TW202012495A - Polymers for use in electronic devices - Google Patents

Abstract

Disclosed is a polyimide film, where the polyimide has a weight average molecular weight of at least 100,000, and includes a repeat unit structure of Formula V

. In Formula V: 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, where 30-100 mol% of R^b has Formula II or Formula III

. In Formula II and Formula III: R¹ and R² are the same or different and are F, R_f , or OR_f ; R_f is a C_1-3 perfluoroalkyl; and * indicates a point of attachment.

Description

Polymers for electronic devices

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

Materials used in electronic applications usually have strict requirements in terms of their structural properties, optical properties, thermal properties, electronic properties, and other properties. As the number of commercial electronic applications continues to increase, the breadth and specificity of the required characteristics require innovation in materials with new and/or improved characteristics. Polyimide represents a class of polymeric compounds widely used in various electronic applications. They can serve as a flexible substitute for glass in electronic display devices, provided they have suitable characteristics. These materials can be used as components of liquid crystal displays ("LCDs"), where their moderate electrical power consumption, light weight, and layer flatness are key characteristics of practical utility. Other uses in electronic display devices that preferentially set such parameters include device substrates, 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 ("OLEDs"). Due to 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, palmtop/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 like polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) ), they are often better in flexible display applications.

However, due to the priority given to optical transparency, the use of traditional amber-colored polyimide has been hampered in some display applications such as filters and touch screen panels. In addition, 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 the refractive index (birefringence) between the parallel and vertical directions of the film, resulting in optical retardation that may adversely affect display performance. If you are looking for additional uses of polyimide in the display market, you need a solution that maintains its desired properties while improving its optical transparency and reducing amber and birefringence that causes light retardation.

Therefore, there is a continuing demand for polymer materials suitable for electronic devices.

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；並且 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30-100 mol%的R^b 具有式II或式III

其中： R¹ 和R² 係相同或不同的，並且選自由F、R_f 、以及OR_f 組成之群組； R_f 係C_1-3 全氟烷基；並且 *表示附接點； 其中R¹ 和R² 兩者均與附接點相鄰；以及 (b) 高沸點非質子溶劑。Provided is a liquid composition having a solid content of at least 10 wt% and a viscosity of at least about 3000 cps, the composition comprising (a) a polyamic acid having a repeating unit structure of Formula I

Where: R ^a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R ^b is the same or different at each occurrence and represents one or more aromatics Diamine residues; of which 30-100 mol% of R ^b have formula II or formula III

Where: R ¹ and R ² are the same or different, and are selected from the group consisting of F, R _f , and OR _f ; R _f is C _1-3 perfluoroalkyl; and * represents the attachment point; where R Both ¹ and R ² are adjacent to the point of attachment; and (b) a high boiling aprotic solvent.

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；並且 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30-100 mol%的R^b 具有式II或式III

其中： R¹ 和R² 係相同或不同的，並且選自由F、R_f 、以及OR_f 組成之群組； R_f 係C_1-3 全氟烷基；並且 *表示附接點； 其中R¹ 和R² 兩者均與附接點相鄰； 並且進一步地，其中該聚醯亞胺膜 根據按順序並且不重複地包括以下步驟的方法製備： 將在高沸點非質子溶劑中包含一種或多種四羧酸組分和一種或多種二胺組分的聚醯胺酸溶液塗佈到基體上； 軟烘該經塗佈的基體； 以多個預先選擇的時間間隔在多個預先選擇的溫度下處理該軟烘的經塗佈的基體。Further provided is a polyimide film, wherein the polyimide has a number average molecular weight of at least 100,000, and includes a repeating unit structure of formula V

Where: R ^a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R ^b is the same or different at each occurrence and represents one or more aromatics Diamine residues; of which 30-100 mol% of R ^b have formula II or formula III

Where: R ¹ and R ² are the same or different, and are selected from the group consisting of F, R _f , and OR _f ; R _f is C _1-3 perfluoroalkyl; and * represents the attachment point; where R Both ¹ and R ² are adjacent to the attachment point; and further, wherein the polyimide membrane is prepared according to a method that includes the following steps in order and without repeating: a high boiling point aprotic solvent will contain one or Polyamide solutions of multiple tetracarboxylic acid components and one or more diamine components are applied to the substrate; the coated substrate is soft baked; at multiple preselected temperatures at multiple preselected intervals The soft-baked coated substrate is processed next.

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；並且 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30-100 mol%的R^b 具有式II或式III

其中： R¹ 和R² 係相同或不同的，並且選自由F、R_f 、以及OR_f 組成之群組； R_f 係C_1-3 全氟烷基；並且 *表示附接點； 其中R¹ 和R² 兩者均與附接點相鄰； 並且進一步地，其中該聚醯亞胺膜 根據按順序並且不重複地包括以下步驟的方法製備： 將在高沸點非質子溶劑中包含一種或多種四羧酸組分和一種或多種二胺組分的聚醯胺酸溶液塗佈到基體上； 軟烘該經塗佈的基體； 以多個預先選擇的時間間隔在多個預先選擇的溫度下處理該軟烘的經塗佈的基體。A polyimide film is further provided, wherein the polyimide has a weight average molecular weight of at least 100,000, and includes a repeating unit structure of formula V

Where: R ^a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R ^b is the same or different at each occurrence and represents one or more aromatics Diamine residues; of which 30-100 mol% of R ^b have formula II or formula III

Where: R ¹ and R ² are the same or different, and are selected from the group consisting of F, R _f , and OR _f ; R _f is C _1-3 perfluoroalkyl; and * represents the attachment point; where R Both ¹ and R ² are adjacent to the attachment point; and further, wherein the polyimide membrane is prepared according to a method that includes the following steps in order and without repeating: a high boiling point aprotic solvent will contain one or Polyamide solutions of multiple tetracarboxylic acid components and one or more diamine components are applied to the substrate; the coated substrate is soft baked; at multiple preselected temperatures at multiple preselected intervals The soft-baked coated substrate is processed next.

There is further provided a flexible substitute for glass in an electronic device, wherein the flexible substitute for glass is the polyimide film described above.

There is further provided an electronic device having at least one layer including the polyimide film described above.

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

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

A polyamide having formula I is provided, as described in detail below.

There is further provided a composition comprising (a) a polyamic acid having formula I and (b) a high-boiling aprotic solvent.

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

Further provided is one or more methods for preparing a polyimide film, wherein the polyimide film has a repeating unit of Formula IV.

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

There is further provided an electronic device having at least one layer including a polyimide film having a repeating unit of Formula IV.

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

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

Other features and benefits of any one or more embodiments will be apparent from the detailed description below and from the scope of patent applications. The detailed description first proposes the definition and clarification of terms, and then the liquid composition, polyimide, the method for preparing the polyimide film, the electronic device, and finally the example. 1. Definition and clarification of terms

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

Those are the same or different 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 in the formula.

The term "orientation layer" is intended to refer to the organic polymer layer in a liquid crystal device (LCD), which results in the molecules closest to each as a result of its rubbing onto the LCD glass in a preferred direction during the LCD manufacturing process The board is 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 hydrocarbon groups. In some embodiments, the alkyl group can be mono-, di-, and tri-substituted. An example of a substituted alkyl group is trifluoromethyl. Other substituted alkyl groups are formed from 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 class of solvents that lack acidic hydrogen atoms and therefore cannot serve as hydrogen donors. 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 refer to an organic compound containing at least one unsaturated cyclic group having 4n + 2 unlocalized π electrons. The term is intended to cover both aromatic compounds and heteroaromatic compounds. The aromatic compound has only carbon and hydrogen atoms. One or more carbon atoms in the cyclic group in the heteroaromatic compound have been replaced by another Replace atoms such as nitrogen, oxygen, and sulfur.

