Polymer for use in electronic device

Abstract

To provide a polyimide having a novel rigid structure capable of giving a polymer with low CTE, high Tg, and high thermal stability.SOLUTION: It is a diamine having Formula IV or Formula VII [Ar2, Ar3, and Ar4 are independently selected from groups consisting of carbocyclic aryl, heteroaryl, and the like; Q1 is selected from groups consisting of a single bond, alkyl, silyl, ester, siloxane, oligosiloxane, polysiloxane, O, S, SO2, BR3, NR3, P(O)R3, carbocyclic aryl, heteroaryl, and the like].SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Claiming the benefit of a prior application This application claims the benefit of U.S. Provisional Patent Application No. 62 / 978,579, filed February 19, 2020, which is incorporated herein by reference in its entirety.

[0002] The present disclosure relates to novel polymeric compounds. The present disclosure further relates to methods for preparing such polymeric compounds and to electronic devices having at least one layer comprising these materials. [Background technology]

[0003] Materials used in electronics applications often have strict requirements for their structural, optical, thermal, electrical, and other properties. As the number of commercial electronics applications continues to grow, the breadth and specificity of required properties strongly demands the innovation of materials with new and / or improved properties. Polyimides refer to a class of polymer compounds that have been widely used in a variety of electronics applications. With the right properties, they can serve as flexible alternatives to glass in electronic display devices. These materials can function as components of liquid crystal displays ("LCDs"), where their modest power consumption, light weight, and flat layer structure are crucial characteristics for effective use. Other uses for electronic display devices where such parameters are important include device substrates, substrates for color filter sheets, cover films, touchscreen panels, and the like.

[0004] Some of these components are also important in the construction and operation of organic electronic devices, including organic light-emitting diodes ("OLEDs"). OLEDs are promising for numerous display applications due to their high power conversion efficiency and wide range of end-user applicability. They are increasingly being used in mobile phones, tablet devices, handheld / laptop computers, and other commercial products. These applications require displays with large information content, full color, and fast video-speed response times, in addition to low power consumption.

[0005] Polyimide films generally have sufficient thermal stability, high glass transition temperatures, and mechanical toughness to merit such use. Furthermore, polyimides generally do not develop haze when subjected to repeated flexing, so polyimides are often preferred over other transparent substrates such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) in flexible display applications. Thus, there is a continuing need for polymeric materials that are suitable for use in electronic devices. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 5,166,308 [Patent Document 2] U.S. Patent No. 5,298,331 [Non-patent literature]

[0007] [Non-Patent Document 1] CRC Handbook of Chemistry and Physics,81st Edition(2000-2001) Summary of the Invention [Means for solving the problem]

[0008] It remains a challenge to discover novel rigid structures that can lead to polymers with low CTE, high Tg, and high thermal stability. The use of 1,8-naphthalic dianhydride and imide-containing polymers has been overlooked in the literature due to their low reactivity, despite the great interest recently shown in various aromatic compounds.

[0009] Disclosed herein are monomers that can be used to fabricate polyimide films with low CTE, high Tg, and high thermal stability. The disclosed diimide-containing naphthalic acid monomers are reactive and form high molecular weight polymers at ambient conditions.

[0010] Additionally, the monomer can be used in small amounts as an additive to enhance the color of the polyimide film.

[0011] Formula I

[0012] [ka]

[0013] [In formula: Y is alkyl, silyl, ester, siloxane, oligosiloxane, polysiloxane, O, S, SO2, BR 3 , N.R. 3 , P(O)R 3 , unsubstituted or substituted carbocyclic aryl, and unsubstituted or substituted heteroaryl; R 1 ~R 2 are the same or different at each occurrence and are selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, unsubstituted or substituted carbocyclic aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy, and deuterated analogs thereof; R 3 is selected from the group consisting of alkyl and unsubstituted or substituted carbocyclic aryl, and deuterated analogs thereof; and a and b are the same or different and are integers from 0 to 5. A dianhydride having the formula:

[0014] Formula II

[0015] [ka]

[0016] [In formula: R a may be the same or different in each occurrence and represent the residue of one or more tetracarboxylic acid moieties; and R b may be the same or different at each occurrence and represent one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R a is a dianhydride residue from one or more dianhydrides having formula 1] Further provided is a polyamic acid having repeat units of:

[0017] Further provided is a composition comprising: (a) a polyamic acid having repeating units of Formula II; and (b) a high-boiling aprotic solvent.

[0018] The repeating unit is of formula III

[0019] [ka]

[0020] [In the formula, R a and R b is as defined in Formula II] There is further provided a polyimide having the structure:

[0021] Further provided is a polyimide film comprising a repeating unit of formula III.

[0022] Formula IV

[0023] [ka]

[0024] [In formula: Ar 2 and Ar 3 are the same or different and are selected from the group consisting of carbocyclic aryl, heteroaryl, and substituted derivatives thereof; Q 1 is a single bond, alkyl, silyl, ester, siloxane, oligosiloxane, polysiloxane, O, S, SO2, BR 3 , N.R. 3 , P(O)R 3 , unsubstituted or substituted carbocyclic aryl, and unsubstituted or substituted heteroaryl; R 1 and R 2 are the same or different at each occurrence and are selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, unsubstituted or substituted carbocyclic aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy, and deuterated analogs thereof; R 3 is selected from the group consisting of alkyl and unsubstituted or substituted carbocyclic aryl; and a and b are the same or different and are integers from 0 to 5; and c is 0 or 1. Further provided is a diamine having the formula:

[0025] Formula V

[0026] [ka]

[0027] [In formula: R a1are the same or different at each occurrence and represent the residue of one or more tetracarboxylic acid moieties; and R b1 are the same or different at each occurrence and represent one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R b1 is a diamine residue from one or more diamines having formula IV. Further provided is a polyamic acid having the repeating unit:

[0028] Further provided is a composition comprising: (a) a polyamic acid having repeating units of Formula V; and (b) a high-boiling aprotic solvent.

[0029] The repeating unit is of formula VI

[0030] [ka]

[0031] [In the formula, R a1 and R b1 is as defined in formula IV] There is further provided a polyimide having the structure:

[0032] Formula VII

[0033] [ka]

[0034] [In formula: Ar 2 , Ar 3 and Ar 4 are the same or different and are selected from the group consisting of carbocyclic aryl, heteroaryl, and substituted derivatives thereof; R 1 and R 2are the same or different at each occurrence and are selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, unsubstituted or substituted carbocyclic aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy, and deuterated analogs thereof; and a and b are the same or different and are integers from 0 to 5. Further provided is a diamine having the formula:

[0035] Formula VIII

[0036] [ka]

[0037] [In formula: R a2 are the same or different at each occurrence and represent the residue of one or more tetracarboxylic acid moieties; and R b2 are the same or different at each occurrence and represent one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R b2 is a diamine residue from one or more diamines having formula VII. Further provided is a polyamic acid having the repeating unit:

[0038] Further provided is a composition comprising: (a) a polyamic acid having repeating units of Formula VIII; and (b) a high-boiling aprotic solvent.

[0039] The repeating unit is of formula IX

[0040] [ka]

[0041] [In the formula, R a2 and R b2 is as defined in Formula VIII. There is further provided a polyimide having the structure:

[0042] Further provided are polyimide films comprising repeating units of Formula III, Formula VI, or Formula IX.

[0043] Further provided are one or more methods of preparing a polyimide film, wherein the polyimide film has repeating units of Formula III, Formula VI, or Formula IX.

[0044] Further provided is a flexible replacement for glass in electronic devices, wherein the flexible replacement for glass is a polyimide film having repeating units of Formula III, Formula VI, or Formula IX.

[0045] Further provided is an electronic device having at least one layer comprising a polyimide film having repeating units of Formula III, Formula VI, or Formula IX.

[0046] Further provided are organic electronic devices, such as, for example, OLEDs, where the organic electronic devices include flexible alternatives to glass as disclosed herein.

[0047] The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims.

[0048] To facilitate understanding of the concepts presented herein, embodiments are illustrated in the accompanying figures. [Brief explanation of the drawings]

[0049] [Figure 1] Included is an illustration of one example of a polyimide film that can be used as a flexible alternative to glass. [Figure 2] Included is an illustration of one example of an electronic device that includes a flexible alternative to glass. DETAILED DESCRIPTION OF THE INVENTION

[0050] Those skilled in the art will appreciate that objects in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the objects in the figures may be exaggerated relative to other objects to facilitate an improved understanding of the embodiments.

[0051] Many aspects and embodiments have been described above, and are illustrative only, and not limiting. After reading this specification, skilled artisans will recognize that other aspects and embodiments are possible without departing from the scope of the invention.

[0052] Other features and advantages of any one or more embodiments will be apparent from the following detailed description and claims. The detailed description first addresses definitions and clarification of terms, followed by dianhydrides, diamines, polyamic acids, polyimides, methods of preparing polyimide films, electronic devices, and finally examples.

[0053] 1. Definitions and Clarifications Before addressing the details of the embodiments below, some terms will be defined or clarified.

[0054] When used in the "Definitions and Explanations of Terms" section, R, R a , R b , R', R'' and any other variables are generic and may be the same or different from those defined in the formula.

[0055] The term "alkyl" is intended to mean a group derived from an aliphatic hydrocarbon and includes linear, branched, or cyclic groups, which may be unsubstituted or substituted. In some embodiments, an alkyl group has 1 to 20 carbon atoms. In some embodiments, the group has 1 to 6 carbon atoms. A "heteroalkyl" group is an alkyl group in which at least one carbon in the chain is replaced by a heteroatom. In some embodiments, a heteroalkyl group has 1 to 20 carbon atoms.

[0056] The term "aprotic" refers to a class of solvents that lack an acidic hydrogen atom and therefore cannot act as a hydrogen donor. Common aprotic solvents include alkanes, carbon tetrachloride (CCl4), benzene, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and many other solvents.

[0057] The term "aromatic compound" is intended to mean an organic compound containing at least one unsaturated cyclic group having 4n+2 delocalized π-electrons. The term is intended to encompass both aromatic compounds having only carbon and hydrogen atoms, and heteroaromatic compounds in which one or more of the carbon atoms in the cyclic group are replaced by another atom, such as nitrogen, oxygen, sulfur, etc.

[0058] The term "aryl" or "aryl group" refers to a moiety formed by removing one or more hydrogens ("H") or deuteriums ("D") from an aromatic compound. An aryl group can have a single ring (monocyclic) or multiple rings (bicyclic or higher) fused together or covalently linked. A "carbocyclic aryl" has only carbon atoms in the aromatic ring(s). A "heteroaryl" has one or more heteroatoms in at least one aromatic ring. In some embodiments, a carbocyclic aryl group has 6 to 60 ring carbon atoms; in some embodiments, 6 to 30 ring carbon atoms. In some embodiments, a heteroaryl group has 4 to 50 ring carbon atoms; in some embodiments, 4 to 30 ring carbon atoms.

[0059] The term "alkoxy" is intended to mean the group --OR, where R is alkyl.

[0060] The term "aryloxy" is intended to mean the group --OR, where R is aryl.

[0061] Unless otherwise specified, all groups may be substituted or unsubstituted. Optionally substituted groups, such as, but not limited to, alkyl or aryl, can be substituted with one or more substituents, which can be the same or different. Suitable substituents include alkyl, aryl, nitro, cyano, -N(R')(R"), halo, hydroxy, carboxy, 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 (wherein s=0 to 2) or -S(O) s -heteroaryl (wherein s=0 to 2).

[0062] The term "amine" is intended to mean a compound containing a basic nitrogen atom with a lone pair of electrons. The term "amino" refers to the functional groups -NH2, -NHR, or -NR2, where R is the same or different in each occurrence and can be an alkyl or aryl group. The term "diamine" is intended to mean a compound containing two basic nitrogen atoms with associated lone pairs of electrons. The term "aromatic diamine" is intended to mean an aromatic compound having two amino groups. The term "bent diamine" is intended to mean a compound in which the two basic nitrogen atoms and associated lone pairs are oriented in a corresponding compound or functional group, such as m-phenylenediamine:

[0063] [ka]

[0064] is intended to mean diamines asymmetrically arranged around the center of symmetry of

[0065] The term "aromatic diamine residue" is intended to mean the moiety bonded to two amino groups in an aromatic diamine. The term "aromatic diisocyanate residue" is intended to mean the moiety bonded to two isocyanate groups in an aromatic diisocyanate compound. This is further exemplified below.

