Polymers used in electronic devices

Abstract

To provide monomers that can be used for fabrication of low CTE, high Tg, high thermal stability polyimide films.SOLUTION: The present invention provides a specific 1,8-naphthalic dianhydride, and diamines having formula IV and formula VII.SELECTED DRAWING: Figure 1

Description

[Technical Field] 【0001】 Claims of the benefit of prior applications This application claims the benefit of the specification of U.S. Provisional Patent Application No. 62 / 978,579, filed February 19, 2020, which is incorporated in its entirety herein by reference. 【0002】 This disclosure relates to novel polymer compounds. This disclosure further relates to methods for preparing such polymer compounds and to electronic devices having at least one layer containing these materials. [Background technology] 【0003】 Materials used in electronics applications often have stringent requirements regarding their structural, optical, thermal, electronic, and other properties. As the number of commercial electronics applications continues to grow, the breadth and specificity of required properties necessitates innovation in materials with novel and / or improved properties. Polyimides refer to a category of polymer compounds that have been widely used in a variety of electronics applications. If they possess the appropriate properties, they can function as flexible substitutes for glass in electronic display devices. These materials can function as components in liquid crystal displays ("LCDs"), where moderate power consumption, light weight, and planar layers are crucial properties for effective practicality. Other uses in electronic display devices where such parameters are important include device substrates, substrates for color filter sheets, cover films, and touchscreen panels. 【0004】 Some of these components are also important in the construction and operation of organic electronic devices having organic light-emitting diodes ("OLEDs"). OLEDs are promising for numerous display applications due to their high power conversion efficiency and broad end-user applicability. They are increasingly used in mobile phones, tablet devices, handheld / laptop computers, and other commercial products. These applications require displays that offer large amounts of information, full color, and fast video response times, in addition to low power consumption. 【0005】 Polyimide films generally possess sufficient thermal stability, a high glass transition temperature, and mechanical toughness suitable for such applications. Furthermore, since polyimide generally does not develop a cloudy value when subjected to repeated bending, it is often preferred over other transparent substrates such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) in flexible display applications. Therefore, there is a continuing need for polymer materials 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) [Overview of the project] [Means for solving the problem] 【0008】 Discovering novel rigid structures that can yield polymers with low CTE, high Tg, and high thermal stability remains a challenge. The use of 1,8-naphthalic acid dianhydride and imide-containing polymers has been overlooked in the literature despite recent significant interest in various aromatic compounds, due to their low reactivity. 【0009】 This specification discloses monomers that can be used to produce 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 under ambient conditions. 【0010】 Furthermore, monomers can be used in small amounts as additives to improve the color of polyimide films. 【0011】 Equation I 【0012】 [ka] 【0013】 [In formula: Y is alkyl, silyl, ester, siloxane, oligosiloxane, polysiloxane, O, S, SO2, BR 3 , NR 3 P(O)R 3 Selected from the group consisting of unsubstituted or substituted carbocyclic aryls and unsubstituted or substituted heteroaryls; R 1 ~R 2 Each of these is either identical or different upon appearance, and is 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 their deuterated analogs; R 3 This is selected from the group consisting of alkyl and unsubstituted or substituted carbocyclic aryls, and their deuterated analogs; and a and b are the same or different and are integers from 0 to 5] There is provided a dianhydride having [it]. 【0014】 Formula II 【0015】 [Chemical formula] 【0016】 [In the formula: R a each appears the same or different and represents the residue of one or more tetracarboxylic acid components; and R b each appears the same or different and represents one or more aromatic diamine residues; here, 0.001 to 100 mol% of R a is the dianhydride residue from one or more dianhydrides having Formula 1] There is further provided a polyamic acid having a repeating unit of [it]. 【0017】 There is further provided a composition comprising (a) a polyamic acid having a repeating unit of Formula II and (b) a high-boiling aprotic solvent. 【0018】 whose repeating unit is Formula III 【0019】 [Chemical formula] 【0020】 [In the formula, R a and R b are as defined in Formula II] There is further provided a polyimide having the structure of [it]. 【0021】 There is further provided a polyimide film containing the repeating unit of Formula III. 【0022】 Formula IV 【0023】 [ka] 【0024】 [In formula: Ar 2 and Ar 3 They are either identical or different, and are selected from the group consisting of carbocyclic aryls, heteroaryls, and their substituted derivatives; Q 1 These include single bonds, alkyl, silyl, ester, siloxane, oligosiloxane, polysiloxane, O, S, SO2, BR 3 , NR 3 P(O)R 3 Selected from the group consisting of unsubstituted or substituted carbocyclic aryls and unsubstituted or substituted heteroaryls; R 1 and R 2 These are either identical or different at the time of their appearance, 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 their deuterated analogs. R 3 This is selected from the group consisting of alkyl and unsubstituted or substituted carbocyclic aryls; and a and b are either the same or different integers between 0 and 5; and c is either 0 or 1. A diamine having the following properties is further provided. 【0025】 Formula V 【0026】 [ka] 【0027】 [In formula: R a1Each of these is either identical or different when it appears, and represents one or more tetracarboxylic acid residues; and R b1 Each of these is either identical or different when it appears, and represents 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 are polyamic acids having repeating units. 【0028】 A composition comprising (a) a polyamic acid having repeating units of formula V, and (b) a high-boiling point aprotic solvent is further provided. 【0029】 The repeating unit is, Equation VI 【0030】 [ka] 【0031】 [In the formula, R a1 and R b1 This is as defined in Equation IV. A polyimide having the structure is further provided. 【0032】 Formula VII 【0033】 [ka] 【0034】 [In formula: Ar 2 Ar 3 and Ar 4 They are either identical or different, and are selected from the group consisting of carbocyclic aryls, heteroaryls, and their substituted derivatives; R 1 and R 2Each of these is either identical or different at the time of appearance and is 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 their deuterated analogs; and a and b are either the same or different integers between 0 and 5. A diamine having the following properties is further provided. 【0035】 Formula VIII 【0036】 [ka] 【0037】 [In formula: R a2 Each of these is either identical or different when it appears, and represents one or more tetracarboxylic acid residues; and R b2 Each of these is either identical or different when it appears, and represents 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 are polyamic acids having repeating units. 