The term "aryl" or "aryl group" refers to a portion formed by removing one or more hydrogen ("H") or deuterium ("D") from an aromatic compound. The aryl group may be a single ring (monocyclic) or have multiple rings (bicyclic, or more) fused together or covalently linked. 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 4-50 ring carbon atoms; in some embodiments, 4-30 ring carbon atoms.

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

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

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, silaneoxy 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 some embodiments. The substituent may also be a crosslinking group.

The term "amine" is intended to mean a compound containing a basic nitrogen atom with a lone pair of electrons. The term "amino" means a functional group -NH _2, -NHR or -NR _2, wherein R in each occurrence can be the same or different and is an alkyl group or an aryl group. The term "diamine" is intended to refer to a compound containing two basic nitrogen atoms with associated lone pairs. The term "aromatic diamine" is intended to refer to an aromatic compound having two amine groups. The term "bent diamine" is intended to refer to a diamine in which two basic nitrogen atoms and associated lone pairs of electrons are arranged asymmetrically around the center of symmetry of the corresponding compound or functional group, such as m-benzene Diamine:

The term "aromatic diamine residue" is intended to refer to a portion bonded to two amine groups in the aromatic diamine. The term "aromatic diisocyanate residue" is intended to refer to a portion bonded to two isocyanate groups in an aromatic diisocyanate compound. This is explained further below.

The terms "diamine residue" and "diisocyanate residue" are intended to refer to moieties bonded to two amine groups or two isocyanate groups, respectively, where the moieties can be aromatic or aliphatic.

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 positive b* values, and blue is represented by negative b* values. 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 characteristics of the solvent and/or characteristics related to low levels of impurities contained in various solvents. Usually a specific solvent is pre-selected to achieve the desired b* value 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 x-axis or y-axis (in-plane) and the z-axis (out-of-plane) refractive index.

When referring to a layer, material, component, or structure, the term "charge transport" is intended to mean that such layer, material, component, or structure promotes such charge to pass through such layer, material with relative efficiency and small charge loss , Thickness of components, or structures. Hole transport materials are conducive to positive charges; electron transport materials are conducive to negative charges. Although the luminescent material may also have some charge transport characteristics, 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 that further include 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 "linear thermal expansion coefficient (CTE or α)" is intended to refer to a parameter that defines the amount by which a material expands or contracts with temperature. It is expressed as a change in length per degree Celsius and is usually expressed in units of µm/m/ºC or ppm/ºC. α = (ΔL/L ₀ )/ΔT

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

The term "dopant" is intended to refer to the material within a layer that includes the host material, and is related to one or more electronic properties or one or more wavelengths of the layer's radiation emission, reception, or filtering 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 "electrically active" is intended to mean a layer or material that electronically facilitates the operation of the device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block charges, where the charges can be electrons or holes, or materials that emit radiation or exhibit electron-hole pair concentration changes when receiving radiation. Examples of inactive materials include but are not limited to planarizing materials, insulating materials, and environmental barrier materials.

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

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

The term "glass transition temperature (or _Tg )" is intended to refer to the temperature at which a reversible change occurs in an amorphous polymer or in an amorphous region of a semi-crystalline polymer, where the material suddenly changes from a hard, glassy or brittle state Become flexible or elastic. Under the microscope, a glass transition occurs when the normally wound static polymer chains become freely rotating and can move through each other. You can use differential scanning calorimetry (DSC), thermal mechanical analysis (TMA) and dynamic mechanical analysis (DMA) or other methods for measuring T _g.

The prefix "hetero" indicates 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 130ºC.

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

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

The term "liquid composition" is intended to refer to a liquid medium in which the material is dissolved to form a solution, a liquid medium in which the material is dispersed to form a dispersion, or a liquid medium in which the 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, for example, in the formation of 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 (not including 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), which is then multiplied by the thickness of the film or coating . The light delay is typically measured for light of a given frequency, and the units are 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 measurement of the particle content can be carried out on the solution itself or on the finished materials (sheets, films, etc.) prepared from those films. Various optical methods can be used to evaluate this characteristic.

The term "photoactive" refers to emitting light when activated by an applied voltage (as in a light-emitting diode or chemical cell), emitting light after absorbing photons (as in a down-converter phosphor device), or responding to A material or layer that radiates energy and generates a signal with or without an applied bias (as in a photodetector or photovoltaic cell).

The term "polyamide solution" refers to a solution of a polymer containing an amide acid unit that has an intramolecular cyclization ability to form an imidate group.

The term "polyimide" refers to a condensate obtained by reacting one or more bifunctional carboxylic acid components with one or more primary diamines or diisocyanates. They contain amide imide 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 satisfies all requirements/requirements of the material in use. For example, in the context of the polyimide film disclosed herein, an isothermal weight loss of less than 1% in nitrogen at 350ºC for 3 hours can be considered as a non-limiting example of "satisfactory" characteristics.

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

The term "substrate" refers to a base material that can be rigid or flexible and can include one or more layers of one or more materials, which can include, but is 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, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced with Si.

The term "Silane group" means a group R ₃ SiO-, wherein R at each occurrence are the same or different and are H, C1-20 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, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced with Si.

The term "spin coating" is intended to refer to a process for depositing a uniform thin film onto a flat substrate. Generally, a small amount of coating material is applied to the center of the substrate, which rotates at a low speed or does not rotate at all. The substrate is then rotated at a prescribed speed to spread the coating material uniformly by centrifugal force.

The term "laser particle counter test" refers to a method for evaluating the particle content of polyamide and other polymer solutions, whereby a representative sample of the test solution is spin-coated onto a 5" silicon wafer and soft-bake /Dry. Evaluate the particle content of the film thus prepared by any number of standard measurement techniques. Such techniques include laser particle detection and other techniques known in the art.

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

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

The term "tetracarboxylic acid component residue" is intended to refer to the portion 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 that impinges on the film through the film so as to be detectable on the other side. The measurement of light transmittance in the visible region (380 nm to 800 nm) is particularly useful for characterizing the film color characteristics that are most important for understanding the characteristics of the polyimide film disclosed in this article in use.

The term "yellowness index (or YI)" refers to the magnitude of the yellowness relative to the standard. A positive value of YI indicates the presence and magnitude of yellow. The material with negative YI looks blue. Especially for polymerization and/or curing processes operating at high temperatures, it should also be noted that YI can be solvent dependent. For example, the magnitude of the color introduced using DMAC as the solvent may be different from the magnitude of the color introduced using NMP as the solvent. This can occur as a result of the inherent characteristics of the solvent and/or characteristics related to low levels of impurities contained in various solvents. Usually a specific solvent is pre-selected to achieve the desired YI value for a specific application.

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。In the structure where the substituent bond passes through one or more rings as shown below,

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

When used to refer to a layer 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 R groups immediately adjacent to each other in the chemical formula (ie, R groups on atoms bonded by bonds). Exemplary adjacent R groups are shown below:

In this specification, unless otherwise clearly indicated by the context of use or otherwise indicated, embodiments in which the subject of the present invention is stated or described as comprising, including, containing, having certain features or When an element, consists of, or consists of certain features or elements, one or more features or elements other than those expressly stated or described may also exist in this embodiment. The disclosed alternative embodiments of the inventive subject matter are described as consisting essentially of certain features or elements, where implementation features or elements that would substantially change the operating principles or distinguishing features of the embodiments do not exist here. Another alternative embodiment of the described subject matter of the invention is described as consisting of certain features or elements, and in this embodiment or in its non-essential variants, only the features or elements specifically stated or described are present.

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).