[0066] [ka]

[0067] The terms "diamine residue" and "diisocyanate residue" are intended to mean a moiety that is bonded to two amino groups or two isocyanate groups, respectively, where the moiety is aliphatic or aromatic.

[0068] The term “b * " is the b in the CIELab color space, which represents the yellow / blue opponent color. * Yellow indicates positive b * blue is represented by a negative b * The measured color is expressed by a value. The choice of solvent can affect the measured color, especially for materials exposed to high temperature processing conditions. * The b can be affected by the solvent. This can occur as a result of the inherent properties of the solvent and / or properties associated with low levels of impurities present in various solvents. Particular solvents may have the desired b for a particular application. * Often preselected to achieve a value.

[0069] The term "birefringence" is intended to mean the difference in the refractive index in different directions within a polymer film or coating. This term usually refers to the difference between the x-axis or y-axis (in-plane) and z-axis (out-of-plane) refractive indices.

[0070] The term "charge transport," when referring to a layer, material, component, or structure, is intended to mean that such layer, material, component, or structure facilitates the movement of such charges through the thickness of such layer, material, component, or structure with relative efficiency and low charge loss. Hole transport materials facilitate positive charges; electron transport materials facilitate negative charges. Although light-emitting materials may also have some charge transport properties, the term "charge transport layer, material, component, or structure" is not intended to include layers, materials, components, or structures whose primary function is to emit light.

[0071] The term "compound" is intended to mean an uncharged substance composed of molecules further comprising atoms which cannot be separated from their corresponding molecules by physical means without breaking chemical bonds. This term is intended to include oligomers and polymers.

[0072] The term "coefficient of linear thermal expansion (CTE or α)" is intended to mean the parameter that defines the amount a material expands or contracts as a function of temperature. The coefficient of linear thermal expansion is expressed as change in length per degree Celsius, and is typically expressed in units of μm / m / °C or ppm / °C. α=(ΔL / L0) / ΔT The measured CTE values ​​disclosed herein are obtained by known methods during the first or second heating scan. Understanding the relative expansion / contraction properties of materials can be an important consideration in the fabrication and / or reliability of electronic devices.

[0073] The term "dopant" is intended to mean a material that, in a layer containing a host material, changes the electronic properties or the targeted wavelengths of radiation emission, reception or filtering of that layer compared to the electronic properties or the wavelengths of radiation emission, reception or filtering of that layer in the absence of such material.

[0074] The term "electroactive" when referring to a layer or material is intended to indicate a layer or material that electronically facilitates the operation of a device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block charge (charges can be either electrons or holes), or materials that emit radiation, or materials that exhibit a change in concentration of electron-hole pairs when subjected to radiation. Examples of inactive materials include, but are not limited to, planarizing materials, insulating materials, and environmental barrier materials.

[0075] The terms "tensile elongation" or "tensile strain" are intended to mean the percentage increase in length that occurs in a material before it breaks under an applied tensile stress, which can be measured, for example, by ASTM method D882.

[0076] The prefix "fluoro" is intended to indicate that one or more hydrogen atoms in the group have been replaced with fluorine.

[0077] The term "glass transition temperature (T g "Glass transition" is intended to mean the temperature at which an irreversible change occurs in an amorphous polymer, or within the amorphous regions of a semi-crystalline polymer, when the material suddenly changes from a hard, glassy, ​​or brittle state to a flexible or elastic state. Microscopically, the glass transition occurs when normally coiled, motionless polymer chains become free to rotate and pass through one another. T g ' may be measured using differential scanning calorimetry (DSC), thermomechanical analysis (TMA) or dynamic mechanical analysis (DMA) or other methods.

[0078] The prefix "hetero" indicates that one or more carbon atoms have been replaced with a different atom. In some embodiments, the heteroatom is O, N, S, or a combination thereof.

[0079] The term "high boiling point" is intended to indicate a boiling point above 130°C.

[0080] The term "host material" is intended to mean a material to which a dopant is added. The host material may or may not have electronic properties or the ability to emit, receive, or filter radiation. In some embodiments, the host material is present in a higher concentration.

[0081] The term "laser particle counter testing" refers to a method used to evaluate the particle content of polyamic acid and other polymer solutions whereby a representative sample of the test solution is spin-coated onto a 5-inch silicon wafer and soft-baked / dried. Films thus prepared are evaluated for particle content by any number of standard measurement techniques, including laser particle detection, as known in the art.

[0082] The term "liquid composition" is intended to mean a liquid medium in which a material is dissolved to form a solution, dispersed to form a dispersion, or suspended to form a suspension or emulsion.

[0083] The term "substrate" is intended to mean a base upon which one or more layers are placed, for example, in forming an electronic device. Non-limiting examples include glass, silicon, etc.

[0084] The term "1% TGA weight loss" is intended to mean the temperature at which 1% of the original polymer weight is lost due to decomposition (elimination of absorbed water).

[0085] The term "optical retardation (or R TH )" is intended to mean the difference between the average in-plane refractive index and the out-of-plane refractive index (i.e., birefringence), which is then multiplied by the thickness of the film or coating. Typically, optical retardation is measured for a particular frequency of light and is reported in units of nanometers.

[0086] The term "organic electronic device" or sometimes "electronic device" is intended herein to mean a device that includes one or more organic semiconductor layers or materials.

[0087] The term "particle content" is intended to mean the number or count of insoluble particles present in a solution. Measurement of particle content can be performed on the solution itself or on product materials (parts, films, etc.) prepared from those films. This property can be assessed using a variety of optical methods.

[0088] The term "photoactive" refers to a material or layer that emits light when activated by an applied voltage (as in a light-emitting diode or chemical cell), emits light after absorbing a photon (as in a down-converting phosphor device), or responds to radiant energy (as in a photodetector or photovoltaic cell) to produce a signal with or without an applied bias voltage.

[0089] The term "polyamic acid solution" refers to a solution of a polymer containing amic acid units capable of intramolecular cyclization to form imide groups.

[0090] The term "polyimide" refers to condensation polymers resulting from the reaction of one or more difunctional carboxylic acid components with one or more primary diamines or diisocyanates. They contain the imide structure -CO-NR-CO- as linear or heterocyclic units along the main chain of the polymer backbone.

[0091] The term "satisfactory" when referring to a property or characteristic of a material shall mean that the property or characteristic meets all requirements / demands for the material in use.

[0092] The term "soft bake" is intended to mean a process commonly used in electronics manufacturing in which coated materials are heated to drive off solvents and solidify the film. Soft bake is typically performed on a hot plate or in an exhaust oven at temperatures between 90°C and 110°C in preparation for subsequent heat treatment of the coated layer or film.

[0093] The term "substrate" refers to a base material that may be either rigid or flexible and may include one or more layers of one or more materials, which may include, but are not limited to, glass, polymer, metal, or ceramic materials, or combinations thereof. The substrate may or may not include electronic components, electronic circuits, or conductive members.

[0094] The term "siloxane" refers to the group RSiORSi-, or the divalent group -SiRORSi-, where R is the same or different in each occurrence and is selected from the group consisting of H, C 1~20 In some embodiments, one or more carbons in the R alkyl group are replaced with Si. Oligomeric siloxanes have 2 to 5 repeating siloxane units. Polymeric siloxanes have more than 5 repeating siloxane units; in some embodiments, 6 to 12 repeating siloxane units.

[0095] The term "siloxy" refers to the group RSiO-, where R may be the same or different at each occurrence, and is substituted with H, C 1~20 alkyl, fluoroalkyl, or aryl).

[0096] The term "silyl" refers to the group R(RSi) n -, or the divalent radical -(R2Si) n - (wherein R is the same or different at each occurrence; H, C 1~20In some embodiments, n is 1 to 10. ...

[0097] The term "spin coating" is intended to mean a process used to deposit uniform thin films on a flat substrate. Typically, a small amount of coating material is applied to the center of the substrate, and the substrate is rotating slowly or not at all. The substrate is then spun at a specific speed to spread the coating material evenly by centrifugal force.

[0098] The term "tensile modulus" is intended to mean a measure of the stiffness of a solid material that defines the initial relationship between stress (force per unit area) and strain (proportional deformation) in a material such as a film. A commonly used unit is gigapascals (GPa).

[0099] 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.

[0100] The term "tetracarboxylic acid moiety residue" is intended to mean the moiety bonded to the four carboxy groups in the tetracarboxylic acid moiety, as further exemplified below.

[0101] [ka]

[0102] The term "transmittance" refers to the percentage of light of a given wavelength impinging on a film that passes through the film so that it is detectable on the other side. Light transmittance measurements within the visible region (380 nm to 800 nm) are particularly useful for characterizing film color characteristics that are most important for understanding the in-use properties of the polyimide films disclosed herein.

[0103] The term "yellowness index (or YI)" refers to the magnitude of yellowness compared to a standard. A positive YI value indicates the presence and magnitude of yellow color. Materials with a negative YI appear bluish. It should also be noted that YI can be solvent dependent, particularly for polymerization and / or curing processes carried out at elevated temperatures. The magnitude of color introduced using DMAC as a solvent may differ from the magnitude of color introduced using, for example, NMP as a solvent. This can occur as a result of the inherent properties of the solvent and / or properties associated with low levels of impurities contained in various solvents. A particular solvent is often pre-selected to achieve a desired YI value for a particular application.

[0104] In the structure shown below, where the bond of a substituent passes through one or more rings,

[0105] [ka]

[0106] It is meant that the substituent R may be attached at any available position on the ring or rings.

[0107] The phrase "adjacent to," when used to refer to layers in a device, does not necessarily mean that one layer is directly next to another layer. In contrast, the phrase "adjacent R groups" is used to refer to R groups that are adjacent to each other in a chemical formula (i.e., R groups that are on atoms that are joined by a bond). Exemplary adjacent R groups are shown below.

[0108] [ka]

[0109] Unless otherwise expressly stated or indicated in connection with use to the contrary, when an embodiment of the subject matter herein is stated or described as comprising, including, containing, containing, having, consisting of, or consisting of particular features or elements, one or more features or elements in addition to those expressly stated or described may be present in the embodiment. Although alternative embodiments of the disclosed subject matter herein may be described as consisting essentially of particular features or elements, in that embodiment, no features or elements are present therein that materially alter the principles of operation or distinguishing characteristics of the embodiment. Although further alternative embodiments of the described subject matter herein may be described as consisting of particular features or elements, in that embodiment, or in an intangible variation thereof, only the specifically stated or described features or elements are present.

[0110] Furthermore, unless expressly stated to the contrary, "or" means an inclusive or, not an exclusive or. For example, condition A or B is satisfied by any one 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 A and B are both true (or exist).

[0111] Similarly, the use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted to include one or at least one, and the singular also includes the plural unless it is clear that it has a different meaning.

[0112] The group numbers, which correspond to columns in the periodic table of elements, use the "modern notation" convention as seen in (Non-Patent Document 1).

[0113] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one 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 present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific section is cited. In case of conflict, the present specification, including definitions, will control. Furthermore, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0114] To the extent not described herein, many details regarding specific materials, processing operations and circuitry are conventional and can be found in textbooks and other sources of information in organic light emitting diode display, photodetector, photovoltaic and semiconductor component technology.

[0115] 2. Dianhydride The dianhydrides described herein have the formula I

[0116] [ka]

[0117] [In formula: Y is alkyl, silyl, ester, siloxane, oligosiloxane, polysiloxane, O, S, SO2, BR 3 , N.R. 3 , P(O)R 3 , unsubstituted or substituted carbocyclic aryl, and unsubstituted or substituted heteroaryl, and deuterated analogs thereof; R 1 ~R 2are the same or different at each occurrence and are selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, unsubstituted or substituted carbocyclic aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy, and deuterated analogs thereof; R 3 is selected from the group consisting of alkyl and unsubstituted or substituted carbocyclic aryl, and deuterated analogs thereof; and a and b are the same or different and are integers from 0 to 5. It has.