【0038】 A composition comprising (a) a polyamic acid having repeating units of formula VIII and (b) a high-boiling point aprotic solvent is further provided. 【0039】 The repeating unit is equation IX 【0040】 [ka] 【0041】 [In the formula, R a2 and R b2 This is as defined in Equation VIII. A polyimide having the structure is further provided. 【0042】 A polyimide film comprising repeating units of formula III, formula VI, or formula IX is further provided. 【0043】 One or more methods for preparing a polyimide film having repeating units of formula III, formula VI, or formula IX are further provided. 【0044】 Further flexible substitutes for glass in electronic devices are provided, in which case the flexible substitute 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】 For example, organic electronic devices such as OLEDs are further provided, in which case the organic electronic device includes flexible alternatives to the glass disclosed herein. 【0047】 The general description above and the detailed description below are illustrative and explanatory only and do not limit the invention as set forth in the attached claims. 【0048】 Embodiments are illustrated in the accompanying figures to facilitate understanding of the concepts presented herein. [Brief explanation of the drawing] 【0049】 [Figure 1] This includes an example of a polyimide film that can be used as a flexible alternative to glass. [Figure 2] This includes examples of electronic devices that include flexible alternatives to glass. [Modes for carrying out the invention] 【0050】 It will be apparent to those skilled in the art that the objects in the figures are illustrative for the sake of brevity and clarity, and are not necessarily drawn to scale. For example, the dimensions of some objects in the figures may be exaggerated relative to others to facilitate a better understanding of the embodiment. 【0051】 Many aspects and embodiments have been described above, but these are illustrative and not limiting. After reading this specification, those skilled in the art 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 are evident from the following detailed description and claims. The detailed description first deals with definitions and clarifications of terms, then deals with dianhydrides, diamines, polyamic acids, polyimides, methods for preparing polyimide films, electronic devices, and finally examples. 【0053】 1. Definition and clarification of terms Before discussing the details of the embodiments described later, we will define or clarify some terms. 【0054】 When used in "Definitions and Explanations of Terms," ​​R, R a , R b R', R'', and any other variables are generic terms and may be the same as or different from those defined in the expression. 【0055】 The term "alkyl" refers to a group derived from an aliphatic hydrocarbon, which may enclose a chain, branched, or cyclic group, and which may be unsubstituted or substituted. In some embodiments, the 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 atom in the chain is replaced by a heteroatom. In some embodiments, the heteroalkyl group has 1 to 20 carbon atoms. 【0056】 The term "aprotic" refers to a class of solvents that lack acidic hydrogen atoms and therefore cannot act as hydrogen donors. Common aprotic solvents include alkanes, carbon tetrachloride (CCl4), benzene, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and many other solvents. 【0057】 The term "aromatic compound" shall mean an organic compound containing at least one unsaturated cyclic group having 4n+2 delocalized π electrons. This term is intended to encompass both aromatic compounds having only carbon and hydrogen atoms, and heteroaromatic compounds in which one or more carbon atoms in the cyclic group are substituted by other atoms such as nitrogen, oxygen, sulfur, etc. 【0058】 The term "aryl" or "aryl group" refers to a site formed by removing one or more hydrogen atoms ("H") or deuterium atoms ("D") from an aromatic compound. An aryl group may be monocyclic (monocyclic formula) or may have multiple rings (bicyclic or more) bonded together by condensation or covalent bonds. A "carbocyclic aryl" has only carbon atoms in the aromatic ring. 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, it has 6 to 30 ring carbon atoms. In some embodiments, a heteroaryl group has 4 to 50 ring carbon atoms; in some embodiments, it has 4 to 30 ring carbon atoms. 【0059】 The term "alkoxy" refers to the group -OR (where R is alkyl). 【0060】 The term "aryloxy" refers to the group -OR (where R is aryl). 【0061】 Unless otherwise specified, all groups may be substituted or unsubstituted. Optionally substituted groups, such as alkyl or aryl groups, may be substituted with one or more substituents, which may be the same or different. Preferred 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, and -S(O). s -aryl (where s = 0 to 2) or -S(O) s -Heteroaryls (where s = 0 to 2 in the formula) are an example. 【0062】 The term "amine" refers to a compound containing a basic nitrogen atom along with a lone pair of electrons. The term "amino" refers to the functional group -NH2, -NHR, or -NR2 (wherein R is the same or different when it appears, and may be an alkyl group or an aryl group). The term "diamine" refers to a compound containing two basic nitrogen atoms along with associated lone pairs of electrons. The term "aromatic diamine" refers to an aromatic compound having two amino groups. The term "bent diamine" refers to a compound in which two basic nitrogen atoms and associated lone pairs of electrons are connected to the corresponding compound or functional group, e.g., m-phenylenediamine: 【0063】 [ka] 【0064】 This refers to diamines arranged asymmetrically around the center of symmetry. 【0065】 The term "aromatic diamine residue" refers to the portion of an aromatic diamine bonded to two amino groups. The term "aromatic diisocyanate residue" refers to the portion of an aromatic diisocyanate compound bonded to two isocyanate groups. Further examples are given below. 【0066】 [ka] 【0067】 The terms "diamine residue" and "diisocyanate residue" refer to the portion attached to two amino groups or two isocyanate groups, respectively, where the portion is aliphatic or aromatic. 【0068】 The term “b * " represents the opposite color of yellow / blue in the CIELab color space, b * This represents the axis. Yellow represents positive b. * Represented by a value, the blue color represents negative b. * It is expressed by a value. In particular, the choice of solvent can affect the color measured for materials exposed to high-temperature processing conditions, so the measured value b * This can be affected by the solvent. This can result from the inherent properties of the solvent and / or properties related to the low levels of impurities present in various solvents. Certain solvents may be desired for specific applications. * Values ​​are often pre-selected to achieve a specific outcome. 【0069】 The term "birefringence" refers to the difference in refractive indices in different directions within a polymer film or coating. This term typically refers to the difference between the x-axis or y-axis (in-plane) and z-axis (out-of-plane) refractive indices. 