Also, use "a/an" to describe the elements and components described herein. This is done for convenience only and to give a general meaning of the scope of the invention. The description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it clearly indicates otherwise.

The family number corresponding to the column in the periodic table of elements uses the convention of "New Notation" as seen in 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 of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the 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 by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and are 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 fields of organic light-emitting diode displays, photodetectors, photovoltaics, and semiconductor components. 2. Liquid composition

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；並且 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30-100 mol%的R^b 具有式II或式III

其中： R¹ 和R² 係相同或不同的，並且選自由F、R_f 、以及OR_f 組成之群組； R_f 係C_1-3 全氟烷基；並且 *表示附接點； 其中R¹ 和R² 兩者均與附接點相鄰；以及 (b) 高沸點非質子溶劑。Provided is a liquid composition having a solid content of at least 10 wt% and a viscosity of at least about 3,000 cps (cps = centipoise), the composition comprising (a) a polyamic acid having a repeating unit structure of formula I

Where: R ^a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R ^b is the same or different at each occurrence and represents one or more aromatics Diamine residues; of which 30-100 mol% of R ^b have formula II or formula III

Where: R ¹ and R ² are the same or different, and are selected from the group consisting of F, R _f , and OR _f ; R _f is C _1-3 perfluoroalkyl; and * represents the attachment point; where R Both ¹ and R ² are adjacent to the point of attachment; and (b) a high boiling aprotic solvent.

This liquid composition is also called "polyamide solution" in the text.

In some embodiments of the liquid composition, the solids content is at least 12 wt%; in some embodiments, it is at least 15 wt%. In some embodiments, the solids content is 10-20 wt%.

In some embodiments of the liquid composition, the viscosity is at least about 5000 cps; in some embodiments, at least about 10,000 cps.

In certain embodiments of Formula I, R ^a represents a single tetracarboxylic acid component residue.

In certain embodiments of Formula I, R ^a represents two tetracarboxylic acid component residue.

In certain embodiments of Formula I, R ^a represents a three tetracarboxylic acid residue.

In certain embodiments of Formula I, R ^a represents a four tetracarboxylic acid residue.

In certain embodiments of Formula I, 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 diphthalic anhydride (6FDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenylbenzene tetracarboxylic dianhydride (DSDA), 4,4'-bisphenol-A dianhydride (BPADA), hydroquinone diphthalic anhydride (HQDEA ), ethylene glycol bis(trimellitic anhydride) (TMEG-100), 4-(2,5-bi- pendant tetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-di Formic anhydride (DTDA); 4,4'-bisphenol A dianhydride (BPADA), etc. and combinations thereof. These aromatic dianhydrides may be substituted with groups known in the art as needed, such groups include alkyl, aryl, nitro, cyano, -N(R')(R ^" ), halogen, hydroxyl , Carboxyl, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl , Silyl, siloxy, siloxane, thioalkoxy, -S(O) ₂ -, -C(=O)-N(R')(R”), (R')(R” )N-alkyl, (R')(R")N-alkoxyalkyl, (R')(R")N-alkylaryloxyalkyl, -S(O) _s -aryl ( Where s = 0-2) or -S(O) _s -heteroaryl (where s = 0-2). Each R'and R" is independently an optionally substituted alkyl, cycloalkyl or aryl Group. R'and R", together with the nitrogen atom to which they are bound, may form a ring system in some embodiments. The substituent may also be a crosslinking group.

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

In certain embodiments of Formula I, R ^a represents a residue of PMDA.

In certain embodiments of Formula I, R ^a represents a residue of BPDA.

In certain embodiments of Formula I, R ^a represents a residue of 6FDA.

In certain embodiments of Formula I, R ^a represents a residue BTDA.

In certain embodiments of Formula I, R ^a represents a residue of PMDA and BPDA residues.

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

In certain embodiments of Formula I, R ^a represents a residue of PMDA and BTDA residues.

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

In certain embodiments of Formula I, R ^a represents a residue of BPDA and BTDA residues.

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

In Formula I, 30-100 mol% of R ^b represents having a diamine residue of Formula II or Formula III as shown above. In some embodiments of Formula I, 40-100 mol% of R ^b has Formula II; 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 mol%.

In some embodiments of Formula II, R ¹ is F.

In some embodiments of Formula II, R ¹ is C _1-3 perfluoroalkyl; in some embodiments, it is trifluoromethyl.

In some embodiments of Formula II, R ¹ is C _1-3 perfluoroalkoxy; in some embodiments it is trifluoromethoxy.

In some embodiments of Formula II, R ¹ = R ² .

In some embodiments of Formula II, R ¹ ≠ R ² .

All of the above-described embodiments for R ¹ in formula II also apply to R ² in formula II.

For all embodiments of Formula ^II, R ¹ and R ² described above apply equally to formula ^III, R ¹ and R ^2.

In some embodiments of Formula I, R ^b represents a residue from a diamine selected from the group consisting of compounds IV-A to IV-F shown below.

(2)

The diamine can be prepared as shown in the following scheme. (1)

(2)

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

In some embodiments of Formula I, R ^b represents a diamine residue having Formula II or Formula III and an additional diamine residue.

In some embodiments of Formula I, R ^b represents a diamine residue having Formula II or Formula III and two additional diamine residues.

In some embodiments of Formula I, R ^b represents a diamine residue having Formula II or Formula III and three additional 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-toluidine), 3,3'-dimethyl-4,4'-diaminobiphenyl (o-tolidine), 3,3'-dihydroxy-4,4'-diaminobiphenyl (HAB), 9,9'-bis(4-aminophenyl) stilbene (FDA), o-toluidine sulfone (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'-methylenedi 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'-diaminodiphenylbenzene (3,3'-DDS), 4,4'-diaminodiphenylbenzene (4 ,4'-DDS), 4,4'-diaminodiphenyl sulfide (ASD), 2,2-bis[4-(4-amino-phenoxy)phenyl] benzene (BAPS), 2 ,2-bis[4-(3-aminophenoxy)-phenyl] benzene (m-BAPS), 1,4'-bis(4-aminophenoxy)benzene (TPE-Q), 1 ,3'-bis(4-aminophenoxy)benzene (TPE-R), 1,3'-bis(4-amino-phenoxy)benzene (APB-133), 4,4'-bis (4-aminophenoxy) biphenyl (BAPB), 4,4'-diaminobenzidine (DABA), methylene bis(o-aminobenzoic 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'-di Aminodiphenylmethane (TMMDA), etc. and combinations thereof.

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

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

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

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

In some embodiments of Formula I, 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 analogs and derivatives thereof.

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

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

In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a weight average molecular weight (M _W ) greater than 150,000.

In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a molecular weight (M _W ) greater than 200,000.

In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a weight average molecular weight (M _W ) greater than 250,000.

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

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

In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a weight average molecular weight (M _W ) between 200,000 and 400,000.

In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a weight average molecular weight (M _W ) between 250,000 and 350,000.

In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a weight average molecular weight (M _W ) between 200,000 and 300,000.

Any of the above-mentioned embodiments of polyamic acid may be combined with one or more of other embodiments as long as they are not mutually exclusive. For example, the embodiment where R ^a represents a PMDA residue can be combined with the embodiment where R ^b has Formula II.

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), dimethylsulfoxide (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 γ-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 high boiling aprotic solvent indicated above is used in the liquid composition.

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

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

The polyamic acid solution can be prepared using various methods available for introducing components (ie, monomers and solvents). Some methods for producing polyamide solutions include:

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

(b) A method in which a solvent is added to a stirred mixture of diamine and dianhydride components. (Contrary to (a) above)

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

(d) A method in which the dianhydride component is separately dissolved in a solvent, and then the amine component is added thereto in a ratio that allows the reaction rate to be controlled.