[0118] In some embodiments of Formula I, Y is C 1~6 alkyl; in some embodiments, C 4~6 and cycloalkyl. In some embodiments, the alkyl is further substituted with one or more substituents selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, unsubstituted or substituted carbocyclic aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy, and deuterated analogs thereof. In some embodiments, the one or more substituents are selected from the group consisting of F, CN, alkyl, fluoroalkyl, and fluoroalkoxy, and deuterated analogs thereof.

[0119] In some embodiments of Formula I, Y is C 2~6 This is Cyril.

[0120] In some embodiments of Formula I, Y is an ester.

[0121] In some embodiments of Formula I, Y is a siloxane.

[0122] In some embodiments of Formula I, Y is an oligosiloxane.

[0123] In some embodiments of Formula I, Y is a polysiloxane.

[0124] In some embodiments of Formula I, Y is O.

[0125] In some embodiments of Formula I, Y is S.

[0126] In some embodiments of Formula I, Y is SO2.

[0127] In some embodiments of Formula I, Y is BR 3 is.

[0128] In some embodiments of Formula I, Y is NR 3 is.

[0129] In some embodiments of Formula I, Y is P(O)R 3 is.

[0130] In some embodiments of Formula I, Y is an unsubstituted carbocyclic aryl having from 6 to 20 ring carbon atoms; in some embodiments, it is an unsubstituted carbocyclic aryl having from 6 to 12 ring carbon atoms.

[0131] In some embodiments of Formula I, Y is a substituted carbocyclic aryl having 6 to 20 ring carbon atoms and having one or more substituents selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy, and deuterated analogs thereof.

[0132] In some embodiments, the carbocyclic aryl is selected from the group consisting of phenyl, biphenyl, naphthyl, binaphthyl, and anthracenyl.

[0133] In some embodiments of Formula I, Y is an unsubstituted heteroaryl having 6 to 18 ring carbon atoms and at least one ring heteroatom selected from the group consisting of N, O, and S.

[0134] In some embodiments of Formula I, Y is a substituted heteroaryl having 6 to 18 ring carbon atoms and having one or more substituents selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

[0135] In some embodiments of Formula I, the heteroaryl group is derived from a compound selected from the group consisting of pyridine, carbazole, dibenzofuran, and dibenzothiophene.

[0136] In some embodiments of Formula I, a=0.

[0137] In some embodiments of Formula I, a=1.

[0138] In some embodiments of Formula I, a=2.

[0139] In some embodiments of Formula I, a=3.

[0140] In some embodiments of Formula I, a=4.

[0141] In some embodiments of Formula I, a=5.

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

[0143] In some embodiments of Formula I, a>0 and at least one R 1 is F.

[0144] In some embodiments of Formula I, a>0 and at least one R 1 is CN.

[0145] In some embodiments of Formula I, a>0 and at least one R 1 is C 1~20 alkyl; in some embodiments, C 1~10 It is alkyl.

[0146] In some embodiments of Formula I, a>0 and at least one R 1 is C 1~20 fluoroalkyl; in some embodiments, C 1~10 It is a fluoroalkyl.

[0147] In some embodiments of Formula I, a>0 and at least one R 1 is C 1~20 perfluoroalkyl; in some embodiments, C 1~10 It is a perfluoroalkyl.

[0148] In some embodiments of Formula I, a>0 and at least one R 1 is C 1~20 alkoxy; in some embodiments C 1~10 It is an alkoxy.

[0149] In some embodiments of Formula I, a>0 and at least one R 1 is C 1~20 In some embodiments, C 1~10 It is a fluoroalkoxy.

[0150] In some embodiments of Formula I, a>0 and at least one R 1 is C 1~20 perfluoroalkoxy; in some embodiments, C 1~10 It is a perfluoroalkoxy.

[0151] In some embodiments of Formula I, a>0 and at least one R1 is SiH3.

[0152] In some embodiments of Formula I, a>0 and at least one R 1 is C 1~12 silyl; in some embodiments, C 3~6 This is Cyril.

[0153] In some embodiments of Formula I, a>0 and at least one R 1 is C 1~12 siloxy; in some embodiments, C 3~6 It's siloxy.

[0154] In some embodiments of Formula I, a>0 and at least one R 1 is unsubstituted or substituted C 6~30 In some embodiments, unsubstituted or substituted C 6~18 It is a hydrocarbon aryl; in some embodiments, it is unsubstituted.

[0155] In some embodiments of Formula I, a>0 and at least one R 1 is unsubstituted or substituted C 3~30 heteroaryl; in some embodiments, unsubstituted or substituted C 3~18 It is heteroaryl; and in some embodiments, it is unsubstituted.

[0156] In some embodiments of Formula I, a>0 and at least one R 1 is unsubstituted or substituted C 6~30 hydrocarbon aryloxy; in some embodiments, unsubstituted or substituted C 6~18 It is a hydrocarbon aryloxy; in some embodiments, it is unsubstituted.

[0157] In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups are further substituted with one or more substituents selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

[0158] In some embodiments of Formula I, a=1 and R 1 is selected from the group consisting of F, trifluoromethyl, and trifluoromethoxy.

[0159] All of the above embodiments relating to a in Formula I apply equally to b in Formula I.

[0160] In some embodiments, b>0 and R 1 All of the above embodiments relating to R 2 applies equally to

[0161] In some embodiments of Formula I, b=1 and R 2 is selected from the group consisting of F, trifluoromethyl, and trifluoromethoxy.

[0162] In some embodiments of Formula I, R 3 is C 1~20 alkyl; in some embodiments, C 1~10 It is alkyl.

[0163] In some embodiments of Formula I, R 3 is an unsubstituted carbocyclic aryl having 6 to 20 ring carbon atoms; in some embodiments, it is an unsubstituted carbocyclic aryl having 6 to 12 ring carbon atoms.

[0164] In some embodiments of Formula I, R 3is a substituted carbocyclic aryl having 6 to 20 ring carbon atoms and having one or more substituents selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

[0165] In some embodiments of Formula I, the dianhydride is of Formula IA

[0166] [ka]

[0167] [In formula: R 5 are the same or different at each occurrence and are selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, unsubstituted or substituted carbocyclic aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy, and deuterated analogs thereof; d is an integer from 0 to 4; e is an integer from 1 to 5; and R 1 , R 2 , a, and b are as defined in Formula I. It has.

[0168] In some embodiments of formula IA, d=0.

[0169] In some embodiments of formula IA, d=1.

[0170] In some embodiments of formula IA, d=2.

[0171] In some embodiments of formula IA, d=3.

[0172] In some embodiments of formula IA, d=4.

[0173] In some embodiments of formula IA, d>0.

[0174] In some embodiments of formula IA, e=1.

[0175] In some embodiments of formula IA, e=2.

[0176] In some embodiments of formula IA, e=3.

[0177] In some embodiments of formula IA, e=4.

[0178] In some embodiments of Formula IA, e=5.

[0179] In some embodiments of Formula IA, d>0 and R of Formula I 1 All of the above embodiments relating to R of formula IA 5 applies equally to

[0180] R in Formula I 1 , R 2 All of the above embodiments for a, a, and b are R of formula IA 1 , R 2 , a, and b equally.

[0181] The novel compounds can be prepared using any technique that results in a C-C or C-N bond, or other desired bond. A variety of such techniques are known, including Suzuki, Yamamoto, Stille, Negishi, and metal-catalyzed C-N coupling, as well as metal-catalyzed and oxidative direct arylation. One synthetic scheme is shown below:

[0182] [ka]

[0183] Any of the above-described embodiments of Formula I can be combined with one or more other embodiments, provided they are not mutually inconsistent. For example, an embodiment in which the dianhydride has formula IA includes those in which a=1 and R 1 is CF3, as well as embodiments where b=1 and R 2 can be combined with an embodiment where is CF3. One of ordinary skill in the art would understand which embodiments are mutually exclusive and, as a result, would be able to readily determine the combinations of embodiments contemplated by this application.

[0184] Some non-limiting examples of compounds having Formula I are shown below.

[0185] [ka]

[0186] [ka]

[0187] 3. Diamine The diamines described herein may be of formula IV or formula VII

[0188] [ka]

[0189] [In formula: Ar 2 , Ar 3 , and Ar 4 are the same or different and are selected from the group consisting of carbocyclic aryl, heteroaryl, substituted derivatives thereof and deuterated analogs thereof; Q 1 is a single bond, alkyl, silyl, ester, siloxane, oligosiloxane, polysiloxane, S, SO2, BR 3 , N.R. 3 , P(O)R 3, unsubstituted or substituted carbocyclic aryl, unsubstituted or substituted heteroaryl and deuterated analogs thereof; R 1 and R 2 are the same or different at each occurrence and are selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, unsubstituted or substituted carbocyclic aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy, and deuterated analogs thereof; R 3 is selected from the group consisting of alkyl and unsubstituted or substituted carbocyclic aryl; and a and b are the same or different and are integers from 0 to 5; and c is 0 or 1. It has.

[0190] In some embodiments, the diamine has formula IV:

[0191] In some embodiments of Formula IV, c=0.

[0192] In some embodiments of Formula IV, c=1 and Q 1 is a single bond.

[0193] In some embodiments of Formula IV, c=1 and Q 1 is C 1~6 alkyl; in some embodiments, C 4~6 and cycloalkyl. In some embodiments, the alkyl is further substituted with one or more substituents selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, unsubstituted or substituted carbocyclic aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, siloxy, and deuterated analogs thereof. In some embodiments, the one or more substituents are selected from the group consisting of F, CN, alkyl, fluoroalkyl, and fluoroalkoxy.

[0194] In some embodiments of Formula IV, c=1 and Q 1 is C 2~6 This is Cyril.

[0195] In some embodiments of Formula IV, c=1 and Q 1 is an ester.

[0196] In some embodiments of Formula IV, c=1 and Q 1 is a siloxane.

[0197] In some embodiments of Formula IV, c=1 and Q 1 is an oligosiloxane.

[0198] In some embodiments of Formula IV, c=1 and Q 1 is a polysiloxane.

[0199] In some embodiments of Formula IV, c=1 and Q 1 is O.

[0200] In some embodiments of Formula IV, c=1 and Q 1 is S.

[0201] In some embodiments of Formula IV, c=1 and Q 1 is SO2.

[0202] In some embodiments of Formula IV, c=1 and Q 1 BR 3 is.

[0203] In some embodiments of Formula IV, c=1 and Q 1 is NR 3 is.

[0204] In some embodiments of Formula IV, c=1 and Q 1 is P(O)R 3 is.

[0205] In some embodiments of Formula IV, c=1 and Q 1 is an unsubstituted carbocyclic aryl having 6 to 20 ring carbon atoms; in some embodiments, it is an unsubstituted carbocyclic aryl having 6 to 12 ring carbon atoms.

[0206] In some embodiments of Formula IV, c=1 and Q 1 is a substituted carbocyclic aryl having 6 to 20 ring carbon atoms and having one or more substituents selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

[0207] In some embodiments, the carbocyclic aryl is selected from the group consisting of phenyl, biphenyl, naphthyl, binaphthyl, and anthracenyl.

[0208] In some embodiments of Formula IV, c=1 and Q 1 is an unsubstituted heteroaryl having 6 to 18 ring carbon atoms and at least one ring heteroatom selected from the group consisting of N, O, and S.

[0209] In some embodiments of Formula IV, c=1 and Q 1 is a substituted heteroaryl having 6 to 18 ring carbon atoms and having one or more substituents selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

[0210] In some embodiments, the heteroaryl group is derived from a compound selected from the group consisting of pyridine, carbazole, dibenzofuran, and dibenzothiophene.

[0211] In some embodiments of Formula IV, Ar 2 is an unsubstituted carbocyclic aryl having 6 to 20 ring carbon atoms; in some embodiments, it is an unsubstituted carbocyclic aryl having 6 to 12 ring carbon atoms.

[0212] In some embodiments of Formula IV, Ar 2 is a substituted carbocyclic aryl having 6 to 20 ring carbon atoms and having one or more substituents selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

[0213] In some embodiments, the carbocyclic aryl is selected from the group consisting of phenyl, biphenyl, naphthyl, binaphthyl, and anthracenyl.

[0214] In some embodiments of Formula IV, Ar 2 is an unsubstituted heteroaryl having 6 to 18 ring carbon atoms and at least one ring heteroatom selected from the group consisting of N, O, and S.