【0070】 When the term "charge transport" refers to a layer, material, component, or structure, it means that such a layer, material, component, or structure facilitates the movement of such charges through its thickness with relatively efficient and small charge loss. Hole-transporting materials facilitate positive charges; electron-transporting materials facilitate negative charges. Light-emitting materials may also have some charge-transporting properties, but the term "charge-transporting layer, material, component, or structure" is not intended to include layers, materials, components, or structures whose primary function is light emission. 【0071】 The term "compound" refers to a non-charged substance composed of molecules containing atoms that cannot be separated from their corresponding molecules by physical means without breaking chemical bonds. This term includes oligomers and polymers. 【0072】 The term "linear thermal expansion coefficient (CTE or α)" refers to a parameter that defines the amount by which a material expands or contracts as a function of temperature. The linear thermal expansion coefficient is expressed as the change in length per degree Celsius, and is generally 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 may be an important consideration in the fabrication and / or reliability of electronic devices. 【0073】 The term "dopant" means a material that, within a layer containing a host material, alters the target wavelength of radiation emission, reception, or filtering of that layer compared to the wavelength of radiation emission, reception, or filtering of that layer in which such material is not present. 【0074】 When referring to a layer or material, the term "electroactive" 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 electric charge (which can be either electrons or holes), or materials that emit radiation, or materials that exhibit a change in electron-hole pair concentration when exposed to radiation. Examples of inert materials include, but are not limited to, planarizing materials, insulating materials, and environmental barrier materials. 【0075】 The terms "tensile elongation" or "tensile strain" refer to the rate of increase in length that occurs within a material before fracture under applied tensile stress. It 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 base are substituted with fluorine. 【0077】 The term "glass transition temperature (or T)" g "Glass transition" refers to the temperature at which an irreversible change occurs in amorphous polymers, or within the amorphous region of semi-crystalline polymers, when a material suddenly changes from a hard, glassy, ​​or brittle state to a flexible or elastic state. Microscopically, a glass transition occurs when normal, coiled, motionless polymer chains become freely rotatable and can pass through each other. g ' may be measured using differential scanning calorimetry (DSC), thermomechanical analysis (TMA), dynamic mechanical analysis (DMA), or other methods. 【0078】 The prefix "hetero" indicates that one or more carbon atoms are substituted with different atoms. In some embodiments, the heteroatoms are O, N, S, or a combination thereof. 【0079】 The term "high boiling point" refers to a boiling point exceeding 130°C. 【0080】 The term "host material" refers to the material to which the 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 at higher concentrations. 【0081】 The term "laser particle counter test" refers to a method used to evaluate the particle content of polyamic acid and other polymer solutions, thereby spin-coating representative samples of the test solutions onto a 5-inch silicon wafer and soft-baking / drying them. The resulting films are then evaluated for particle content by any number of standard measurement techniques. Such techniques include laser particle detection, which is well known in the art. 【0082】 The term "liquid composition" refers to a liquid medium in which materials dissolve to form a solution, a liquid medium in which materials disperse to form a dispersion, or a liquid medium in which materials are suspended to form a suspension or emulsion. 【0083】 The term "substrate" refers to the base upon which one or more layers are placed when forming an electronic device, for example. Non-limiting examples include glass and silicon. 【0084】 The term "1% TGA weight loss" refers to the temperature at which 1% of the original polymer weight is lost due to decomposition (removal of absorbed water). 【0085】 The term "optical delay (or R)" TH ")" refers to the difference between the mean 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, the light delay is measured for light of a specific frequency, and the unit is reported in nanometers. 【0086】 The terms “organic electronic device” or, as used herein, “electronic device” mean a device comprising one or more organic semiconductor layers or materials. 【0087】 The term "particle content" refers to the number or count of insoluble particles present in a solution. Particle content can be measured in the solution itself or in product raw materials (components, films, etc.) prepared from those films. This characteristic can be evaluated using various optical methods. 【0088】 The term "photoactive" refers to a material or layer that emits light when activated by an applied voltage (such as in a light-emitting diode or chemical cell), emits light after the absorption of a photon (such as in a down-converting phosphor device), or generates a signal with or without an applied bias voltage in response to radiant energy (such as in a photodetector or photovoltaic cell). 【0089】 The term "polyamidic acid solution" refers to a solution of a polymer containing amide acid units that have the ability to undergo intramolecular cyclization to form imide groups. 【0090】 The term "polyimide" refers to condensed polymers resulting from the reaction of one or more bifunctional carboxylic acid components with one or more primary diamines or diisocyanates. They contain imide structures -CO-NR-CO- as linear or heterocyclic units along the main chain of the polymer backbone. 【0091】 The term "satisfactory," when relating to the properties or characteristics of a material, means that the properties or characteristics meet all requirements / demands for the material in use. 【0092】 The term "soft bake" refers to a process commonly used in electronics manufacturing in which a coated material is heated to expel the solvent and solidify the film. Soft bake is typically performed on a hot plate or in an oven with exhaust at a temperature of 90°C to 110°C as a preparatory step 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, but is not limited to, one or more layers of one or more materials, such as glass, polymers, metals, or ceramic materials, or combinations thereof. The substrate may or may not contain electronic components, electronic circuits, or conductive members. 【0094】 The term "siloxane" refers to a group R3SiOR2Si- or a divalent group -SiR2OR2Si- (wherein R is the same or different when it appears, H, C 1~20 This refers to alkyl, fluoroalkyl, or aryl groups. In some embodiments, one or more carbon atoms in the R-alkyl group are substituted with Si. Oligomer siloxanes have 2 to 5 repeating siloxane units. Polymeric siloxanes have more than 5 siloxane repeating units; in some embodiments, they have 6 to 12 siloxane repeating units. 【0095】 The term "siloxy" refers to the group R3SiO- (where R is the same or different when it appears, and H is C). 1~20 This refers to alkyl, fluoroalkyl, or aryl compounds. 