(e) A method in which the diamine component and the dianhydride component are separately dissolved in a solvent and then such solutions are mixed in the reactor.

(f) A method in which a polyamic acid having an excess amine component and another polyamic acid having an excess dianhydride component are formed in advance, and then reacted with each other in the reactor, in particular to produce Random or block copolymers react with each other in this way.

(g) A method in which a specific portion of the amine component and the dianhydride component are reacted first, and then the residual diamine component is reacted, or vice versa.

(h) A method in which these components are added to part or all of the solvent in any order in part or in whole, and in addition part or all of any of the components may be added as a solution in part or all of the solvent.

(i) A method in which one of the dianhydride components and one of the diamine components are first reacted to obtain the first polyamic acid. Then another dianhydride component is reacted with another amine component to obtain a second polyamide. This polyamic acid is then combined in any of a variety of ways before film formation.

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

The polyamide solution can then be filtered one or more times to reduce the particle content. The polyimide membrane produced from this filtered solution can show a reduced number of defects, and thus produce excellent performance in the electronic applications disclosed herein. Filtration efficiency can be evaluated by laser particle counter testing, where a representative sample of polyamide solution is cast onto a 5" silicon wafer. After soft baking/drying, by any number of lasers The particle counting technique evaluates the particle content of the membrane on commercially available and known in the art instruments.

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

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

In some embodiments, a polyamide 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 polyamic 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 polyamic 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.

Exemplary preparations of polyamic acid solutions are given in the examples.

The overall polyamide composition can be named via symbols commonly used in the art. For example, a polyamic acid having a tetracarboxylic acid component of 100% ODPA and a diamine component of 90 mol% Bis-P and 10 mol% TFMB can be expressed as: ODPA//Bis-P/TFMB 100//90/10. 3. Polyimide film

A polyimide film is provided, which is made of the polyamic acid solution described above.

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；並且 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30-100 mol%的R^b 具有式II或式III

其中： R¹ 和R² 係相同或不同的，並且選自由F、R_f 、以及OR_f 組成之群組； R_f 係C_1-3 全氟烷基；並且 *表示附接點； 其中R¹ 和R² 兩者均與附接點相鄰； 並且進一步地，其中該聚醯亞胺膜 根據按順序並且不重複地包括以下步驟的方法製備： 將在高沸點非質子溶劑中包含一種或多種四羧酸組分和一種或多種二胺組分的聚醯胺酸溶液塗佈到基體上； 軟烘該經塗佈的基體； 以多個預先選擇的時間間隔在多個預先選擇的溫度下處理該軟烘的經塗佈的基體。The polyimide has a repeating unit structure of formula V

Where: R ^a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R ^b is the same or different at each occurrence and represents one or more aromatics Diamine residues; of which 30-100 mol% of R ^b have formula II or formula III

Where: R ¹ and R ² are the same or different, and are selected from the group consisting of F, R _f , and OR _f ; R _f is C _1-3 perfluoroalkyl; and * represents the attachment point; where R Both ¹ and R ² are adjacent to the attachment point; and further, wherein the polyimide membrane is prepared according to a method that includes the following steps in order and without repeating: a high boiling point aprotic solvent will contain one or Polyamide solutions of multiple tetracarboxylic acid components and one or more diamine components are applied to the substrate; the coated substrate is soft baked; at multiple preselected temperatures at multiple preselected intervals The soft-baked coated substrate is processed next.

For all the embodiments of formula I R ^a and R ^b are described above apply equally to formula V R ^a and R ^b are.

All of the above-described embodiments for R ¹ and R ² in Formula II as applicable to Formula I also apply to R ¹ and R ² in Formula II and Formula III as applicable to Formula V.

The polyimide film is made by applying the above-described polyamic acid solution onto the substrate and then imidizing. This can be achieved by thermal conversion methods or chemical conversion methods. Any known coating method can be used.

Some fluorinated diamines are known to have low reactivity. In order to use these low-reactivity diamines to form a polyimide film having a sufficient molecular weight, multiple polymerization steps are used. Typically, a low-reactivity diamine is used to prepare a polyamic acid solution, the solution is coated and imidized, and the imidized product is dissolved, recoated, and reimidized. The additional steps of dissolving, recoating and re-imidization are repeated several times.

Surprisingly and unexpectedly, diamines with residues of formula II or formula III have been found to have better reactivity. Using a single polymerization and amide imidization step, the polyimide membrane has sufficient molecular weight and good mechanical properties. With the polyamic acid solution described herein, there is no need to form an imidate product, dissolve, recoat, and amidate multiple times.

In some embodiments of the polyimide membrane, based on gel permeation chromatography and polystyrene standards, the polyimide polymer has a weight average molecular weight (M _W ) greater than 100,000.

In some embodiments of the polyimide membrane, based on gel permeation chromatography and polystyrene standards, the polyimide polymer has a weight average molecular weight (M _W ) greater than 150,000.

In some embodiments of the polyimide membrane, based on gel permeation chromatography and polystyrene standards, the polyimide polymer has a molecular weight (M _W ) greater than 200,000.

In some embodiments of the polyimide membrane, based on gel permeation chromatography and polystyrene standards, the polyimide polymer has a weight average molecular weight (M _W ) greater than 250,000.

In some embodiments of the polyimide membrane, based on gel permeation chromatography and polystyrene standards, the polyimide polymer has a weight average molecular weight (M _W ) greater than 300,000.

In some embodiments of the polyimide membrane, based on gel permeation chromatography and polystyrene standards, the polyimide polymer has a weight average molecular weight (M _W ) between 100,000 and 400,000.

In some embodiments of the polyimide membrane, based on gel permeation chromatography and polystyrene standards, the polyimide polymer has a weight average molecular weight (M _W ) between 200,000 and 400,000.

In some embodiments of the polyimide membrane, based on gel permeation chromatography and polystyrene standards, the polyimide polymer has a weight average molecular weight (M _W ) between 250,000 and 350,000.

In some embodiments of the polyimide membrane, based on gel permeation chromatography and polystyrene standards, the polyimide polymer has a weight average molecular weight (M _W ) between 200,000 and 300,000.

In some embodiments of the polyimide film, the in-plane thermal expansion coefficient (CTE) is less than 45 ppm/ºC between 50ºC and 200ºC; in some embodiments, it is less than 30 ppm/ºC; in some embodiments Is less than 20 ppm/ºC; in some embodiments it is less than 15 ppm/ºC; in some embodiments it is between 0 ppm/ºC and 15 ppm/ºC; in some embodiments it is 0 Between ppm/ºC and 10 ppm/ºC.

In some embodiments of the polyimide film, the glass transition temperature (T _g ) is greater than 250ºC for the polyimide film cured at a temperature in excess of 300ºC; in some embodiments, it is greater than 300ºC; In some embodiments, it is greater than 350ºC.

In some embodiments of the polyimide film, the 1% TGA weightlessness temperature is greater than 350ºC; in some embodiments, it is greater than 400ºC; in some embodiments, it is greater than 450ºC.

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 12.0 GPa.

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

In some embodiments of the polyimide film, the optical retardation is less than 500 at 550 nm; in some embodiments, it is less than 200.

In some embodiments of the polyimide film, the birefringence index at 633 nm is less than 0.15; in some embodiments, it is less than 0.10; in some embodiments, it is less than 0.05.

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

In some embodiments of the polyimide film, b* is less than 7.5; in some embodiments, it is less than 5.0; in some embodiments, it is less than 3.0. In some embodiments of the polyimide film, YI is less than 12; in some embodiments, it is less than 10; in some embodiments, it is less than 5.