[0215] In some embodiments of Formula IV, Ar 2 is a substituted heteroaryl having 6 to 18 ring carbon atoms and having one or more substituents selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

[0216] In some embodiments, the heteroaryl group is derived from a compound selected from the group consisting of pyridine, carbazole, dibenzofuran, and dibenzothiophene.

[0217] Ar of Formula IV 2 All of the above embodiments relating to Ar of formula IV 3 applies equally to

[0218] R in Formula I 1 , R2 , R 3 All of the above embodiments for a, a, and b are R of formula IV 1 , R 2 , R 3 , a, and b equally.

[0219] In some embodiments of Formula IV, the diamine is of Formula IVA, Formula IVB, or Formula IVC.

[0220] [ka]

[0221] [In formula: R 5 are the same or different at each occurrence and are selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, unsubstituted or substituted carbocyclic aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, siloxy, and deuterated analogs thereof; d is an integer from 0 to 4; and Ar 2 , Ar 3 , R 1 , R 2 , a, and b are as defined in Formula IV. It has.

[0222] In some embodiments of Formula IVC, d=0.

[0223] In some embodiments of Formula IVC, d=1.

[0224] In some embodiments of Formula IVC, d=2.

[0225] In some embodiments of Formula IVC, d=3.

[0226] In some embodiments of Formula IVC, d=4.

[0227] In some embodiments of Formula IVC, d>0.

[0228] In some embodiments of Formula IVC, d>0 and R of Formula I 1 All of the above embodiments relating to R of formula IVC 5 applies equally to

[0229] Ar of Formula IV 2 , Ar 3 , R 1 , R 2 All of the above embodiments relating to a, a, and b are also applicable to Ar of Formula IVA, Formula IVB, and Formula IVC. 2 , Ar 3 , R 1 , R 2 , a, and b equally.

[0230] In some embodiments, the diamine has Formula VII:

[0231] In some embodiments of Formula VII, Ar 4 is an unsubstituted carbocyclic aryl having 6 to 20 ring carbon atoms; in some embodiments, it is an unsubstituted carbocyclic aryl having 6 to 12 ring carbon atoms.

[0232] In some embodiments of Formula VII, Ar 4 is a substituted carbocyclic aryl having 6 to 20 ring carbon atoms and having one or more substituents selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

[0233] In some embodiments, the carbocyclic aryl is selected from the group consisting of phenyl, biphenyl, naphthyl, binaphthyl, and anthracenyl.

[0234] In some embodiments of Formula VII, Ar 4is an unsubstituted heteroaryl having 6 to 18 ring carbon atoms and at least one ring heteroatom selected from the group consisting of N, O, and S.

[0235] In some embodiments of Formula VII, Ar 4 is a substituted heteroaryl having 6 to 18 ring carbon atoms and having one or more substituents selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

[0236] In some embodiments of Formula VII, the heteroaryl group is derived from a compound selected from the group consisting of pyridine, carbazole, dibenzofuran, and dibenzothiophene.

[0237] Ar of Formula IV 2 , Ar 3 , R 1 , R 2 All of the above embodiments for a, a, and b are also contemplated for Ar of Formula VII. 2 , Ar 3 , R 1 , R 2 , a, and b equally.

[0238] The novel compounds can be prepared using any technique that results in a C-C or C-N bond, or other desired bond. A variety of such techniques are known, including Suzuki, Yamamoto, Stille, Negishi, and metal-catalyzed C-N coupling, as well as metal-catalyzed and oxidative direct arylation. Two synthetic schemes are shown below.

[0239] [ka]

[0240] Any of the above-described embodiments of formula IV can be combined with one or more other embodiments, provided they are not mutually inconsistent. For example, an embodiment in which the diamine has formula IVB is one in which a=1 and R 1is CF3, and embodiments where b=1 and R 2 can be combined with an embodiment where is CF3. One of ordinary skill in the art would understand which embodiments are mutually exclusive and, as a result, would be able to readily determine the combinations of embodiments contemplated by this application.

[0241] Any of the above-described embodiments of formula VII can be combined with one or more other embodiments, provided they are not mutually inconsistent. For example, Ar 4 The embodiment where a is phenyl can be combined with the embodiment where a=b=0. One of ordinary skill in the art will understand which embodiments are mutually exclusive and, as a result, will be able to readily determine the combinations of embodiments contemplated by this application.

[0242] Some non-limiting examples of compounds having formula IV are shown below.

[0243] [ka]

[0244] [ka]

[0245] Some non-limiting examples of compounds having formula VII are shown below.

[0246] [ka]

[0247] 4. Polyamic acid In some embodiments, the polyamic acid has Formula II

[0248] [ka]

[0249] [In formula: R a may be the same or different in each occurrence and represent the residue of one or more tetracarboxylic acid moieties; and R b may be the same or different at each occurrence and represent one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R a is the residue from one or more dianhydrides having formula I It has the repeating unit structure:

[0250] In some embodiments of Formula II, residues of a dianhydride having Formula I are present as an additive to enhance the color of polyamic acids and polyimide films formed from the polyamic acids. The dianhydride having Formula I can attenuate the apparent color, so that the film appears pale yellow.

[0251] In some embodiments of Formula II, a dianhydride having Formula I is present as an additive and 0.001 to 10 mole % of R a are residues from one or more dianhydrides having Formula I; in some embodiments, 0.01 to 5 mol %; in some embodiments, 0.1 to 1.0 mol %. In some embodiments, a single dianhydride having Formula I is used as the additive.

[0252] In some embodiments of Formula II, the dianhydride having Formula I is present to improve properties such as CTE, Tg, and thermal stability of polyimide films made from the polyamic acid.

[0253] In some embodiments of Formula II, a dianhydride having Formula I is present to improve the properties of the final polyimide film, and 10 to 100 mole % of R aare residues from one or more dianhydrides having formula I; in some embodiments, 20 to 100 mol %; in some embodiments, 30 to 100 mol %; in some embodiments, 40 to 100 mol %; in some embodiments, 50 to 100 mol %; in some embodiments, 60 to 100 mol %; in some embodiments, 70 to 100 mol %; in some embodiments, 80 to 100 mol %; in some embodiments, 90 to 100 mol %; in some embodiments, 100 mol %.

[0254] In some embodiments of Formula II, 10 to 100 mole percent of R a represents the dianhydride residue from one dianhydride having formula I as shown above.

[0255] In some embodiments of Formula II, 10 to 100 mole percent of R a represents the dianhydride residue from two different dianhydrides, both having formula I, as shown above.

[0256] In some embodiments of Formula II, 10 to 100 mole percent of R a represents the dianhydride residue from three different dianhydrides, all having formula I, as shown above.

[0257] In some embodiments of Formula II, 10 to 100 mole percent of R a represents a dianhydride residue from four or more different dianhydrides, all having formula I, as shown above.

[0258] In some embodiments of Formula II, 10 to 90 mole % of R a are residues from one or more dianhydrides having Formula I; in some embodiments, 20 to 80 mole %; in some embodiments, 30 to 70 mole %.

[0259] Any of the above embodiments of formula I of formula II can be combined with one or more other embodiments, provided they are not mutually inconsistent.

[0260] In some embodiments of Formula II, R a represents a dianhydride residue from one or more dianhydrides having formula I, and at least one additional dianhydride residue.

[0261] In some embodiments of Formula II, R a represents a dianhydride residue from one or more dianhydrides having formula I, and one additional dianhydride residue.

[0262] In some embodiments of Formula II, R a represents a dianhydride residue from one or more dianhydrides having formula I, and two additional dianhydride residues.

[0263] In some embodiments of Formula II, R a represents a dianhydride residue from one or more dianhydrides having formula I, and three additional dianhydride residues.

[0264] In some embodiments, the additional dianhydride residue is selected from the group consisting of pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4'-hexafluoroisopropylidenebisphthalic dianhydride (6FDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene ester (TAHQ), 3,3',4,4'-diphenyl The residue is from a dianhydride selected from the group consisting of sulfonetetracarboxylic dianhydride (DSDA), 4,4'-bisphenol-A dianhydride (BPADA), hydroquinone diphthalic anhydride (HQDEA), ethylene glycol bis(trimellitic anhydride) (TMEG-100), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronapthalene-1,2-dicarboxylic anhydride (DTDA); 4,4'-bisphenol A dianhydride (BPADA), and the like, combinations thereof, and deuterated analogs thereof. These aromatic dianhydrides include deuterium, alkyl, aryl, nitro, cyano, -N(R')(R''), halo, hydroxy, carboxy, 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 (wherein s=0 to 2) or -S(O) s-heteroaryl (where s=0-2) and their deuterated analogs, and can be optionally substituted with groups known in the art. R' and R" are each independently an optionally substituted alkyl, cycloalkyl, or aryl group. In certain embodiments, R' and R" together with the nitrogen atom to which they are attached can form a ring system. The substituents can also be bridging groups.

[0265] In some embodiments of Formula II, the additional dianhydride residues are from one or more tetracarboxylic dianhydrides selected from the group consisting of PMDA, BPDA, 6FDA, and BTDA.

[0266] In some embodiments of Formula II, R b represents a single diamine residue.

[0267] In some embodiments of Formula II, R b represents two diamine residues.

[0268] In some embodiments of Formula II, R b represents three diamine residues.

[0269] In some embodiments of Formula II, R b represents four diamine residues.

[0270] In some embodiments of Formula II, R b represents one or more diamine residues.

[0271] Examples of suitable aromatic diamines include, but are not limited to, p-phenylenediamine (PPD), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 3,3'-dimethyl-4,4'-diaminobiphenyl (o-tolidine), 3,3'-dihydroxy-4,4'-diaminobiphenyl (HAB), 9,9'-bis(4-aminophenyl)fluorene (FDA), o-tolidine sulfone (TSN), 2,3,5,6-tetramethyl-1,4-phenylenediamine (TMPD), 2,4-diamino-1,3,5-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'-methylenedianiline (MDA), 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]bisaniline (Bis-M), 4,4'-[1,4-phenylenebis(1-methyl-ethylidene)]bisaniline (Bis-P), 4,4'-oxydianiline (4,4'-ODA), m -phenylenediamine (MPD), 3,4'-oxydianiline (3,4'-ODA), 3,3'-diaminodiphenyl sulfone (3,3'-DDS), 4,4'-diaminodiphenyl sulfone (4,4'-DDS), 4,4'-diaminodiphenyl sulfide (ASD), 2,2-bis[4-(4-amino-phenoxy)phenyl]sulfone (BAPS), 2,2-bis[4-(3-aminophenoxy)-phenyl]sulfone (m-BAPS), 1,4'-bis(4-aminophenoxy)benzene (TPE-Q), 1,3'-bis(4-aminophenoxy)phenyl (phenoxy)benzene (TPE-R), 1,3'-bis(4-amino-phenoxy)benzene (APB-133), 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), 4,4'-diaminobenzanilide (DABA), methylenebis(anthranilic acid) (MBAA), 1,3'-bis(4-aminophenoxy)-2,2-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'-diaminodiphenylmethane (TMMDA), and the like, as well as combinations and deuterated analogs thereof.

[0272] In some embodiments of Formula II, R b represents a diamine residue from one or more diamines selected from the group consisting of PPD, 4,4'-ODA, 3,4'-ODA, TFMB, Bis-A-AF, Bis-AT-AF, and Bis-P.

[0273] In some embodiments, the polyamic acid has the formula V

[0274] [ka]

[0275] [In formula: R a1 may be the same or different in each occurrence and represent the residue of one or more tetracarboxylic acid moieties; and R b1 may be the same or different at each occurrence and represent one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R b1 is the residue from one or more diamines having formula IV. It has the repeating unit structure:

[0276] In some embodiments of Formula V, R a1 represents the residue of a single tetracarboxylic acid component.

[0277] In some embodiments of Formula V, R a1 represents the residues of two tetracarboxylic acid components.

[0278] In some embodiments of Formula V, R a1 represents the residues of three tetracarboxylic acids.

[0279] In some embodiments of Formula V, R a1 represents the residues of four tetracarboxylic acids.

[0280] In some embodiments of Formula V, R a1 represents the residue of one or more tetracarboxylic dianhydrides.

[0281] Examples of suitable aromatic tetracarboxylic dianhydrides include, but are not limited to, those dianhydrides given above for Formula II.