【0096】 The term "silyl" is derived from the base R(R2Si) n -, or divalent group-(R2Si) n -(In the formula, R is either the same or different when it appears, H, C 1~20This refers to an alkyl, fluoroalkyl, or aryl group. In some embodiments, one or more carbon atoms in the R alkyl group are substituted with Si. In some embodiments, n is 1 to 10. 【0097】 The term "spin coating" refers to the process used to deposit a uniform, thin film onto a flat substrate. Generally, a small amount of coating material is applied to the center of the substrate, which is rotated slowly or not at all. The substrate is then rotated at a specific speed to evenly spread the coating material by centrifugal force. 【0098】 The term "tensile modulus" refers to a measure of the stiffness of a solid material that defines the initial relationship between stress (force per unit area) and strain (proportional deformation) in a material such as a film. The commonly used unit is gigapascal (GPa). 【0099】 The term "tetracarboxylic acid component" means 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 component residue" refers to the portion of the tetracarboxylic acid component bonded to the four carboxyl groups. Further examples are provided below. 【0101】 [ka] 【0102】 The term "transmittance" refers to the percentage of light of a given wavelength that strikes the film and passes through it in a way that is detectable on the opposite side. Light transmittance measurements within the visible region (380 nm to 800 nm) are particularly useful for characterizing the film color characteristics, which are most important for understanding the properties of the polyimide films disclosed herein in use. 【0103】 The term "Yellowness Index (or YI)" refers to the degree of yellowness compared to a standard. A positive YI value indicates the presence and magnitude of yellow. Materials with a negative YI appear bluish. It should also be noted that YI can be solvent-dependent, especially in polymerization and / or curing processes carried out at high temperatures. The magnitude of color introduced using DMAC as the solvent may differ from, for example, the magnitude of color introduced using NMP as the solvent. This can occur as a result of the inherent properties of the solvent and / or properties related to low levels of impurities contained in various solvents. Certain solvents are often pre-selected to achieve the desired YI value for specific applications. 【0104】 In a structure in which the substituent bond passes through one or more rings, as shown below, 【0105】 [ka] 【0106】 This means that the substituent R can be attached at any available position on one or more rings. 【0107】 The phrase "adjacent" does not necessarily mean that one layer is directly next to another when used to refer to layers in a device. On the other hand, 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 on atoms linked by a bond). Typical adjacent R groups are shown below. 【0108】 [ka] 【0109】 In this specification, unless otherwise explicitly stated or indicated in connection with use, where an embodiment of the subject matter herein is stated or described as including, encompassing, containing, having, consisting of, or being by or composed of, certain features or elements, one or more features or elements may be present in the embodiment in addition to those explicitly stated or described. An alternative embodiment of the subject matter disclosed herein is described as consisting of certain features or elements, but in that embodiment, there are no features or elements that substantially alter the principle of operation or the distinguishing characteristics of the embodiment. A further alternative embodiment of the subject matter described herein is described as consisting of certain features or elements, but in that embodiment or any non-substantial variation thereof, only the features or elements specifically stated or described are present. 【0110】 Furthermore, unless explicitly stated otherwise, "or" means inclusive or not exclusive. 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 both A and B are true (or exist). 【0111】 Similarly, the use of “one (a)” or “one (an)” is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one or at least one, and unless it becomes clear that it has a different meaning, the singular also includes the plural. 【0112】 The group numbers, which correspond to the columns in the periodic table of elements, use the "new 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 those commonly understood by those skilled in the art to which the present invention pertains. Similar or equivalent methods and materials may be used in the implementation or testing of embodiments of the present invention, but preferred methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety unless a specific section is cited. In case of any inconsistency, this specification, including definitions, shall prevail. Furthermore, materials, methods, and examples are illustrative and not intended to be limiting. 【0114】 For details not included in this specification, many specific materials, processing operations, and circuits can be found in conventional textbooks and other sources of information on organic light-emitting diode displays, photodetectors, photovoltaics, and semiconductor material technologies. 【0115】 2. Dianhydride The dianhydrous compounds described herein are of formula I 【0116】 [ka] 【0117】 [In formula: Y is alkyl, silyl, ester, siloxane, oligosiloxane, polysiloxane, O, S, SO2, BR 3 , NR 3 P(O)R 3 Selected from the group consisting of unsubstituted or substituted carbocyclic aryls, unsubstituted or substituted heteroaryls, and their deuterated analogs; R 1 ~R 2Each of these is either identical or different upon appearance, and is 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 their deuterated analogs; R 3 This is selected from the group consisting of alkyl and unsubstituted or substituted carbocyclic aryls, and their deuterated analogs; and a and b are either the same or different integers between 0 and 5. It holds. 【0118】 In some embodiments of formula I, Y is C 1~6 It is alkyl; in some embodiments, C 4~6 It is a 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 their deuterated analogs. In some embodiments, one or more substituents are selected from the group consisting of F, CN, alkyl, fluoroalkyl, and fluoroalkoxy, and their deuterated analogs. 【0119】 In some embodiments of formula I, Y is C 2~6 It's 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 That is the case. 【0128】 In some embodiments of formula I, Y is NR 3 That is the case. 【0129】 In some embodiments of formula I, Y is P(O)R 3 That is the case. 【0130】 In some embodiments of formula I, Y is an unsubstituted carbocyclic aryl having 6 to 20 ring carbon atoms; in some embodiments, Y is an unsubstituted carbocyclic aryl having 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 one or more substituents selected from the group consisting of F, CN, deuterium, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy, and their deuterated analogs. 【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 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 equation I, a = 0. 【0137】 In some embodiments of Equation I, a = 1. 【0138】 In some embodiments of Equation I, a = 2. 【0139】 In some embodiments of Equation I, a = 3. 【0140】 In some embodiments of Equation I, a = 4. 【0141】 In some embodiments of Equation I, a = 5. 【0142】 In some embodiments of Equation I, a > 0. 【0143】 In some embodiments of Equation I, a > 0 and at least one R 1 It is F. 【0144】 In some embodiments of Equation I, a > 0 and at least one R 1 This is CN. 