In some embodiments of the polyimide film, the transmittance at 400 nm is greater than 40%; in some embodiments, it is greater than 50%; in some embodiments, it is greater than 60%.

In some embodiments of the polyimide film, the transmission at 430 nm is greater than 60%; in some embodiments, it is greater than 70%.

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

In some embodiments of the polyimide film, the transmittance at 750 nm is greater than 70%; in some embodiments, it is greater than 80%; in some embodiments, it is greater than 90%.

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

Polyimide membranes are prepared from 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 thermal conversion or improved thermal conversion methods and chemical conversion methods.

Chemical conversion 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 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 dehydrating materials are typically used in a slight molar excess of the amount of amidic acid groups present in the polyamic acid solution. The amount of acetic anhydride used is typically about 2.0-3.0 moles per equivalent of polyamide. 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 polyamic acid casting solution to polyimide. If conversion chemicals are used, this method can be considered as an improved thermal conversion method. In the two types of thermal conversion methods, only the thermal energy is used to heat the membrane to not only dry the membrane of the solvent but also perform the amide imidization reaction. Thermal conversion methods with or without conversion catalysts are generally used to prepare the polyimide membranes disclosed herein.

Considering that not only the composition of the film produces the characteristics of interest, the specific method parameters are pre-selected. in contrast,

The curing temperature and temperature ramp curve also play an important role in achieving the most desirable characteristics of the intended use disclosed herein. The polyamic acid should be at or above the maximum temperature of any subsequent processing steps (such as deposition of one or more inorganic or other layers required to produce a functional display), but below the polyimide Acetylimidization at a temperature where 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 imidateization.

For the polyamic acid/polyimide disclosed herein, when a subsequent processing temperature exceeding 300ºC is required, a temperature of 300ºC to 320ºC is typically used. The selection of an appropriate curing temperature allows to obtain 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 imidate process effectively achieves a higher level of imidate at a curing temperature between about 200ºC and 300ºC. If the flexible device was prepared at the higher curing temperature T _g of the polyimide is less than, then the method can be employed as necessary.

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 320ºC curing, the curing time can be up to about 1 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 skilled in the art will recognize the balance between temperature and time in order to optimize the characteristics of the polyimide for a specific end use.

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

In some embodiments of the thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 50 µm.

In some embodiments of the thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 40 µm.

In some embodiments of the thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 30 µm.

In some embodiments of the thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 20 µm.

In some embodiments of the thermal conversion method, the polyamic acid solution is applied to the substrate so that the soft-baking thickness of the resulting film is between 10 µm and 20 µm.

In some embodiments of the thermal conversion method, the polyamic acid solution is applied to the substrate so that the soft-baking thickness of the resulting film is between 15 µm and 20 µm.

In some embodiments of the thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of 18 μm.

In some embodiments of the thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of 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 hold 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 the 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, the coated substrate is soft baked using a hot plate set at 80°C.

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

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

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

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

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

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

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 may 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, wherein each of these time intervals may be the same or different.

In some embodiments of the thermal conversion method, the soft baked coated substrate is subsequently cured at 4 preselected temperatures at 4 preselected time intervals, wherein each of these time intervals may be the same or different.

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

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

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

In some embodiments of the thermal conversion method, the soft baked coated substrate is subsequently cured at 8 pre-selected temperatures and 8 pre-selected time intervals, wherein each of these time intervals may be the same or different of.

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

In some embodiments of the thermal conversion method, the soft baked coated substrate is subsequently cured at 10 pre-selected temperatures for 10 pre-selected time intervals, wherein each of these time intervals may 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 150ºC.

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 200ºC.

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 250ºC.

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

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

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 350ºC.

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 400ºC.

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 is 2 minutes.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 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 polyamic acid solution onto the substrate; soft-baking the coated substrate; in multiple The soft-baked coated substrate is treated at a pre-selected temperature for a plurality of pre-selected time intervals, whereby the polyimide film exhibits characteristics satisfactory for those electronic applications as disclosed herein.

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

In some embodiments of the thermal conversion method, the method for preparing the polyimide film is mainly composed of the following steps in order: coating the polyamic acid solution onto 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 exhibits characteristics satisfactory for those electronic applications as disclosed herein.

Typically, the polyamic acid solution/polyimide disclosed herein is coated/cured onto a 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 mechanical or laser lift-off processes. These processes separate the polyimide, which is a film with a deposited display layer, from the glass and realize a flexible form. Typically, the polyimide film with the deposited layer is then bonded to a thicker but still flexible plastic film to provide support for subsequent fabrication of the display.

An improved thermal conversion process is also provided, in which the conversion catalyst generally allows the amide imidization reaction to be carried out at a lower temperature than is possible in the absence of such conversion catalysts.

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

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

In some embodiments of the improved thermal conversion method, the polyamic 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 polyamic acid solution further contains a conversion catalyst selected from the group consisting of tributylamine, dimethylethanolamine, isoquinoline, 1,2- Dimethylimidazole, N-methylimidazole, 2-methylimidazole, 2-ethyl-4-imidazole, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethyl Pyridine, 5-methylbenzimidazole, etc.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the improved thermal conversion method, the polyamic acid solution is applied to the substrate so that the soft baking thickness of the resulting film is less than 50 µm.

In some embodiments of the improved thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 40 µm.

In some embodiments of the improved thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 30 µm.

In some embodiments of the improved thermal conversion method, the polyamic acid solution is applied to the substrate so that the soft baking thickness of the resulting film is less than 20 µm.

In some embodiments of the improved thermal conversion method, the polyamic acid solution is applied to the substrate so that the soft baking thickness of the resulting film is between 10 µm and 20 µm.

In some embodiments of the improved thermal conversion method, the polyamic acid solution is applied to the substrate so that the soft baking thickness of the resulting film is between 15 µm and 20 µm.

In some embodiments of the improved thermal conversion method, the polyamic acid solution is applied to the substrate so that the soft baking thickness of the resulting film is 18 µm.

In some embodiments of the improved thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 10 µm.

In some embodiments of the improved thermal conversion method, the coated substrate is soft baked in proximity mode on a hot plate, where nitrogen is used to hold 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 a hot plate, where 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, the coated substrate is soft-baked using a hot plate set at 80°C.

In some embodiments of the improved thermal conversion method, the coated substrate is soft-baked using a hot plate set at 90ºC.

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

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

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

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

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

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 improved 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 subsequently cured at 2 pre-selected temperatures at 2 pre-selected time intervals, where the time intervals may be the same or different .

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

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

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

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

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

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

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

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

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

In some embodiments of the improved 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 100ºC.

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

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

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

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

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

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

In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 230ºC.

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

In some embodiments of the improved 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 240ºC.

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

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

In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 260ºC.

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

In some embodiments of the improved 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 270ºC.

In some embodiments of the improved 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 improved 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 300ºC.

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

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 270ºC.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 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: applying a solution of a polyamic acid containing a conversion chemical onto a substrate; soft-baking the coated The substrate of the cloth; the soft-baked coated substrate is treated at a plurality of pre-selected temperatures at a plurality of pre-selected time intervals, whereby the polyimide film appears to be satisfactory for those electrons as disclosed herein Application characteristics.

In some embodiments of the improved thermal conversion method, the method for preparing the polyimide film is composed of the following steps in order: a solution of a polyamic acid containing a conversion chemical is coated on the substrate; Coated substrate; treating the soft-baked coated substrate at pre-selected temperatures at pre-selected time intervals, whereby the polyimide film appears to be satisfactory for those as disclosed herein Characteristics of electronic applications.