[0282] In some embodiments of Formula V, R a1 represents one or more residues from a tetracarboxylic dianhydride selected from the group consisting of PMDA, BPDA, 6FDA, and BTDA.

[0283] In some embodiments of Formula V, R a1 represents a PMDA residue.

[0284] In some embodiments of Formula V, R a1 represents a BPDA residue.

[0285] In some embodiments of Formula V, R a1 represents the 6 FDA residues.

[0286] In some embodiments of Formula V, R a1 represents a BTDA residue.

[0287] In some embodiments of Formula V, R a1 represents a PMDA residue and a BPDA residue.

[0288] In some embodiments of Formula V, R a1 represents the PMDA residue and 6FDA residues.

[0289] In some embodiments of Formula V, R a1 represents a PMDA residue and a BTDA residue.

[0290] In some embodiments of Formula V, R a1 represents a BPDA residue and 6FDA residues.

[0291] In some embodiments of Formula V, R a1 represents BPDA and BTDA residues.

[0292] In some embodiments of Formula V, R a1 represents 6 FDA residues and BTDA residues.

[0293] In some embodiments of Formula V, R a1 represents a PMDA residue, a BPDA residue, and a 6FDA residue.

[0294] In some embodiments of Formula V, the residue of a diamine having Formula IV is present as an additive to enhance the color of polyamic acids and polyimide films formed from the polyamic acids. The diamine having Formula IV can attenuate the apparent color, so that the film appears pale yellow.

[0295] In some embodiments of Formula V, a diamine having Formula IV is present as an additive and 0.001 to 10 mole % of R b1 is the residue from one or more diamines having formula IV; in some embodiments, 0.01 to 5 mol %; in some embodiments, 0.1 to 1.0 mol %. In some embodiments, a single diamine having formula IV is used as the additive.

[0296] In some embodiments of Formula V, a diamine having Formula IV is present to enhance properties such as CTE, Tg, and thermal stability of polyimide films made from the polyamic acid.

[0297] In some embodiments of Formula V, a diamine having Formula IV is present to improve the properties of the final polyimide film, and 10 to 100 mole % of R b1 are residues from one or more diamines having formula IV; in some embodiments, 20 to 100 mol %; in some embodiments, 30 to 100 mol %; in some embodiments, 40 to 100 mol %; in some embodiments, 50 to 100 mol %; in some embodiments, 60 to 100 mol %; in some embodiments, 70 to 100 mol %; in some embodiments, 80 to 100 mol %; in some embodiments, 90 to 100 mol %; in some embodiments, 100 mol %.

[0298] In some embodiments of Formula V, 10 to 100 mole percent of R b1 represents the diamine residue from one diamine having formula IV as shown above.

[0299] In some embodiments of Formula V, 10 to 100 mole percent of R b1 represents diamine residues from two different diamines, both having formula IV, as shown above.

[0300] In some embodiments of Formula V, 10 to 100 mole percent of R b1 represents diamine residues from three different diamines, all having formula IV, as shown above.

[0301] In some embodiments of Formula V, 10 to 100 mole percent of R b1 represents diamine residues from four or more different diamines, all having formula IV, as shown above.

[0302] Any of the above embodiments of formula V with respect to formula IV can be combined with one or more other embodiments, provided they are not mutually inconsistent.

[0303] In some embodiments of Formula V, R b1 represents diamine residues from one or more diamines having formula IV, and at least one additional diamine residue.

[0304] In some embodiments of Formula V, R b1 represents diamine residues from one or more diamines having formula IV, and one additional diamine residue.

[0305] In some embodiments of Formula V, R b1 represents a diamine residue from one or more diamines having formula IV, and two additional diamine residues.

[0306] In some embodiments of Formula V, R b1 represents a diamine residue from one or more diamines having formula IV, and three additional diamine residues.

[0307] Examples of suitable additional diamines include, but are not limited to, those diamines provided above for Formula II.

[0308] In some embodiments of Formula V, R b1 represents a diamine residue from one or more diamines having formula IV and at least one additional diamine, wherein the additional diamine is selected from the group consisting of PPD, 4,4′-ODA, 3,4′-ODA, TFMB, Bis-A-AF, Bis-AT-AF, and Bis-P.

[0309] In some embodiments, the polyamic acid has the formula VII

[0310] [ka]

[0311] [In formula: R a2 are the same or different at each occurrence and represent the residue of one or more tetracarboxylic acid moieties; and R b2 are the same or different at each occurrence and represent one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R b2 is the residue from one or more diamines having formula VII. It has the repeating unit structure:

[0312] R in Equation V a1 All of the above embodiments relating to R of formula VIII a2 applies equally to

[0313] In some embodiments of Formula VIII, the residue of a diamine having Formula VII is present as an additive to enhance the color of polyamic acids and polyimide films formed from the polyamic acids. The diamine having Formula VII can attenuate the apparent color, so that the film appears pale yellow.

[0314] In some embodiments of Formula VIII, a diamine having Formula VII is present as an additive and comprises 0.001 to 10 mole % of R b2 is the residue from one or more diamines having Formula VII; in some embodiments, 0.01 to 5 mol %; in some embodiments, 0.1 to 1.0 mol %. In some embodiments, a single diamine having Formula VII is used as the additive.

[0315] In some embodiments of Formula VIII, the diamine having Formula VII is present to enhance properties such as CTE, Tg, and thermal stability of polyimide films made from the polyamic acid.

[0316] In some embodiments of Formula VIII, a diamine having Formula VII is present to improve the properties of the final polyimide film, and 10 to 100 mole % of R b2 are residues from one or more diamines having Formula VII; in some embodiments, 20 to 100 mol %; in some embodiments, 30 to 100 mol %; in some embodiments, 40 to 100 mol %; in some embodiments, 50 to 100 mol %; in some embodiments, 60 to 100 mol %; in some embodiments, 70 to 100 mol %; in some embodiments, 80 to 100 mol %; in some embodiments, 90 to 100 mol %; in some embodiments, 100 mol %.

[0317] In some embodiments of Formula VIII, 10 to 100 mole % of R b2 represents the diamine residue from one diamine having formula VII as shown above.

[0318] In some embodiments of Formula VIII, 10 to 100 mole percent of R b2 represents diamine residues from two different diamines, both having formula VII, as shown above.

[0319] In some embodiments of Formula VIII, 10 to 100 mole % of R b2 represents diamine residues from three different diamines, all having formula VII, as shown above.

[0320] In some embodiments of Formula VIII, 10 to 100 mole percent of R b2 represents diamine residues from four or more different diamines, all having formula VII, as shown above.

[0321] In some embodiments of Formula VIII, 20 to 100 mole % of R b2are residues from one or more diamines having Formula VII; in some embodiments, 30 to 100 mol %; in some embodiments, 40 to 100 mol %; in some embodiments, 50 to 100 mol %; in some embodiments, 60 to 100 mol %; in some embodiments, 70 to 100 mol %; in some embodiments, 80 to 100 mol %; in some embodiments, 90 to 100 mol %; in some embodiments, 100 mol %.

[0322] Any of the above embodiments of formula VIII with respect to formula VII can be combined with one or more other embodiments, provided they are not mutually inconsistent.

[0323] In some embodiments of Formula VIII, R b2 represents diamine residues from one or more diamines having formula VII, and at least one additional diamine residue.

[0324] In some embodiments of Formula VIII, R b2 represents a diamine residue from one or more diamines having formula VII, and one additional diamine residue.

[0325] In some embodiments of Formula VIII, R b2 represents a diamine residue from one or more diamines having formula VII, and two additional diamine residues.

[0326] In some embodiments of Formula VIII, R b2 represents a diamine residue from one or more diamines having formula VII, and three additional diamine residues.

[0327] Examples of suitable additional diamines include, but are not limited to, those diamines provided above for Formula II.

[0328] In some embodiments of Formula VIII, R b2represents a diamine residue from one or more diamines having Formula VII and at least one additional diamine, wherein the additional diamine is selected from the group consisting of PPD, 4,4′-ODA, 3,4′-ODA, TFMB, Bis-A-AF, Bis-AT-AF, and Bis-P.

[0329] In some embodiments of Formula II, Formula V, and Formula VIII, the moiety derived from the monoanhydride monomer is present as an end-capping group.

[0330] In some embodiments, the monoanhydride monomer is selected from the group consisting of phthalic anhydride, and the like, and derivatives thereof.

[0331] In some embodiments, the monoanhydride is present in an amount up to 5 mole % of the total tetracarboxylic acid composition.

[0332] In some embodiments of Formula II, Formula V, and Formula VIII, the moiety derived from a monoamine monomer is present as an end-capping group.

[0333] In some embodiments, the monoamine monomer is selected from the group consisting of aniline and the like and derivatives thereof.

[0334] In some embodiments, the monoamine is present in an amount up to 5 mole % of the total amine composition.

[0335] In some embodiments, the polyamic acid has a weight average molecular weight (M) of greater than 100,000 as determined by gel permeation chromatography using standard polystyrene standards. W )

[0336] In some embodiments, the polyamic acid has a weight average molecular weight (M) of greater than 150,000 as determined by gel permeation chromatography using standard polystyrene standards. W )

[0337] In some embodiments, the polyamic acid has a molecular weight (M) of greater than 200,000 as determined by gel permeation chromatography using standard polystyrene standards. W )

[0338] In some embodiments, the polyamic acid has a weight average molecular weight (M) of greater than 250,000 as determined by gel permeation chromatography using standard polystyrene standards. W )

[0339] In some embodiments, the polyamic acid has a weight average molecular weight (M) of greater than 300,000 as determined by gel permeation chromatography using standard polystyrene standards. W )

[0340] In some embodiments, the polyamic acid has a weight average molecular weight (M) of 100,000 to 400,000 as calculated by gel permeation chromatography using standard polystyrene standards. W )

[0341] In some embodiments, the polyamic acid has a weight average molecular weight (M) of 200,000 to 400,000 as calculated by gel permeation chromatography using standard polystyrene standards. W )

[0342] In some embodiments, the polyamic acid has a weight average molecular weight (M) of 250,000 to 350,000 as calculated by gel permeation chromatography using standard polystyrene. W )

[0343] In some embodiments, the polyamic acid has a weight average molecular weight (M) of 200,000 to 300,000 as calculated by gel permeation chromatography using standard polystyrene standards. W )

[0344] Any of the foregoing embodiments relating to polyamic acids can be combined with one or more other embodiments, provided they are not mutually inconsistent.

[0345] The overall polyamic acid composition can be designated via notation commonly used in the art, for example, a polyamic acid having a tetracarboxylic acid component that is 100% ODPA and a diamine component that is 90 mole % Bis-P and 10 mole % TFMB would be represented as follows: ODPA / / Bis-P / 22TFMB 100 / / 90 / 10.

[0346] Also provided is a liquid composition, also referred to herein as a "polyamic acid solution," comprising (a) a polyamic acid having repeating units of Formula II and (b) a high-boiling aprotic solvent.

[0347] Also provided is a liquid composition comprising (a) a polyamic acid having repeating units of formula V, and (b) a high-boiling aprotic solvent.

[0348] Also provided is a liquid composition comprising (a) a polyamic acid having repeating units of formula VIII, and (b) a high-boiling aprotic solvent.

[0349] In some embodiments, the high boiling aprotic solvent has a boiling point of 150° C. or greater.

[0350] In some embodiments, the high boiling aprotic solvent has a boiling point of 175° C. or greater.

[0351] In some embodiments, the high boiling aprotic solvent has a boiling point of 200° C. or greater.

[0352] In some embodiments, the high boiling point aprotic solvent is a polar solvent. In some embodiments, the solvent has a dielectric constant greater than 20.

[0353] Some examples of high boiling point 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, and the like, and combinations thereof.

[0354] In some embodiments of the liquid composition, the solvent is selected from the group consisting of NMP, DMAc, and DMF.

[0355] In some embodiments of the liquid composition, the solvent is NMP.

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

[0357] In some embodiments of the liquid composition, the solvent is DMF.

[0358] In some embodiments of the liquid composition, the solvent is gamma-butyrolactone.

[0359] In some embodiments of the liquid composition, the solvent is dibutyl carbitol.

[0360] In some embodiments of the liquid composition, the solvent is butyl carbitol acetate.

