and are selected from the following Item composition group: F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, silalkoxy, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl , And unsubstituted or substituted aryloxy; R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same or different, and are selected from the group consisting of: H, F, CN, alkane Group, fluoroalkyl group, alkoxy group, fluoroalkoxy group, silyl group, silalkoxy group, unsubstituted or substituted hydrocarbon aryl group, unsubstituted or substituted heteroaryl group, and unsubstituted or substituted aryloxy group; R ^{8 is} selected from the group consisting of: alkyl, silyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl; R ⁹ is the same or different in each occurrence, And is selected from the group consisting of NH ₂ and ArNH ₂ ; Ar is the same or different each time, and is an unsubstituted or substituted C _6-18 hydrocarbon aryl group; and a and b are the same or different, and It is an integer from 0 to 3; the premise is that at least two of Q ¹ to Q ⁵ are R ⁹ . The polyamine described in item 1 of the scope of patent application has formula IA:

. The polyamine described in item 1 of the scope of patent application has the formula IB:

. The polyamine described in item 1 of the scope of patent application has the formula IC:

. A polyamide acid having a repeating unit of formula II:

, Where: 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; wherein 10-100 mol% of R ^b is derived from one or more diamine residues having the diamine of formula I as described in item 1 of the patent application. A liquid composition comprising (a) the polyamide acid described in item 5 of the scope of the patent application, and (b) a high-boiling aprotic solvent. A polyimide having a repeating unit of formula III:

, Where: 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; wherein 10-100 mol% of R ^b is derived from one or more diamine residues having the diamine of formula I as described in item 1 of the patent application. An organic electronic device having at least one layer, the at least one layer comprising a polyimide film having a repeating unit of formula III as described in item 7 of the scope of the patent application. The organic electronic device described in item 8 of the scope of patent application, wherein the layer is used in device components selected from the group consisting of: device substrate, color filter substrate, cover film, and touch Style screen panel.

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