In some embodiments of the improved thermal conversion method, the method for preparing the polyimide film is mainly composed of the following steps in order: applying a polyamic acid solution containing a conversion chemical onto the substrate; soft baking the The coated substrate; the soft-baked coated substrate is treated at a plurality of preselected temperatures at a plurality of preselected time intervals, whereby the polyimide film appears to be satisfactory for use as disclosed herein The characteristics of those electronic applications. 5. 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, filter substrates, cover films, and the like. The specific material requirements for each application are unique and can be solved by one or more suitable compositions and one or more processing conditions of the polyimide film disclosed herein.

In some embodiments, the flexible alternative to glass in electronic devices is a polyimide film having repeating units of formula IV as described in detail above.

Organic electronic devices that may 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 (eg, light-emitting diodes, light-emitting diodes Displays, lighting devices, light sources, or diode lasers), (2) Devices that detect signals by electronic means (such as photodetectors, photoconductive cells, photoresistors, photocontrol relays, phototransistors, photocells, 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 of light (such as Frequency conversion phosphor device); and (5) a device including one or more electronic components including one or more organic semiconductor layers (eg, transistors or diodes). Other uses of the composition according to the 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 substitute for glass as described herein is shown in FIG. The flexible film 100 may have the 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 case 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 therebetween. There may be additional layers as needed. Adjacent to the anode may be a hole injection layer (not shown), sometimes referred to as a buffer layer. Adjacent to the hole injection layer may be a hole transport layer (not shown) containing hole transport material. Adjacent to the cathode may be an electron transport layer (not shown) containing electron transport material. Alternatively, the device may use one or more additional hole injection layers or hole transport layers (not shown) next to the anode 110 and/or one or more additional electron injection layers or electron transport next 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 filters, touch panels, and/or shields. One or more of these layers (other than the substrate 100) may also be made of the polyimide film disclosed herein.

The different layers will be further discussed here 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; photoactive 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 implementations In the mode, 300-5000 Å. The desired ratio of layer thickness will depend on the exact nature of the materials used.

In some embodiments, the organic electronic device (OLED) contains a flexible alternative to glass as disclosed herein.

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 layer is both a hole transport layer and an electron transport layer.

The anode 110 is an electrode that is particularly effective for injecting positive charge carriers. It can be made of, for example, materials containing metals, mixed metals, alloys, metal oxides, or mixed metal oxides, or it can be conductive polymers, and mixtures thereof. Suitable metals include Group 11 metals, metals in Groups 4, 5 and 6, and transition metals in Groups 8-10. If the anode is to be transparent, a mixed metal oxide of Group 12, 13 and 14 metals, such as indium tin oxide, is generally used. The anode may also contain organic materials such as polyaniline, as described in "Flexible light-emitting diodes made from soluble conducting polymer", Nature [Natural], Vol. 357, No. Pp. 477-479 (June 11, 1992). At least one of the anode and cathode should be at least partially transparent to allow the generated light to be observed.

The hole injection layer as needed may include a hole injection material. The term "hole injection layer" or "hole injection material" is intended to guide electrical or semi-conductive materials, and may have one or more functions in organic electronic devices, including but not limited to planarization of lower layers, charge transport and/or Or charge injection characteristics, the 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 may be a polymer, oligomer, or small molecule, and may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture, or other composition.

The hole injection layer may be formed of a polymer material, such as polyaniline (PANI) or polyethylene dioxythiophene (PEDOT), which is usually doped with protonic acid. The protonic acid may be, for example, poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), or the like. The hole injection layer 120 may include a charge transfer compound and the like, such as copper phthalocyanine and tetrathiofulvalene-tetracyano-p-phthalodiquinone dimethane system (TTF-TCNQ). In some embodiments, the hole injection layer 120 is made of a dispersion of a conductive polymer and a colloid-forming 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-transporting materials used in hole-transporting layers have been outlined in, for example, Kirk-Othmer Encyclopedia of Chemical Technology by Y. Wang [Kirk-Othmer Encyclopedia of Chemical Technology], Fourth Edition, Volume 18, 837 -860 pages, 1996. Both hole transporting small molecules and polymers can be used. Commonly used hole transport molecules include, but are not limited to: 4,4',4"-tri(N,N-diphenyl-amino)-triphenylamine (TDATA); 4,4',4"-tri(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(carbazol-9-yl)biphenyl (CBP); 1,3-bis(carbazole-9- Group) 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); pair -(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) polysilane, poly(dioxythiophene), polyaniline, and polypyrrole. It is also possible to obtain hole transport polymers by incorporating hole transport molecules such as those described above into polymers such as polystyrene and polycarbonate. In some cases, triarylamine polymers are used, especially triarylamine-stilbene copolymers. In some cases, the polymer and copolymer systems are crosslinkable. Examples of crosslinkable hole transport polymers can be found in, for example, published US 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 the applied voltage (as in a light-emitting diode or light-emitting electrochemical cell), a material layer that absorbs light and emits light with a longer wavelength (such as (In a down-converted phosphor device), or a layer of material that responds to radiant energy and generates a signal with or without an applied bias (as in a photodetector or photovoltaic device).

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

In some embodiments, the photoactive layer contains (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. The suitable second host compound is described above.

In some embodiments, the photoactive layer includes only (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, where there are no additional materials that will substantially change the operating principle or distinguishing characteristics of the layer.

In some embodiments, the first host is present at 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 photoactive layer is in the range of 10:1 to 1:10. In some embodiments, the weight ratio is in the range of 6:1 to 1:6; in some embodiments, 5:1 to 1:2; in some embodiments, 3:1 to 1:1.

In some embodiments, the weight ratio of dopant to total host is in the range of 1:99 to 20:80; in some embodiments, 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 green-emitting dopant, (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.

The optional layer can simultaneously promote electron transport and also serve as a confinement layer to prevent the exciton from quenching 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 quinoline salt derivatives such as tris(8-hydroxyquinoline) aluminum (AlQ), bis (2-methyl-8-hydroxyquinoline) (p-phenylphenolo) aluminum (BAlq), tetra-(8-hydroxyquinoline) hafnium (HfQ) and tetra-(8-hydroxyquinoline) Zirconium (ZrQ); and azole compounds, such as 2-(4-biphenyl)-5-(4-tertiary butylphenyl)-1,3,4-㗁diazole (PBD), 3-( 4-biphenyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (TAZ) and 1,3,5-tris(phenyl-2- Benzimidazole)benzene (TPBI); quinoline derivatives, such as 2,3-bis(4-fluorophenyl)quinoline; morpholine, such as 4,7-diphenyl-1,10-morpholine (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-morpholine (DDPA); three; fullerene; and mixtures thereof. In some embodiments, the electron transport material is selected from the group consisting of metal quinoline salts and morpholine 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 quinoline; 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 cobaltocene, tetrathiotetraphenyl, bis(ethylidenedithio)tetrathiofulvalene, heterocyclic or divalent groups, 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, organometallic compounds containing Li, LiF, Li ₂ O, and lithium quinoline; organometallic compounds containing Cs, 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, in some embodiments 1-10 Å.

The cathode 130 is an electrode that is 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 Group 1 alkali metals (eg, 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 to provide band gap matching of the layers, or to serve as a protective layer . Ultra-thin layers known in the art, such as copper phthalocyanine, silicon oxynitride, fluorocarbon, silane, or 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 transfer efficiency. It is preferable to determine the material selection of each component layer by balancing the positive and negative charges in the emitter 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. Substrates such as glass, plastic and metal can be used. Conventional vapor deposition techniques such as thermal evaporation, chemical vapor deposition, etc. can be used. 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 solutions or dispersions in suitable solvents To apply the organic layer.