[0361] In some embodiments of the liquid composition, the solvent is diethylene glycol monoethyl ether acetate.

[0362] In some embodiments of the liquid composition, the solvent is propylene glycol monoethyl ether acetate.

[0363] In some embodiments, two or more of the above-specified high boiling aprotic solvents are used in the liquid composition.

[0364] In some embodiments, an additional co-solvent is used in the liquid composition.

[0365] In some embodiments, the liquid composition is less than 1 wt. % polyamic acid in greater than 99 wt. % high boiling aprotic solvent.

[0366] In some embodiments, the liquid composition is 1-5 wt % polyamic acid in 95-99 wt % high boiling aprotic solvent.

[0367] In some embodiments, the liquid composition is 5-10 wt % polyamic acid in 90-95 wt % high boiling aprotic solvent.

[0368] In some embodiments, the liquid composition is 10-15 wt % polyamic acid in 85-90 wt % high boiling aprotic solvent.

[0369] In some embodiments, the liquid composition is 15-20 wt % polyamic acid in 80-85 wt % high boiling aprotic solvent.

[0370] In some embodiments, the liquid composition is 20-25 wt % polyamic acid in 75-80 wt % high boiling aprotic solvent.

[0371] In some embodiments, the liquid composition is 25-30 wt % polyamic acid in 70-75 wt % high boiling aprotic solvent.

[0372] In some embodiments, the liquid composition is 30-35 wt % polyamic acid in 65-70 wt % high boiling aprotic solvent.

[0373] In some embodiments, the liquid composition is 35-40 wt % polyamic acid in 60-65 wt % high boiling aprotic solvent.

[0374] In some embodiments, the liquid composition is 40-45 wt % polyamic acid in 55-60 wt % high boiling aprotic solvent.

[0375] In some embodiments, the liquid composition is 45-50 wt % polyamic acid in 50-55 wt % high boiling aprotic solvent.

[0376] In some embodiments, the liquid composition is 50% by weight polyamic acid in 50% by weight high boiling aprotic solvent.

[0377] The polyamic acid solution can optionally further contain any one of a number of additives, such as antioxidants, heat stabilizers, adhesion promoters, coupling agents (e.g., silanes), inorganic fillers, or various toughening agents, provided they do not adversely affect the desired polyimide properties.

[0378] The polyamic acid solution can be prepared using a variety of available methods for the introduction of the components (i.e., monomers and solvents). Some methods for producing a polyamic acid solution include: (a) The diamine and dianhydride components are premixed together and then added portionwise to the solvent while the mixture is being stirred. (b) A method in which the solvent is added to a stirred mixture of the diamine and dianhydride components (as opposed to (a) above). (c) A method in which the diamine is dissolved exclusively in a solvent and the dianhydride is then added to it in a ratio that makes it possible to control the reaction rate. (d) A method in which the dianhydride component is dissolved exclusively in a solvent and the amine component is then added thereto in a ratio that makes it possible to control the reaction rate. (e) A method in which the diamine component and the dianhydride component are dissolved separately in a solvent and then these solutions are mixed in a reactor. (f) A process in which a polyamic acid containing an excess of an amine component and another polyamic acid containing an excess of a dianhydride component are preformed and then reacted with each other in a reactor in such a way as to produce, inter alia, a non-random or block copolymer. (g) A method in which a specific portion of the amine component and dianhydride component are reacted first, followed by the remaining diamine component, or vice versa. (h) A process in which the components are added, partially or as a whole, in any order to any part or all of the solvent, and further in which any part or all of the components may be added as a solution in any part or all of the solvent. (i) One of the dianhydride components is first reacted with one of the diamine components to form a first polyamic acid, followed by reaction of the other dianhydride component with the other amine component to form a second polyamic acid, which are then combined in any one of several ways prior to film formation. Generally speaking, the polyamic acid solution can be obtained from any one of the polyamic acid solution preparation methods disclosed above.

[0379] The polyamic acid solution can then be filtered one or more times to reduce particle content. Polyimide films resulting from such filtrates exhibit reduced defect counts and can therefore provide superior performance in the electronics applications disclosed herein. Filtration efficiency can be evaluated by laser particle counting testing, in which a representative sample of the polyamic acid solution is cast onto a 5-inch silicon wafer. After soft baking / drying, the film is evaluated for particle content by any number of laser particle counting techniques on equipment commercially available and known in the art.

[0380] In some embodiments, the polyamic acid solution is prepared and filtered to provide a particle content of less than 40 particles as measured by laser particle counting testing.

[0381] In some embodiments, the polyamic acid solution is prepared and filtered to provide a particle content of less than 30 particles as measured by laser particle counting testing.

[0382] In some embodiments, the polyamic acid solution is prepared and filtered to provide a particle content of less than 20 particles as measured by laser particle counting testing.

[0383] In some embodiments, the polyamic acid solution is prepared and filtered to provide a particle content of less than 10 particles as measured by laser particle counting testing.

[0384] In some embodiments, the polyamic acid solution is prepared and filtered to provide a particle content of between 2 particles and 8 particles as measured by laser particle counting testing.

[0385] In some embodiments, the polyamic acid solution is prepared and filtered to provide a particle content of between 4 particles and 6 particles as measured by laser particle counting testing.

[0386] An exemplary preparation of a polyamic acid solution is provided in the Examples.

[0387] 5. Polyimide In some embodiments, the polyimide has Formula III

[0388] [ka]

[0389] [In the formula, R a may be the same or different in each occurrence and represent the residue of one or more tetracarboxylic acid moieties; and R b may be the same or different at each occurrence and represent one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R a is the residue from one or more dianhydrides having formula I It has the repeating unit structure:

[0390] R in Formula II a and R b All of the above embodiments relating to R of Formula III a and R b applies equally to

[0391] Any of the above embodiments of formula I of formula III can be combined with one or more other embodiments, provided they are not mutually inconsistent.

[0392] In some embodiments, the polyimide has Formula VI

[0393] [ka]

[0394] [In the formula, R a1 are the same or different at each occurrence and represent the residue of one or more tetracarboxylic acid moieties; and R b1 are the same or different at each occurrence and represent one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R b1 is the residue from one or more diamines having formula IV. It has the repeating unit structure:

[0395] R in Equation V a1 and R b1 All of the above embodiments relating to R of formula VI a1 and R b1 applies equally to

[0396] Any of the above embodiments of formula IV of formula VI can be combined with one or more other embodiments, provided they are not mutually inconsistent.

[0397] In some embodiments, the polyimide has Formula IX

[0398] [ka]

[0399] [In the formula, R a2 are the same or different at each occurrence and represent the residue of one or more tetracarboxylic acid moieties; and R b2 are the same or different at each occurrence and represent one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R b2 is the residue from one or more diamines having formula VII. It has the repeating unit structure:

[0400] R of Formula VIII a2 and R b2 All of the above embodiments relating to R of formula IX a2 and R b2 applies equally to

[0401] Any of the above embodiments of formula VII of formula IX can be combined with one or more other embodiments, provided they are not mutually inconsistent.

[0402] Polyimides can be made from any suitable polyimide precursor, such as polyamic acids, polyamic acid esters, polyisoimides, and polyamic acid salts.

[0403] Also provided as described above are polyimide films in which the polyimide has the repeating unit structure of Formula III, Formula VI, or Formula IX.

[0404] Polyimide films can be produced by coating a polyimide precursor onto a substrate, followed by imidization, which can be accomplished by a thermal or chemical conversion process.

[0405] Additionally, if the polyimide is soluble in a suitable coating solvent, it can be provided as an already imidized polymer dissolved in a suitable coating solvent and coated as a polyimide.

[0406] In some embodiments, polyimide films having repeating units of Formula III, Formula VI, or Formula IX have both a high glass transition temperature and low optical retardation.

[0407] In some embodiments of the polyimide film, the glass transition temperature (T g ) is greater than 300°C for polyimide films cured at temperatures greater than 350°C; in some embodiments, greater than 370°C; in some embodiments, greater than 380°C.

[0408] In some embodiments of the polyimide film, the optical retardation at 550 nm is less than 120; in some embodiments, less than 100; in some embodiments, less than 90.

[0409] In some embodiments of the polyimide film, the in-plane coefficient of thermal expansion (CTE) is less than 45 ppm / °C from 50°C to 200°C as measured initially; in some embodiments, less than 30 ppm / °C; in some embodiments, less than 20 ppm / °C; and in some embodiments, less than 15 ppm / °C.

[0410] In some embodiments of the polyimide film, the in-plane coefficient of thermal expansion (CTE) is less than 75 ppm / °C from 50°C to 200°C, as measured a second time; in some embodiments, less than 65 ppm / °C.

[0411] In some embodiments of the polyimide film, the 1% TGA weight loss temperature is greater than 350°C; in some embodiments, greater than 400°C; in some embodiments, greater than 450°C.

[0412] In some embodiments of the polyimide film, the tensile modulus is 1.5 GPa to 15.0 GPa; in some embodiments, 1.5 GPa to 10.0 GPa; in some embodiments, 1.5 to 7.5 GPa; in some embodiments, 1.5 to 5.0 GPa.

[0413] In some embodiments of the polyimide film, the elongation at break is greater than 10%.

[0414] In some embodiments of the polyimide film, the haze is less than 1.0%; in some embodiments, less than 0.5%.

[0415] In some embodiments of the polyimide film, b * is less than 7.5; in some embodiments, less than 5.0.

[0416] In some embodiments of the polyimide film, the YI is less than 12; in some embodiments, less than 10.

[0417] In some embodiments of the polyimide film, the transmittance at 400 nm is greater than 40%; in some embodiments, greater than 50%.

[0418] In some embodiments of the polyimide film, the transmittance at 430 nm is greater than 60%; in some embodiments, greater than 70%.

[0419] In some embodiments of the polyimide film, the transmittance at 450 nm is greater than 70%; in some embodiments, greater than 80%.

[0420] In some embodiments of the polyimide film, the transmittance at 550 nm is greater than 70%; in some embodiments, greater than 80%.

[0421] In some embodiments of the polyimide film, the transmittance at 750 nm is greater than 70%; in some embodiments, greater than 80%.

[0422] Any of the above-described embodiments relating to polyimide films can be combined with one or more other embodiments, provided they are not mutually inconsistent.

[0423] 6. Preparation method of polyimide film Generally, polyimide films can be prepared from polyimide precursors by chemical or thermal conversion. In some embodiments, the films are prepared from the corresponding polyamic acid solutions by chemical or thermal conversion processes. The polyimide films disclosed herein, particularly when used as flexible alternatives to glass in electronic devices, are prepared by thermal conversion processes.

[0424] Generally, polyimide films can be prepared from the corresponding polyamic acid solutions by chemical or thermal conversion processes. The polyimide films disclosed herein, particularly when used as flexible replacements for glass in electronic devices, are prepared by thermal or modified thermal conversion processes as opposed to chemical conversion processes.

[0425] Chemical conversion processes are described in U.S. Patent No. 5,629,999 and U.S. Patent No. 5,629,999, which are incorporated by reference in their entireties. In such processes, conversion chemicals are added to a polyamic acid solution. Conversion chemicals found to be useful in the present invention include, but are not limited to, (i) one or more dehydrating agents, such as fatty acid anhydrides (e.g., acetic anhydride) and acid anhydrides; and (ii) one or more catalysts, such as aliphatic tertiary amines (e.g., triethylamine), tertiary amines (e.g., dimethylaniline), and heterocyclic tertiary amines (e.g., pyridine, picoline, isoquinoline). The anhydride used to dehydrate the material is typically used in slight molar excess over the amount of amic acid groups present in the polyamic acid solution. The amount of acetic anhydride used is typically about 2.0 to 3.0 moles per equivalent of polyamic acid. An equivalent amount of tertiary amine catalyst is generally used.

[0426] Thermal conversion processes may or may not use a converting chemical (i.e., a catalyst) to convert the cast polyamic acid solution to a polyimide. If a converting chemical is used, the process may be considered a modified thermal conversion process. In both types of thermal conversion processes, only thermal energy is used to heat the film both to dry the film of solvent and to carry out the imidization reaction. Generally, thermal conversion processes with or without a converting catalyst are used to prepare the polyimide films disclosed herein.