【0145】 In some embodiments of Equation I, a > 0 and at least one R 1 C 1~20 It is alkyl; in some embodiments, C 1~10 It is alkyl. 【0146】 In some embodiments of Equation I, a > 0 and at least one R 1 C 1~20 It is a fluoroalkyl; in some embodiments, C 1~10 It is a fluoroalkyl group. 【0147】 In some embodiments of Equation I, a > 0 and at least one R 1 C 1~20 It is a perfluoroalkyl; in some embodiments, C 1~10 It is a perfluoroalkyl group. 【0148】 In some embodiments of Equation I, a > 0 and at least one R 1 C 1~20 It is an alkoxy; in some embodiments, C 1~10 It is an alkoxy. 【0149】 In some embodiments of Equation I, a > 0 and at least one R 1 C 1~20 It is a fluoroalkoxy; in some embodiments, C 1~10 It is a fluoroalkoxy. 【0150】 In some embodiments of Equation I, a > 0 and at least one R 1 C 1~20 It is a perfluoroalkoxy; in some embodiments, C 1~10 It is a perfluoroalkoxy. 【0151】 In some embodiments of Equation I, a > 0 and at least one R1 There 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, it is C 3~6 silyl. 【0153】 In some embodiments of Formula I, a > 0 and at least one R 1 is C 1~12 siloxy; in some embodiments, it is C 3~6 siloxy. 【0154】 In some embodiments of Formula I, a > 0 and at least one R 1 is unsubstituted or substituted C 6~30 hydrocarbon aryl; in some embodiments, it is unsubstituted or substituted C 6~18 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, it is unsubstituted or substituted C 3~18 heteroaryl; 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, it is unsubstituted or substituted C 6~18 hydrocarbon aryloxy; in some embodiments, it is unsubstituted. 【0157】 In some embodiments, any one of the aforementioned hydrocarbon aryl groups, heteroaryl groups, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and 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 aforementioned embodiments regarding a in Formula I are equally applicable to b in Formula I. 【0160】 In some embodiments, b > 0, and all of the aforementioned embodiments regarding R 1 are equally applicable to R 2 In some embodiments of Formula I, b = 1, and R 【0161】 is selected from the group consisting of F, trifluoromethyl, and trifluoromethoxy. 2 In some embodiments of Formula I, R 【0162】 3 is C 1~20 alkyl; in some embodiments, it is C 1~10 alkyl. 1~10 【0163】 In some embodiments of Formula I, R 3 is unsubstituted carbocyclic aryl having 6 to 20 ring carbon atoms; in some embodiments, it is unsubstituted carbocyclic aryl having 6 to 12 ring carbon atoms. 【0164】 In some embodiments of Formula I, R 3This is a substituted carbocyclic aryl having 6 to 20 ring carbon atoms and 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 dianhydrous is formula IA 【0166】 [ka] 【0167】 [In formula: R 5 Each of these is either identical or different upon appearance, and is 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 their deuterated analogs; d is an integer between 0 and 4; e is an integer between 1 and 5; and R 1 , R 2 a and b are as defined in Equation I. It holds. 【0168】 In some embodiments of equation IA, d = 0. 【0169】 In some embodiments of equation IA, d=1. 【0170】 In some embodiments of equation IA, d = 2. 【0171】 In some embodiments of formula IA, d = 3. 【0172】 In some embodiments of equation 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 all of the above-described embodiments regarding R of Formula I 1 are equally applicable to R of Formula IA. 5 【0180】 All of the above-described embodiments regarding R of Formula I 1 and R 2 and a and b are equally applicable to R of Formula IA 1 and R 2 and a and b. 【0181】 The novel compounds can be prepared using any technique that will result in a C-C or C-N bond, or other desired bonds. Various such techniques are known, such as Suzuki, Yamamoto, Stille, Negishi, and metal-catalyzed C-N coupling, and metal-catalyzed and oxidative direct arylation. One synthetic scheme is shown below: 【0182】 【Chemical Structure】 【0183】 Any of the above embodiments of formula I can be combined with one or more other embodiments, as long as they do not contradict each other. For example, an embodiment in which the dianhydride has formula IA is such that a=1 and R 1 Embodiments in which CF3 is, and b=1 and R 2 This can be combined with embodiments where CF3 is present. Those skilled in the art will understand which embodiments are mutually exclusive and will be able to easily determine the combinations of embodiments conceivable by this application. 【0184】 Some non-restrictive examples of compounds having formula I are shown below. 【0185】 [ka] 【0186】 [ka] 【0187】 3. Diamine The diamines described herein are those of formula IV or formula VII. 【0188】 [ka] 【0189】 [In formula: Ar 2 Ar 3 , and Ar 4 They are either identical or different, and are selected from the group consisting of carbocyclic aryls, heteroaryls, their substituted derivatives, and their deuterated analogs. Q 1 These are single bonds, alkyl, silyl, ester, siloxane, oligosiloxane, polysiloxane, S, SO2, BR 3 , NR 3 P(O)R 3, selected from the group consisting of unsubstituted or substituted carbocyclic aryls, unsubstituted or substituted heteroaryls, and their deuterated analogs; R 1 and R 2 Each of these is either identical or different upon appearance, and is 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 their deuterated analogs; R 3 This is selected from the group consisting of alkyl and unsubstituted or substituted carbocyclic aryls; and a and b are either the same or different integers between 0 and 5; and c is either 0 or 1. It holds. 【0190】 In some embodiments, the diamine has formula IV. 【0191】 In some embodiments of Equation IV, c = 0. 【0192】 In some embodiments of equation IV, c=1 and Q 1 It is a single bond. 【0193】 In some embodiments of equation IV, c=1 and Q 1 C 1~6 It is alkyl; in some embodiments, C 4~6 It is a 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 their deuterated analogs. In some embodiments, one or more substituents are selected from the group consisting of F, CN, alkyl, fluoroalkyl, and fluoroalkoxy. 【0194】 In some embodiments of equation IV, c=1 and Q 1 C 2~6 It's Cyril. 【0195】 In some embodiments of equation IV, c=1 and Q 1 It is an ester. 【0196】 In some embodiments of equation IV, c=1 and Q 1 It is a siloxane. 【0197】 In some embodiments of equation IV, c=1 and Q 1 It is an oligosiloxane. 【0198】 In some embodiments of equation IV, c=1 and Q 1 It is a polysiloxane. 【0199】 In some embodiments of equation IV, c=1 and Q 1 It is O. 【0200】 In some embodiments of equation IV, c=1 and Q 1 S is. 【0201】 In some embodiments of equation IV, c=1 and Q 1 It is SO2. 【0202】 In some embodiments of equation IV, c=1 and Q 1 , BR 3 That is the case. 【0203】 In some embodiments of equation IV, c=1 and Q 1 , NR 3 That is the case. 【0204】 In some embodiments of equation IV, c=1 and Q 1 P(O)R 3 That is the case. 【0205】 In some embodiments of equation IV, c=1 and Q 1 This 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 equation IV, c=1 and Q 1 This is a substituted carbocyclic aryl having 6 to 20 ring carbon atoms and 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 equation IV, c=1 and Q 1 This 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 equation IV, c=1 and Q 1 This is a substituted heteroaryl having 6 to 18 ring carbon atoms and 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 This 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 This is a substituted carbocyclic aryl having 6 to 20 ring carbon atoms and 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 This 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 This is a substituted heteroaryl having 6 to 18 ring carbon atoms and 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 in Equation IV 2 All of the above embodiments relating to are Ar of formula IV. 3 It applies equally to [the other thing]. 