For liquid deposition methods, those skilled in the art can easily determine the appropriate solvent for a particular compound or related class of compounds. For some applications, it is desirable to dissolve these compounds 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, tris Fluorotoluene, etc. Other suitable liquids for manufacturing liquid compositions including new compounds (as described herein as solutions or dispersions) include, but are not limited to, chlorinated hydrocarbons (such as methylene chloride, chloroform, chlorobenzene), aromatic hydrocarbons (such as substituted And unsubstituted toluene and xylene, including trifluorotoluene), polar solvents (such as tetrahydrofuran (THP), N-methylpyrrolidone), esters (such as ethyl acetate), alcohols (isopropanol), ketones (Cyclopentanone), and 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 formed 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 onto 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, a more effective cathode such as Ca, Ba or LiF can be used. Molded substrates and new hole-transporting materials that lead to reduced operating voltage or increased 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 structure in order: substrate, anode, hole injection layer, hole transport layer, photoactive 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 are not intended to be limiting. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. Examples

The concepts described herein will be further illustrated in the following examples, which do not limit the scope of the invention described in the patent application. Synthesis Example 1

This example illustrates the synthesis of 2,5-difluoro-1,4-phenylenediamine, compound IV-A.

(a) N-(2,5-difluorophenyl)-acetamide (1) .

In a 1L three-necked flask equipped with a magnetic stir bar, dissolve 2,5-difluoroaniline (152.3 g) in 500 ml of dichloromethane, then add acetic anhydride (134.5 g), and cool the mixture with an ice/water bath, Keep the internal temperature below 14ºC during the addition. The product was filtered, washed with hexane, and dried in vacuum. The filtrate was evaporated to a volume of about 200 ml, diluted with hexane, and an additional amount of product was collected by filtration. A total of 479.4 g of 2,5-difluoroaniline was used for three consecutive reactions. N- (2,5- difluorophenyl) - 1-acetylamino amine composition Yield - 572.4 g (90.4%). ¹ H-NMR (acetone-d ₆ , 500 MHz): 2.19 (s, 3H), 6.81-6.86 (m, 1H), 7.16-7.20 (m, 1H), 8.15-8.19 (m, 1H), 9.10 ( br. s, 1 H).

(b) N-(2,5-difluoro-4-nitrophenyl)-acetamide (2) .

To a stirred suspension of N-(2,5-difluorophenyl)-acetamide 1 (235 g) in acetic acid (30 ml) and concentrated sulfuric acid (350 ml) in a 1 L three-necked flask Add a mixture of nitric acid (120 ml) and concentrated sulfuric acid (120 ml) to keep the internal temperature below 12ºC-13ºC. After the addition was complete (about 2 hours), the reaction mixture was stirred for 3 hours in a water bath. The reaction mixture was poured into ice, precipitated, collected by filtration, and washed with water. A total of 572.3 g of N-(2,5-difluorophenyl)-acetamide was used for three consecutive reactions. The crude N- (2,5- difluoro-4-nitrophenyl) - 2-acetylamino amine composition Yield - 716.5 g, which was used in the next step without further purification. ¹ H-NMR (acetone-d ₆ , 500 MHz): 2.27 (s, 3H), 8.01-8.04 (m, 1H), 8.51-8.55 (m, 1H), 9.74 (br. s, 1 H).

(c) 2,5-difluoro-4-nitro-aniline (3) .

In a 1 L three-necked flask containing 450 ml of concentrated sulfuric acid, approximately 358 g of crude (2,5-difluoro-4-nitrophenyl)-acetamide 2 was added in portions while stirring using a mechanical stirrer. During about 45 min, the mixture is heated to 95ºC-100ºC and kept in the range of 95ºC-100ºC for 10 min. The mixture was cooled with an ice bath, poured into ice and filtered, precipitated, and washed with water (twice). A total of 716.5 g of N-(2,5-difluorophenyl)-acetamide 2 was used for two consecutive reactions. The combined yield of crude 2,5-difluoro-4-nitro-aniline 3-477 g (83%). ¹ H-NMR (acetone-d ₆ , 500 MHz): 6.88 (br. s, 2H), 6.72-6.76 (m, 1H), 7.82-7.86 (m, 1H).

(d) 2,5-difluoro-1,4-phenylenediamine (compound IV-A ).

Add the starting 2,5-difluoro-4-nitro-aniline 3 (100 g) in one portion to tin chloride dihydrate (520 g) in methanol (400 ml) containing concentrated hydrochloric acid (35 ml) The solution. After that, the reaction mixture was heated to about 35ºC-40ºC with a heating mantle. Allow the exothermic reaction to reach a steady reflux, occasionally applying a cooling ice/water bath. After the exothermic reaction has proceeded for about 20 minutes, the mixture is heated at 59°C for 30 minutes and allowed to stand overnight at ambient temperature. The reaction mixture was filtered and washed with methanol to produce the desired hydrochloride salt of diamine. The reaction was repeated four times continuously using a total of 418 g of 2,5-difluoro-4-nitro-aniline 3 . The combined hydrochloride salt was suspended in 700 ml of water and neutralized with 50% aqueous sodium hydroxide solution. The mixture was diluted with 1.5 L of water and sodium hydroxide until the initially formed precipitate dissolved. The mixture was extracted with ethyl acetate (4 times). The combined ethyl acetate extract was passed through a filter filled with silica gel and eluted with ethyl acetate. Use a rotary evaporator to distill out ethyl acetate to a minimum volume and treat with hexane. The precipitated product was collected by filtration and dried in vacuum to produce 167 g of product. The initial filtrate from the reduction step was hydrolyzed with 50% aqueous sodium hydroxide solution, extracted with ethyl acetate (twice), ethyl acetate was distilled to a minimum volume, treated with hexane, the precipitate was collected by filtration, dried, An additional amount of crude product was produced-94.5 g. The total yield of crude product-254.5 g (74%). The crude product was sublimated in batches under vacuum at 150°C to produce 245.5 g of 2,5-difluoro-1,4-phenylenediamine, compound IV-A. Sublimation can be repeated until the desired product purity. ¹ H-NMR (acetone-d ₆ , 500 MHz): 4.41 (br. s, 4H), 6.47 (t, 2H, J = 10 Hz). Synthesis Example 2

This example illustrates the synthesis of 4,6-difluoro-1,3-phenylenediamine, compound IV-E.

4,6-difluoro-1,3-phenylenediamine (compound IV-E ).

2,4-Difluoro-5-nitro-aniline (25 g) was added in one portion to a stirred solution of tin chloride dihydrate (200 g) and concentrated hydrochloric acid (30 ml) in methanol (500 ml) , The reaction mixture was cooled with an ice bath. After that, the mixture was heated at 70ºC for 30 min. The reaction mixture was cooled, quenched with 50% aqueous sodium hydroxide solution, filtered, and the solid was washed with methanol. The residue after evaporating methanol was extracted with acetone, filtered through a filter filled with silica gel, and eluted with acetone. The residue after evaporating acetone was dissolved in a dichloromethane-acetone mixture and passed through a silicone plug again, eluting with acetone. Acetone was distilled off, and the residue was sublimated in a glove box under vacuum at 180ºC to produce 9.5 g of product. The product was sublimed two more times to produce 8.1 g of purified 4,6-difluoro-1,3-phenylenediamine, compound IV-E. ¹ H-NMR (acetone-d ₆ , 500 MHz): 4.63 (br. s, 4H), 6.15 (t, 1H, J = 9 Hz), 6.77 (t, 1H, J = 11 Hz). Synthesis Example 3

This example illustrates the synthesis of 2,3-difluoro-1,4-phenylenediamine, compound IV-C.

(a) 2,3-difluoro-1,4-phthalic acid (6) .