[0427] Specific process parameters are preselected with the understanding that it is not just the film composition that produces the properties of interest. Rather, the cure temperature and temperature ramp profile also play an important role in achieving the most desirable properties for the intended uses disclosed herein. The polyamic acid must be imidized at a maximum temperature that is at or above the temperature of any subsequent processing steps (e.g., deposition of inorganic or other layers required to produce a functional display), but below the temperature at which significant thermal decomposition / discoloration of the polyimide occurs. It should also be mentioned that an inert atmosphere is generally preferred when particularly high processing temperatures are used for imidization.

[0428] For the polyamic acids / polyimides disclosed herein, temperatures between 300°C and 320°C are typically used when subsequent processing temperatures above 300°C are required. Selecting the proper cure temperature allows for a fully cured polyimide that achieves the best balance of thermal and mechanical properties. Due to these extremely high temperatures, an inert atmosphere is required. Typically, an oxygen level of less than 100 ppm in the oven must be used. The extremely low oxygen level allows for the highest cure temperatures to be used without significant degradation / discoloration of the polymer. Catalysts that accelerate the imidization process are effective in achieving higher levels of imidization at cure temperatures of about 200°C to 300°C. This approach allows for flexible devices to be manufactured using the T of polyimides. g may optionally be used if prepared using an upper cure temperature below

[0429] The amount of time in each latent cure step is a further important process consideration. Generally, the time used for curing at the highest temperature should be kept to a minimum. For a 320°C cure, for example, the cure time may be up to an hour or so or under an inert atmosphere; however, at higher cure temperatures, it is desirable to reduce this time to avoid thermal degradation. Generally speaking, the higher the temperature, the shorter the time. Those skilled in the art will recognize the balance of temperature and time to optimize the properties of the polyimide for a particular end use.

[0430] In some embodiments, the polyamic acid solution is converted into a polyimide film by a thermal conversion process.

[0431] In some embodiments of the thermal conversion process, the polyamic acid solution is coated onto a substrate such that the resulting film has a soft bake thickness of 10-50 μm.

[0432] In some embodiments of the thermal conversion process, the coated substrate is soft baked on a hotplate in proximity mode, where nitrogen gas is used to hold the coated substrate directly above the hotplate.

[0433] In some embodiments of the thermal conversion process, the coated substrate is soft baked on a hotplate in full contact mode, where the coated substrate is in direct contact with the hotplate surface.

[0434] In some embodiments of the thermal conversion process, the coated substrate is soft baked on a hotplate using a combination of proximity and full contact modes.

[0435] In some embodiments of the thermal conversion process, the coated substrate is soft baked using a hotplate set at 80-140°C.

[0436] In some embodiments of the thermal conversion process, the coated substrate is soft baked for a total time of 2 to 10 minutes.

[0437] In some embodiments of the thermal conversion process, the soft-baked coating substrate is subsequently cured at 2 to 10 preselected temperatures for 2 to 10 preselected time intervals, the latter of which may be the same or different.

[0438] In some embodiments of the thermal conversion process, the preselected temperature is in the range of 80 to 450°C.

[0439] In some embodiments of the thermal conversion process, one or more of the preselected time intervals is 2 minutes.

[0440] In some embodiments of the thermal conversion process, one or more of the preselected time intervals is 5 minutes.

[0441] In some embodiments of the thermal conversion process, one or more of the preselected time intervals is 10 minutes.

[0442] In some embodiments of the thermal conversion process, one or more of the preselected time intervals is 15 minutes.

[0443] In some embodiments of the thermal conversion process, one or more of the preselected time intervals is greater than 15 minutes.

[0444] In some embodiments of the thermal conversion process, one or more of the preselected time intervals is between 2 minutes and 60 minutes.

[0445] In some embodiments of the thermal conversion process, one or more of the preselected time intervals is between 2 minutes and 120 minutes.

[0446] In some embodiments of the thermal conversion process, a method of preparing a polyimide film comprises the following steps, in order: coating a substrate with the polyamic acid solution described above; soft-baking the coated substrate; and treating the soft-baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic applications as disclosed herein.

[0447] In some embodiments of the thermal conversion process, the method of preparing a polyimide film comprises the following steps in sequence: coating a substrate with the polyamic acid solution described above; soft-baking the coated substrate; and treating the soft-baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic applications as disclosed herein.

[0448] In some embodiments of the thermal conversion process, the method of preparing a polyimide film consists essentially of the following steps, in order: coating a substrate with the polyamic acid solution described above; soft-baking the coated substrate; and treating the soft-baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic applications as disclosed herein.

[0449] Typically, the polyamic acid solution / polyimide disclosed herein is coated / cured onto a supporting glass substrate to facilitate processing through the remainder 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 as a film with the deposited display layers from the glass, enabling flexible formats. Often, this polyimide film with the deposited layers is then adhered to a thicker, yet still flexible, plastic film to provide support for subsequent fabrication of the display.

[0450] Also provided is a modified thermal conversion process in which a conversion catalyst generally causes the imidization reaction to occur at a lower temperature than would be possible in the absence of such conversion catalyst.

[0451] In some embodiments, the polyamic acid solution is converted to a polyimide film by a modified thermal conversion process.

[0452] In some embodiments of the modified thermal conversion process, the polyamic acid solution further comprises a conversion catalyst.

[0453] In some embodiments of the modified thermal conversion process, the polyamic acid solution further comprises a conversion catalyst selected from the group consisting of tertiary amines.

[0454] In some embodiments of the modified thermal conversion process, the polyamic acid solution is coated onto a substrate such that the soft bake thickness of the resulting film is less than 10-50 μm.

[0455] In some embodiments of the modified thermal conversion process, the coated substrate is soft baked on a hotplate in proximity mode, where nitrogen gas is used to hold the coated substrate directly above the hotplate.

[0456] In some embodiments of the modified thermal conversion process, the coated substrate is soft baked on a hotplate in full contact mode, where the coated substrate is in direct contact with the hotplate surface.

[0457] In some embodiments of the modified thermal conversion process, the coated substrate is soft baked on a hotplate using a combination of proximity and full contact modes.

[0458] In some embodiments of the modified thermal conversion process, the coated substrate is soft baked using a hotplate set at 80-150°C.

[0459] In some embodiments of the modified thermal conversion process, the coated substrate is soft baked for a total time of 2 to 10 minutes.

[0460] In some embodiments of the modified thermal conversion process, the soft-baked coating substrate is subsequently cured at 2 to 10 preselected temperatures for 2 to 10 preselected time intervals, the latter of which can be the same or different.

[0461] In some embodiments of the modified thermal conversion process, the preselected temperature is from 80 to over 300°C.

[0462] In some embodiments of the modified thermal conversion process, one or more of the preselected time intervals is between 2 minutes and 120 minutes.

[0463] In some embodiments of the modified thermal conversion process, a method of preparing a polyimide film comprises the following steps, in order: coating a substrate with a polyamic acid solution containing the conversion chemicals described above; soft-baking the coated substrate; and treating the soft-baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic applications as disclosed herein.

[0464] In some embodiments of the modified thermal conversion process, a method for preparing a polyimide film comprises the following steps in sequence: coating a substrate with a polyamic acid solution containing the conversion chemicals described above; soft-baking the coated substrate; and treating the soft-baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic applications as disclosed herein.

[0465] In some embodiments of the modified thermal conversion process, the method of preparing a polyimide film consists essentially of the following steps, in order: coating a substrate with a polyamic acid solution containing the conversion chemicals described above; soft-baking the coated substrate; and treating the soft-baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic applications as disclosed herein.

[0466] 7. Electronic Devices The polyimide films disclosed herein may be suitable for use in several layers in electronic display devices, such as OLED and LCD displays. Non-limiting examples of such layers include device substrates, touch panels, substrates for color filter sheets, cover films, etc. The specific material property requirements for each application are unique and can be addressed by appropriate composition and processing conditions for the polyimide films disclosed herein.

[0467] In some embodiments, as detailed above, the flexible alternative to glass in electronic devices is a polyimide film having repeating units of Formula III, Formula VI, or Formula IX.

[0468] Organic electronic devices that can benefit from one or more layers containing at least one compound described herein include, but are not limited to, (1) devices that convert electrical energy into radiation (e.g., light-emitting diodes, light-emitting diode displays, lighting devices, luminaires, or diode lasers), (2) devices that detect signals through electronic processes (e.g., photodetectors, photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes, infrared detectors, and biosensors), (3) devices that convert radiation into electrical energy (e.g., photovoltaic devices or solar cells), (4) devices that convert light of one wavelength into light of a longer wavelength (e.g., downconverting phosphor devices), and (5) devices that include one or more electronic components containing one or more organic semiconductor layers (e.g., transistors or diodes). Other uses of the compositions according to the present invention include coating materials for memory storage devices, antistatic films, biosensors, electrochemical devices, energy storage devices such as solid electrolyte capacitors and secondary batteries, and electromagnetic shielding applications.

[0469] An example of a polyimide film that can serve as a flexible alternative to glass as described herein is shown in FIG. 1. The flexible film 100 can have the properties described in the embodiments of this disclosure. In some embodiments, the polyimide film that can serve as a flexible alternative to glass is included in an electronic device. FIG. 2 illustrates an organic electronic device 200. The device 200 includes a substrate 100, an anode layer 110 and a second electrical contact layer, a cathode layer 130, and a photoactive layer 120 therebetween. Optionally, additional layers may be present. The layer adjacent to the anode layer may be a hole injection layer (not shown), sometimes referred to as a buffer layer. The layer adjacent to the hole injection layer may be a hole transport layer (not shown) comprising a hole transport material. The layer adjacent to the cathode layer may be an electron transport layer (not shown) comprising an electron transport material. Optionally, the device may employ one or more additional hole-injection or hole-transport layers (not shown) next to the anode 110 and / or one or more additional electron-injection or electron-transport layers (not shown) next to the cathode 130. Layers 110-130 are individually and collectively referred to as organic active layers. Additional layers that may or may not be present include color filters, touch panels, and / or cover sheets. One or more of these layers may also be fabricated from the polyimide films disclosed herein in addition to the substrate 100.

[0470] The different layers will be discussed further herein with reference to Figure 2. However, the discussion applies to other configurations as well.

[0471] In some embodiments, the different layers have thicknesses in the following ranges: substrate 100, 5 to 100 microns; anode 110, 500 to 5,000 Å, and in some embodiments, 1,000 to 2,000 Å; hole injection layer (not shown), 50 to 2,000 Å, and in some embodiments, 200 to 1,000 Å; hole transport layer (not shown), 50 to 3,000 Å, and in some embodiments, 200 to 2,000 Å; photoactive layer 120, 10 to 2,000 Å, and in some embodiments, 100 to 1,000 Å; electron transport layer (not shown), 50 to 2,000 Å, and in some embodiments, 100 to 1,000 Å; and cathode 130, 200 to 10,000 Å, and in some embodiments, 300 to 5,000 Å. The desired ratio of layer thicknesses depends on the exact nature of the materials used.

[0472] In some embodiments, organic electronic devices (OLEDs) include the flexible alternatives to glass disclosed herein.

[0473] In some embodiments, an 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.

[0474] 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.

[0475] 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. Furthermore, the materials, methods, and examples are illustrative only and not intended to be limiting. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. [Example]

[0476] The concepts described herein are further illustrated in the following examples, which do not limit the scope of the invention as claimed.

[0477] Synthesis Example 1 This example illustrates the preparation of compound IV-3, a diamine having formula IV.

[0478] [ka]

[0479] 4-Bromo-N-(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)naphthalimide (3) 4-Bromo-1,8-naphthalenedicarboxylic anhydride 1 (25 g, 90.23 mmol) and 4'-nitro-2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4-amine 2 (31.7 g, 90.5 mmol) were stirred in NMP (100 mL) at 180 °C under a nitrogen atmosphere for 5 h. The reaction mixture was cooled and diluted with water. The precipitate was collected by filtration, washed with water, and dried. The solid was dissolved in 1 L of hot chloroform and passed through a short column packed with silica gel eluted with chloroform. The chloroform was removed to a minimum volume using a rotary evaporator, and methanol was added. The precipitate collected by filtration was dried to give 4-bromo-N-(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)naphthalimide 3 (total yield: 36.43 g). MS:MH+=609. 1H NMR(CDCl3):7.48(d,1H,J=9Hz),7.61(dd,1H,J1=8Hz,J2=2Hz),7.66(d,1H,J=9Hz),7.79(d,1H,J=2Hz),7.95(dd,1H,J1=8Hz,J2=7.5Hz),8.14(d, 1H,J=7.5Hz),8.48(dd,1H,J1=9Hz,J2=2Hz),8.51(d,1H,J=8Hz),8.69(d,1H,J=2Hz),8.71(dd,1H,J1=9Hz,J2=1Hz),8.75(dd,1H,J1=7Hz,J2=1Hz).