【0218】 R in Equation I 1 , R2 , R 3 All of the above embodiments relating to a, b, and R of formula IV 1 , R 2 , R 3 This applies equally to a and b. 【0219】 In some embodiments of formula IV, the diamine is formula IVA, formula IVB, or formula IVC 【0220】 [ka] 【0221】 [In formula: R 5 Each of these is either identical or different at the time of appearance and is 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 their deuterated analogs; d is an integer from 0 to 4; and Ar 2 Ar 3 , R 1 , R 2 a and b are as defined in Equation IV. It holds. 【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 the formula IVC are R 5 It applies equally to [the other thing]. 【0229】 Ar in Equation IV 2 Ar 3 , R 1 , R 2 All of the above embodiments relating to a and b are Ar of formulas IVA, IVB, and IVC. 2 Ar 3 , R 1 , R 2 This applies equally to a and b. 【0230】 In some embodiments, the diamine has formula VII. 【0231】 In some embodiments of formula VII, Ar 4 This 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 This is a substituted carbocyclic aryl having 6 to 20 ring carbon atoms and 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 4This 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. 【0235】 In some embodiments of formula VII, Ar 4 This is a substituted heteroaryl having 6 to 18 ring carbon atoms and 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 in Equation IV 2 Ar 3 , R 1 , R 2 All of the above embodiments relating to a, b, and the Ar of formula VII 2 Ar 3 , R 1 , R 2 This applies equally to a and b. 【0238】 Novel compounds can be prepared using any technique that results in CC or CN bonding, or any other desired bonding. Various such techniques are known, including Suzuki, Yamamoto, Still, Negishi, and metal-catalyzed CN coupling, as well as metal-catalyzed and direct arylation. Two synthesis schemes are shown below. 【0239】 [ka] 【0240】 Any of the above embodiments relating to formula IV can be combined with one or more other embodiments, as long as they do not conflict with each other. For example, an embodiment in which the diamine has formula IVB is such that a=1 and R 1Embodiments in which CF3 and b=1 and R 2 This can be combined with embodiments where CF3 is present. Those skilled in the art will understand which embodiments are mutually exclusive and will be able to easily determine the combinations of embodiments conceivable by this application. 【0241】 Any of the above embodiments relating to Formula VII can be combined with one or more other embodiments, insofar as they do not conflict with each other. For example, Ar 4 Embodiments in which a=b=0 can be combined with embodiments in which a=b=0. Those skilled in the art will understand which embodiments are mutually exclusive and will be able to easily determine the combinations of embodiments conceivable by this application. 【0242】 Some non-restrictive examples of compounds having formula IV are shown below. 【0243】 [ka] 【0244】 [ka] 【0245】 Some non-restrictive examples of compounds having formula VII are shown below. 【0246】 [ka] 【0247】 4. Polyamic acid In some embodiments, the polyamic acid is a polyamic acid of formula II 【0248】 [ka] 【0249】 [In formula: R a Each of these represents a residue of one or more tetracarboxylic acid components, which may or may not be the same when they appear; and R b Each of these may be identical or different when it appears, and represents one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R a However, it is a residue from one or more dianhydrides having formula I. It has a repeating unit structure. 【0250】 In some embodiments of Formula II, a dianhydride residue having Formula I is present as an additive to improve the color of polyamic acid and the polyimide film formed from the polyamic acid. Since the dianhydride having Formula I can weaken the apparent color, 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 mol% of R a However, the residue is from one or more dianhydrides having formula I; in some embodiments, it is 0.01 to 5 mol%; in some embodiments, it is 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, a dianhydride having Formula I is present to improve properties such as CTE, Tg, and thermal stability of polyimide films produced from polyamic acids. 【0253】 In some embodiments of Formula II, a dianhydride having Formula I is present to improve the properties of the final polyimide film, and 10-100 mol% of R aHowever, the residue is from one or more dianhydrides having formula I; in some embodiments, 20-100 mol%; in some embodiments, 30-100 mol%; in some embodiments, 40-100 mol%; in some embodiments, 50-100 mol%; in some embodiments, 60-100 mol%; in some embodiments, 70-100 mol%; in some embodiments, 80-100 mol%; in some embodiments, 90-100 mol%; and in some embodiments, 100 mol%. 【0254】 In some embodiments of formula II, 10 to 100 mol% of R a However, as shown above, it represents a dianhydride residue from a dianhydride having formula I. 【0255】 In some embodiments of formula II, 10 to 100 mol% of R a However, as shown above, both represent dianhydride residues from two different dianhydrides that have formula I. 【0256】 In some embodiments of formula II, 10 to 100 mol% of R a However, as shown above, all of them represent dianhydride residues from three different dianhydrides that have formula I. 【0257】 In some embodiments of formula II, 10 to 100 mol% of R a However, as shown above, all of them represent dianhydride residues from four or more different dianhydrides that have formula I. 【0258】 In some embodiments of formula II, 10 to 90 mol% of R a However, these are residues from one or more dianhydrides having formula I; in some embodiments, 20-80 mol%; in some embodiments, 30-70 mol%. 【0259】 Any of the aforementioned embodiments of Formula II relating to Formula I can be combined with one or more other embodiments, insofar as they do not conflict with each other. 【0260】 In some embodiments of formula II, R a This represents dianhydride residues from one or more dianhydrides having formula I, and at least one additional dianhydride residue. 【0261】 In some embodiments of formula II, R a This represents dianhydride residues from one or more dianhydrides having formula I, and one additional dianhydride residue. 【0262】 In some embodiments of formula II, R a This represents dianhydride residues from one or more dianhydrides having formula I, and two additional dianhydride residues. 【0263】 In some embodiments of formula II, R a This represents dianhydride residues from one or more dianhydrides having formula I, and three additional dianhydride residues. 【0264】 In some embodiments, the additional dianhydride residues include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), 4,4'-oxydiphthalic acid anhydride (ODPA), 4,4'-hexafluoroisopropylidene bisphthalic acid dianhydride (6FDA), 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA), bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene ester (TAHQ), and 3,3',4,4'-diphenyl These are residues from dianhydrides 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-tetrahydronaptalen-1,2-dicarboxylic anhydride (DTDA); 4,4'-bisphenol A dianhydride (BPADA), combinations thereof, and their deuterated analogs. 