Under a nitrogen atmosphere, a 1 L three-necked round bottom flask was filled with 500 ml of 1M LDA in tetrahydrofuran/hexane, and cooled to about -68ºC using a dry ice/acetone bath. After that, a solution of 2,3-difluorobenzoic acid in 75 ml of anhydrous tetrahydrofuran was added dropwise via syringe, while stirring with a mechanical stirrer to keep the internal temperature below -60ºC. The resulting suspension was stirred at -78ºC for 1.5 hours, then poured into dry ice in batches and allowed to reach ambient temperature during 2 hours. The solvent was distilled off, and the residue was suspended in water, followed by acidification with concentrated hydrochloric acid. The precipitated product was collected by filtration, washed with water, and dried in vacuum to produce 32 g of crude product, which was dissolved in acetone (about 500 ml). Acetone was distilled off using a rotary evaporator, and the precipitated product was collected by filtration and dried in vacuum to produce about 16 g of product. An additional amount of precipitate (2.2 g) was formed when the acetone was evaporated to the minimum and the residue was diluted with toluene. ¹ H-NMR (acetone-d ₆ , 500 MHz): 7.83-7.84 (m, 2H), 12.08 (br.s, 2H).

(b) 3,4-difluoro-1,4-phenylenediamine (compound IV-C ) .

Combine the above crude 2,3-difluoro-1,4-phthalic acid (8 g), tertiary butanol (100 ml), toluene (400 ml), and diphenylphosphoryl azide (27.23 g) And a mixture of triethylamine (100 g) was stirred at ambient temperature for 1 hour, then gradually heated from 50ºC to 100ºC over a period of about 1.7 hours, and heated at 100ºC for another 3 hours. The reaction was repeated again using 17 g of crude 2,3-difluoro-1,4-phthalic acid and 57.87 g of diphenylphosphoryl azide. The combined reaction mixture was washed with water (twice), the toluene layer was separated, passed through a short plug of silica gel and diatomaceous earth, and washed with toluene. Toluene was distilled to a volume of about 200 ml using a rotary evaporator, and the intermediate BOC-protected compound was filtered by filtration ( ¹ H-NMR: dmso-d ₆ , 500 MHz: 1.44 (s, 18 H), 7.22- 7.23 (m, 2H), 9.06 (s, 2H).), and heated with 300 ml of toluene and 30 ml of concentrated hydrochloric acid at 90ºC for 3 days. The toluene layer was separated, and the aqueous layer was diluted with 200 ml of water. Extract the aqueous layer with ethyl acetate and pass the extract through a short plug of silicone. Ethyl acetate was distilled off using a rotary evaporator to produce a crude product (8.14 g), which was sublimated in vacuum, and then crystallized from the ethyl acetate-cyclohexane mixture to produce 6 g of purified 3,4-bis Fluorine-1,4-phenylenediamine, compound IV-C. ¹ H-NMR (dmso-d ₆ , 500 MHz): 4.46 (s, 4H), 6.27-6.39 (m, 2H). ¹⁹ F-NMR (dmso-d ₆ , 500 MHz): 159.9. Polymer Example 1

This example illustrates the use of compound IV-A as a diamine to form polyamide.

Combine 2,5-difluoro-1,4-phenylenediamine (6 g), 3,3',4,4'-biphenyltetracarboxylic dianhydride (12.19 g, 0.995 equivalent), N-methylpyrrole Pyridone (103.4 g) was stirred under a nitrogen atmosphere for 2 weeks to produce a polymer solution with a viscosity of 3358 cps. GPC: Mn = 61889, Mw = 143777, Mp = 139220, Mz = 232140, PDI = 2.33. Polymer Example 2

This example illustrates the use of compound IV-E as one of two diamines to form polyamide.

The monomers are reacted as above to form a polymer solution, using DMAc as a solvent. The ratio of Bis-P to compound IV-E is 90:10. GPC: Mn = 61759; Mw = 215,962. Polymer Example 3

This example illustrates the formation of a polyimide film having formula V.

The polyamide solution from Polymer Example 2 was filtered through a micro filter, spin-coated onto a clean silicon wafer, soft-baked on a hot plate at 90ºC, and placed in an oven. Purge the furnace with nitrogen and heat it to the maximum curing temperature of 260ºC in stages. The wafer was removed from the furnace, soaked in water and manually layered to produce a sample of polyimide film. The characteristics of the film are given below: Thickness: 9.78 µm T _g : 260ºC CTE (first scan) 53.1 ppm/ºC CTE (second scan) 59.1 ppm/ºC Optical retardation 15 b* 2.48 YI 4.25 in the range of 50ºC-250ºC CTE is measured internally.

As can be seen from the above examples, the fluorinated diamine compounds of formulae (II) and (III) are sufficiently reactive under ambient conditions to produce polymers with molecular weights greater than 100,000. They can be used to form polyimide films with desired properties.

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 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 skilled in the art understand that various modifications and changes can be made without departing from the scope of the invention as defined in the following patent applications. Therefore, the description and drawings should be regarded as exemplary rather than limiting, and all such modifications are intended to be included within the scope of the present invention.

The benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, benefits, advantages, solutions to problems, and one or more any features that may cause or make any benefits, advantages, or solutions appear will not be interpreted as the key to the scope of any or all patent applications , Necessary or basic characteristics.

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

Embodiments are shown in the drawings to improve understanding of concepts as presented herein.

[Fig. 1] A schematic diagram of one example of a polyimide film including a flexible substitute for glass.

[Fig. 2] A diagram including an example of an electronic device including a flexible substitute of glass.

A skilled technician should understand that the object systems in the figures are shown for simplicity and clarity, and are 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 (6)

A liquid composition having a solid content of at least 10 wt% and a viscosity of at least 3000 cps, the composition comprising (a) a polyamic acid having a repeating unit structure of formula I

Where: R ^a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R ^b is the same or different at each occurrence and represents one or more aromatics Diamine residues; of which 30-100 mol% of R ^b have formula II or formula III

Where: R ¹ and R ² are the same or different, and are selected from the group consisting of F, R _f , and OR _f ; R _f is C _1-3 perfluoroalkyl; and * represents the attachment point; where R Both ¹ and R ² are adjacent to the point of attachment; and (b) a high boiling aprotic solvent. The composition according to item 1 of the patent application scope, wherein R ^b represents a residue derived from a diamine selected from the group consisting of compounds IV-A to IV-F

. The composition as described in item 1 of the patent application scope, wherein R ^a represents two or more residues of a tetracarboxylic acid component, wherein the tetracarboxylic acid component is selected from the group consisting of BPDA, 6FDA, PMDA, and CBDA Group. A polyimide film having a weight average molecular weight of at least 100,000 and containing a repeating unit structure of formula V

Where: R ^a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R ^b is the same or different at each occurrence and represents one or more aromatics Diamine residues; of which 30-100 mol% of R ^b have formula II or formula III

Where: R ¹ and R ² are the same or different, and are selected from the group consisting of F, R _f , and OR _f ; R _f is C _1-3 perfluoroalkyl; and * represents the attachment point; where R Both ¹ and R ² are adjacent to the attachment point; and further, wherein the polyimide membrane is prepared according to a method that includes the following steps in order and without repeating: a high boiling point aprotic solvent will contain one or Polyamide solutions of multiple tetracarboxylic acid components and one or more diamine components are applied to the substrate; the coated substrate is soft baked; at multiple preselected temperatures at multiple preselected intervals The soft-baked coated substrate is processed next. The polyimide film as described in item 4 of the patent application, where the highest pre-selected temperature is 375ºC. The polyimide film as described in item 5 of the patent application scope, wherein the method is performed under an inert atmosphere.

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