[0480] 4-Amino-N-(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)naphthalimide (4) A mixture of 4-bromo-N-(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)naphthalimide 3 (29 g, 47.6 mmol) and tin chloride dihydrate (42.95 g, 190 mmol) in methanol (150 mL) was stirred at reflux for 4 hours. The reaction mixture was cooled, diluted with water (100 mL), and the crude product was collected by filtration and washed with a 1:1 mixture of methanol and water. The crude product was dissolved in acetonitrile and passed through a filter packed with silica gel and basic alumina, eluting with acetonitrile. The acetonitrile was evaporated to a minimum volume to give compound 4, which was used in the next step without further purification. 5.72(s,2H),6.82(dd,1H,J1=9Hz,J2=2Hz),6.99(d,1H,J=2Hz),7.03(d,1H,J=9Hz),7.45(d,1H,J=8Hz),7.69(dd,1H,J1=8Hz,J2=2Hz),7.91 (d,1H,J=2Hz),8.06(dd,1H,J1=8Hz,J2=7.5Hz),8.29(d,1H,J=8Hz),8.37(d,1H,J=8Hz),8.61(d,1H,J=7Hz),8.64(dd,1H,J1=9Hz,J2=1Hz).

[0481] 6,6'-[2,5-bis(trifluoromethyl)-1,4-phenylene]bis[2-(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-1H-benzo[de]isoquinoline-1,3(2H)-dione (6), Compound IV-3 A mixture of 4-amino-N-(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)naphthalimide 4 (7.82 g, 13.5 mmol), 2,2'-[2,5-bis(trifluoromethyl)-1,4-phenylene]bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane 5 (3.15 g, 6.75 mmol), ClPd(amphos) (0.143 g, 0.2025 mmol), and potassium phosphate (7.16 g, 33.75 mmol) in toluene (100 mL), ethanol (40 mL), and water (20 mL) was stirred at 100 °C for 1 h. The reaction mixture was cooled, and the product was filtered, washed with toluene and water, and dried to give 7.48 g of crude product with a purity of approximately 95% by UPLC. The crude product was dissolved in tetrahydrofuran and passed through a filter packed with silica gel, Florisil, and basic alumina, eluting with tetrahydrofuran. After distilling off the tetrahydrofuran, the residue was repeatedly crystallized from a mixture of tetrahydrofuran and hexane, yielding a product with a purity of over 99.5%. 1 H-NMR(dmso-d6):5.74(s,4H),6.85(d,2H,J=8Hz),7.02(d,2H,J=2Hz),7.07(d,2H,J=8Hz), 7.95-8.07(m,6H),8.17(s,2H),8.63(t,2H,J=8Hz),8.66(d,1H,J=8Hz),8.70(d,1H,J=7Hz).

[0482] Synthesis Example 2 This example illustrates the preparation of the dianhydride having formula I, 6,6'-[2,5-bis(trifluoromethyl)-1,4-phenylene]bis-1H,3H-naphtho[1,8-cd]pyran-1,3-dione (7), compound I-2.

[0483] [ka]

[0484] A mixture of 4-bromo-1,8-naphthalenedicarboxylic anhydride 1 (1.249 g, 4.51 mmol), 2,2'-[2,5-bis(trifluoromethyl)-1,4-phenylene]bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane 5 (1 g, 2.15 mmol), ClPd(Amphos) (0.046 g, 0.0645 mmol), and potassium phosphate (2.281 g, 10.75 mmol) in toluene (50 mL), ethanol (20 mL), and water (10 mL) was stirred at 100 °C for 3 h. The reaction mixture was decanted hot, and the precipitate was washed with water and acetone, stirred in concentrated hydrochloric acid (30 mL) in water for 2 h, filtered, and dried to give 1.24 g of crude product. The crude product was treated with 30 ml of dimethyl sulfoxide, filtered, and the precipitate was washed with water to give the desired product with a purity of 99.51% by HPLC. The filtrate was diluted with water (100 ml), and the precipitate was collected by filtration. Acetic anhydride (10 ml) was added and the mixture was stirred at 140°C for 2 hours. The precipitate was collected by filtration to give the desired product with a purity of 99.1%. MS: MH+ = 607. 1 H-NMR (dmso-d6): 7.92-8.04 (m) and 8.29 (d, J = 8.8 Hz) atropisomers (6H), 8.12 (s, 2H), 8.61-8.71 (m, 4H, atropisomers). Photoluminescence: λ = 418 ± 5 nm (in tetrahydrofuran), quantum yield -59%.

[0485] Polymer Example 1 This example illustrates the preparation of a polyamic acid using diamine compound IV-3.

[0486] A mixture of compound IV-3 (3.733 g) from Synthesis Example 1, 3,3',4,4'-biphenyltetracarboxylic dianhydride (0.889 g), and N-methylpyrrolidinone (27 g) was stirred in a glass reactor at ambient temperature, followed by the addition of pyromellitic dianhydride (8 mg) to a final viscosity of 13,670 cP. GPC: Mn = 75,827, Mw = 163,321, Mp = 150,475, Mz = 272,075, PDI = 2.15.

[0487] Polymer Example 2 This example illustrates the preparation of a polyamic acid using diamine compound IV-3.

[0488] A mixture of compound IV-3 (4.919 g) from Synthesis Example 1, 3,3′,4,4′-biphenyltetracarboxylic dianhydride (1.171 g), 5,5′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis-1,3-isobenzofurandione 6FDA (36 mg), and N-methylpyrrolidinone (41 g) was stirred in a glass reactor at ambient temperature, and then 6FDA (36 mg) was added in two portions to a final viscosity of 1565 cP.

[0489] Film Example 1 This example illustrates the preparation of a polyimide film.

[0490] The polyamic acid solution from Polymer Example 1 was filtered through a microfilter, spin-coated onto a clean silicon wafer, soft-baked on a hotplate at 90°C, and placed in a furnace. The furnace was heated in stages under a nitrogen atmosphere to a maximum cure temperature of 375°C. The wafer was removed from the furnace, immersed in water, and manually delaminated to yield a 11.6 μm thick polyimide film sample.

[0491] b along with % transmittance (%T) over the wavelength range of 350 nm to 780 nm using a Hunter Lab spectrophotometer *and Yellowness Index were measured. Thermal measurements of the films were performed using a combination of thermogravimetric and thermomechanical analysis appropriate for the specific parameters reported herein. Mechanical properties were measured using Instron equipment.

[0492] The film properties are as follows: Thickness = 11.6 μm Tg>450℃ CTE=2.66 ppm / ℃ Cloud value = 1.27% b * =14.4 YI=22.5 η=0.1018 birefringence.

[0493] Film Example 2 This example illustrates the preparation of a polyimide film.

[0494] The polyamic acid solution from Polymer Example 2 was filtered through a microfilter, spin-coated onto a clean silicon wafer, soft-baked on a hotplate at 90°C, and placed in a furnace. The furnace was heated in stages under a nitrogen atmosphere to a maximum cure temperature of 375°C. The wafer was removed from the furnace, immersed in water, and manually delaminated to yield a 10.26 μm thick polyimide film sample.

[0495] b along with % transmittance (%T) over the wavelength range of 350 nm to 780 nm using a Hunter Lab spectrophotometer * and Yellowness Index were measured. Thermal measurements of the films were performed using a combination of thermogravimetric and thermomechanical analysis appropriate for the specific parameters reported herein. Mechanical properties were measured using Instron equipment.

[0496] The film properties are as follows: Thickness = 10.26 μm Tg = 495℃ CTE=6.2ppm / ℃ Haze value = 0.5% b * =7.32 YI=12.85 η=0.0954 birefringence.

[0497] It should be noted that not all of the operations described above in the general description or examples are required, some of the specific operations may not be required, and one or more additional operations may be performed in addition to the operations described. Furthermore, the order in which the operations are listed is not necessarily the order in which the operations are performed.

[0498] In the foregoing specification, the present concepts have been described with reference to specific embodiments. However, those skilled in the art will appreciate that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.

[0499] Benefits, other advantages, and solutions to problems have been described above with respect to particular embodiments. However, the benefits, advantages, and solutions to problems, and any features that may produce or enhance any benefit, advantage, or solution, are not to be construed as critical, required, or essential features of any or all claims.

[0500] For clarity, it should be understood that certain features, which are described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, for brevity, various features that are described in the context of a single embodiment may also be provided individually or in any subcombination. The use of various ranges of numerical values ​​specified herein is described as approximations, as if the minimum and maximum values ​​within the stated ranges were both preceded by the word "about." In this manner, slight variations above and below the stated ranges can be used to achieve substantially the same results as the values ​​within the ranges. Furthermore, the disclosure of these ranges is intended to be a continuous range, including every value between the minimum and maximum average values, including fractional values ​​that may result when a portion of a component of one value is mixed with a portion of a component of a different value. Furthermore, when broader and narrower ranges are disclosed, it is within the contemplation of the invention to match the minimum value from one range with the maximum value from another range, and vice versa. [Explanation of symbols]

[0501] 100 boards 110 anode layer 120 Photoactive layer 130 cathode layer 200 Electronic Devices

Claims

1. Diamines of formula IV or VII 【Chemistry 1】 [In the formula: Ar 2 , Ar 3 , and Ar 4 are the same or different and are selected from the group consisting of carbocyclic aryl, heteroaryl, and substituted derivatives and deuterated analogs thereof; Q 1 represents a single bond, alkyl, silyl, ester, siloxane, oligosiloxane, polysiloxane, O, S, SO 2 , B.R. 3 , N.R. 3 , P(O)R 3 , unsubstituted or substituted carbocyclic aryl, and unsubstituted or substituted heteroaryl, and deuterated analogs thereof; R 1 and R 2 are the same or different at each occurrence and are selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, unsubstituted or substituted carbocyclic aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, siloxy, and deuterated analogs thereof; R 3 is selected from the group consisting of alkyl and unsubstituted or substituted carbocyclic aryl, and deuterated analogs thereof; a and b are the same or different and are integers from 0 to 5; and c is 0 or 1. A diamine having the formula:

2. Polyamic acids of formula V or formula VIII 【Chemistry 2】 [In the formula: R a1 are the same or different at each occurrence and represent the residue of one or more tetracarboxylic acid components; and R a2 are the same or different at each occurrence and represent the residue of one or more tetracarboxylic acid components; R b1 are the same or different at each occurrence and represent one or more aromatic diamine residues; and R b2 are the same or different at each occurrence and represent one or more aromatic diamine residues; and 0.001 to 100 mol% of R b1 is a diamine residue from one or more diamines having formula IV according to claim 1; and 0.001 to 100 mol% of R b2 is a diamine residue from one or more diamines having formula VII according to claim 1. A polyamic acid having the repeating unit structure:

3. Polyimides of Formula VI or Formula IX 【Transformation 3】 [In the formula: R a1 are the same or different at each occurrence and represent the residue of one or more tetracarboxylic acid components; and R a2 are the same or different at each occurrence and represent the residue of one or more tetracarboxylic acid components; R b1 are the same or different at each occurrence and represent one or more aromatic diamine residues; and R b2 are the same or different at each occurrence and represent one or more aromatic diamine residues; and 0.001 to 100 mol% of R b1 is a diamine residue from one or more diamines having formula IV according to claim 1; and 0.001 to 100 mol% of R b2 is a diamine residue from one or more diamines having formula VII according to claim 1. A polyimide having the repeating unit structure:

4. 10. A flexible replacement for glass in an electronic device, said flexible replacement for glass comprising a polyimide film having repeat units of Formula VI or Formula IX as recited in claim 3.

5. 10. An electronic device comprising the flexible alternative to glass of claim 4.

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