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, and -S(O) s -aryl (where s = 0 to 2) or -S(O) s-The substituents can be optionally substituted with groups known in the art, including heteroaryl groups (wherein s = 0 to 2) and their deuterated analogs. R' and R'' are each independently optionally substituted alkyl, cycloalkyl, or aryl groups. In certain embodiments, R' and R'' can form a ring system together with the nitrogen atom to which they are bonded. The substituents may also be bridging groups. 【0265】 In some embodiments of Formula II, the additional dianhydride residue is 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 This represents a single diamine residue. 【0267】 In some embodiments of formula II, R b This represents two diamine residues. 【0268】 In some embodiments of formula II, R b This represents three diamine residues. 【0269】 In some embodiments of formula II, R b This represents four diamine residues. 【0270】 In some embodiments of formula II, R b This 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-tolidinesulfone (TSN), 2,3,5,6-tetramethyl-1,4-phenylenediamine (TMPD), and 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-methylethylidene)]bisaniline (Bis-M), 4,4'-[1,4-phenylenebis(1-methylethylidene)]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-aminophenoxy)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) Phenoxy)benzene (TPE-R), 1,3'-bis(4-aminophenoxy)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,Examples include 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 combinations thereof, as well as deuterated analogs. 【0272】 In some embodiments of formula II, R b This 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 is of formula V 【0274】 [ka] 【0275】 [In formula: R a1 Each of these represents a residue of one or more tetracarboxylic acid components, which may or may not be the same when they appear; and R b1 Each of these may be identical or different when it appears, and represents one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R b1 [ is a residue from one or more diamines having formula IV] It has a repeating unit structure. 【0276】 In some embodiments of formula V, R a1 This represents a residue of a single tetracarboxylic acid component. 【0277】 In some embodiments of formula V, R a1 This represents the residues of the two tetracarboxylic acid components. 【0278】 In some embodiments of formula V, R a1 This represents three tetracarboxylic acid residues. 【0279】 In some embodiments of formula V, R a1 This represents four tetracarboxylic acid residues. 【0280】 In some embodiments of formula V, R a1 This represents one or more residues of tetracarboxylic dianhydride. 【0281】 Suitable examples of aromatic tetracarboxylic dianhydrides include, but are not limited to, the dianhydrides given above to formula II. 【0282】 In some embodiments of formula V, R a1 This 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 This represents a PMDA residue. 【0284】 In some embodiments of formula V, R a1 This represents a BPDA residue. 【0285】 In some embodiments of formula V, R a1 This represents the 6 FDA residues. 【0286】 In some embodiments of formula V, R a1 This represents a BTDA residue. 【0287】 In some embodiments of formula V, R a1 These represent PMDA residues and BPDA residues. 【0288】 In some embodiments of formula V, R a1 These represent PMDA residues and 6FDA residues. 【0289】 In some embodiments of formula V, R a1 These represent PMDA residues and BTDA residues. 【0290】 In some embodiments of formula V, R a1 These represent BPDA residues and 6FDA residues. 【0291】 In some embodiments of formula V, R a1 These represent BPDA residues and BTDA residues. 【0292】 In some embodiments of formula V, R a1 These represent 6FDA residues and BTDA residues. 【0293】 In some embodiments of formula V, R a1 These represent PMDA residues, BPDA residues, and 6FDA residues. 【0294】 In some embodiments of formula V, the diamine residue having formula IV is present as an additive to improve the color of polyamic acid and polyimide films formed from polyamic acid. Since the diamine having formula IV can weaken the apparent color, 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 mol% of R b1 is a 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 an additive. 【0296】 In some embodiments of formula V, diamines having formula IV are present to improve properties such as CTE, Tg, and thermal stability of polyimide films produced from polyamic acids. 【0297】 In some embodiments of formula V, a diamine having formula IV is present to improve the properties of the final polyimide film, and 10-100 mol% of R b1 However, the residue is from one or more diamines having formula IV; in some embodiments, 20-100 mol%; in some embodiments, 30-100 mol%; in some embodiments, 40-100 mol%; in some embodiments, 50-100 mol%; in some embodiments, 60-100 mol%; in some embodiments, 70-100 mol%; in some embodiments, 80-100 mol%; in some embodiments, 90-100 mol%; and in some embodiments, 100 mol%. 【0298】 In some embodiments of formula V, 10 to 100 mol% of R b1 However, as shown above, it represents a diamine residue from a single diamine having formula IV. 【0299】 In some embodiments of formula V, 10 to 100 mol% of R b1 However, as shown above, both represent diamine residues from two different diamines that have formula IV. 【0300】 In some embodiments of formula V, 10 to 100 mol% of R b1 However, as shown above, all of them represent diamine residues from three different diamines that have formula IV. 【0301】 In some embodiments of formula V, 10 to 100 mol% of R b1 However, as shown above, all of them represent diamine residues from four or more different diamines that have formula IV. 【0302】 Any of the aforementioned embodiments relating to Equation IV of Equation V can be combined with one or more other embodiments, insofar as they do not conflict with each other. 【0303】 In some embodiments of formula V, R b1 This represents a diamine residue from one or more diamines having formula IV, and at least one additional diamine residue. 【0304】 In some embodiments of formula V, R b1 This represents a diamine residue from one or more diamines having formula IV, and one additional diamine residue. 【0305】 In some embodiments of formula V, R b1 This 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 This represents a diamine residue from one or more diamines having formula IV, and three additional diamine residues. 【0307】 Suitable additional diamines include, but are not limited to, those listed above for formula II. 【0308】 In some embodiments of formula V, R b1 This represents a diamine residue from one or more diamines having formula IV, and a diamine residue from at least one additional diamine, wherein the additional diamine is a residue 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 is of formula VII 【0310】 [ka] 【0311】 [In formula: R a2 Each of these is either identical or different when it appears, and represents one or more tetracarboxylic acid residues; and R b2 Each of these is either identical or different when it appears, and represents one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R b2 [ is a residue from one or more diamines having formula VII] It has a repeating unit structure. 【0312】 R in formula V a1 All of the above embodiments relating to the R of formula VIII a2 It applies equally to [the other thing]. 【0313】 In some embodiments of formula VIII, the diamine residue having formula VII is present as an additive to improve the color of polyamic acid and polyimide films formed from polyamic acid. The diamine having formula VII can weaken the apparent color, so the film appears pale yellow. 【0314】 In some embodiments of formula VIII, a diamine having formula VII is present as an additive, and 0.001 to 10 mol% of R b2 is a 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 an additive. 【0315】 In some embodiments of formula VIII, diamines having formula VII are present to improve properties such as CTE, Tg, and thermal stability of polyimide films produced from polyamic acids. 【0316】 In some embodiments of formula VIII, a diamine having formula VII is present to improve the properties of the final polyimide film, and 10-100 mol% of R b2 However, the residue is from one or more diamines having formula VII; in some embodiments, 20-100 mol%; in some embodiments, 30-100 mol%; in some embodiments, 40-100 mol%; in some embodiments, 50-100 mol%; in some embodiments, 60-100 mol%; in some embodiments, 70-100 mol%; in some embodiments, 80-100 mol%; in some embodiments, 90-100 mol%; and in some embodiments, 100 mol%. 【0317】 In some embodiments of formula VIII, 10 to 100 mol% of R b2 However, as shown above, it represents a diamine residue from a diamine having formula VII. 【0318】 In some embodiments of formula VIII, 10 to 100 mol% of R b2 However, as shown above, both represent diamine residues from two different diamines having formula VII. 【0319】 In some embodiments of formula VIII, 10 to 100 mol% of R b2 However, as shown above, all of them represent diamine residues from three different diamines that have formula VII. 【0320】 In some embodiments of formula VIII, 10 to 100 mol% of R b2 However, as shown above, all of them represent diamine residues from four or more different diamines that have formula VII. 【0321】 In some embodiments of formula VIII, 20-100 mol% of R b2However, the residue is from one or more diamines having formula VII; in some embodiments, 30-100 mol%; in some embodiments, 40-100 mol%; in some embodiments, 50-100 mol%; in some embodiments, 60-100 mol%; in some embodiments, 70-100 mol%; in some embodiments, 80-100 mol%; in some embodiments, 90-100 mol%; and in some embodiments, 100 mol%. 【0322】 Any of the aforementioned embodiments relating to Formula VII of Formula VIII can be combined with one or more other embodiments, insofar as they do not conflict with each other. 【0323】 In some embodiments of formula VIII, R b2 This represents a diamine residue from one or more diamines having formula VII, and at least one additional diamine residue. 【0324】 In some embodiments of formula VIII, R b2 This 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 This 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 This represents a diamine residue from one or more diamines having formula VII, and three additional diamine residues. 【0327】 Suitable additional diamines include, but are not limited to, those listed above for formula II. 【0328】 In some embodiments of formula VIII, R b2This represents a diamine residue from one or more diamines having formula VII, and a diamine residue from at least one additional diamine, wherein the additional diamine is a residue 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 formulas II, V, and VIII, the portion obtained from a monoanhydride monomer exists as a terminal encapsulating group. 【0330】 In some embodiments, the monoanhydride monomer is selected from the group consisting of phthalic anhydride and its derivatives. 【0331】 In some embodiments, the monoanhydride is present in an amount up to 5 mol% of the total tetracarboxylic acid composition. 【0332】 In some embodiments of formulas II, V, and VIII, the portion obtained from the monoamine monomer exists as a terminal encapsulation group. 【0333】 In some embodiments, the monoamine monomer is selected from the group consisting of aniline and its derivatives. 【0334】 In some embodiments, the monoamine is present in an amount of up to 5 mol% of the total amine composition. 【0335】 In some embodiments, the polyamic acid has a weight-average molecular weight (M) greater than 100,000 in terms of standard polystyrene by gel permeation chromatography. W ) has. 【0336】 In some embodiments, the polyamic acid has a weight-average molecular weight (M) greater than 150,000 in terms of standard polystyrene by gel permeation chromatography. W ) has. 【0337】 In some embodiments, the polyamic acid has a molecular weight (M) greater than 200,000 in terms of standard polystyrene in gel permeation chromatography. W ) has. 【0338】 In some embodiments, the polyamic acid has a weight-average molecular weight (M) greater than 250,000 in terms of standard polystyrene by gel permeation chromatography. W ) has. 【0339】 In some embodiments, the polyamic acid has a weight-average molecular weight (M) greater than 300,000 in terms of standard polystyrene by gel permeation chromatography. W ) has. 【0340】 In some embodiments, the polyamic acid has a weight-average molecular weight (M) of 100,000 to 400,000 in terms of standard polystyrene as measured by gel permeation chromatography. W ) has. 【0341】 In some embodiments, the polyamic acid has a weight-average molecular weight (M) of 200,000 to 400,000 in terms of standard polystyrene by gel permeation chromatography. W ) has. 【0342】 In some embodiments, the polyamic acid has a weight-average molecular weight (M) of 250,000 to 350,000 in terms of standard polystyrene by gel permeation chromatography. W ) has. 【0343】 In some embodiments, the polyamic acid has a weight-average molecular weight (M) of 200,000 to 300,000 in terms of standard polystyrene as measured by gel permeation chromatography. W ) has. 【0344】 Any of the above embodiments relating to polyamic acids can be combined with one or more other embodiments, insofar as they do not conflict with each other. 【0345】 The overall polyamic acid composition can be specified through notation commonly used in the art. For example, a polyamic acid having a tetracarboxylic acid component of 100% ODPA and diamine components of 90 mol% Bis-P and 10 mol% TFMB would be expressed as follows: ODPA / / Bis-P / 22TFMB 100 / / 90 / 10. 【0346】 Furthermore, a liquid composition is provided comprising (a) a polyamic acid having repeating units of formula II and (b) a high-boiling point aprotic solvent. The liquid composition is referred to herein as "polyamic acid solution". 【0347】 Furthermore, a liquid composition is provided comprising (a) a polyamic acid having repeating units of formula V, and (b) a high-boiling point aprotic solvent. 【0348】 Furthermore, a liquid composition is provided comprising (a) a polyamic acid having repeating units of formula VIII and (b) a high-boiling point aprotic solvent. 【0349】 In some embodiments, the high-boiling aprotic solvent has a boiling point of 150°C or higher. 【0350】 In some embodiments, the high-boiling aprotic solvent has a boiling point of 175°C or higher. 【0351】 In some embodiments, the high-boiling aprotic solvent has a boiling point of 200°C or higher. 【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, but not limited to these, include N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), γ-butyrolactone, dibutylcarbitol, butylcarbitol acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 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 γ-butyrolactone. 【0359】 In some embodiments of the liquid composition, the solvent is dibutylcarbitol. 【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 high-boiling aprotic solvents specified above are used in the liquid composition. 【0364】 In some embodiments, additional cosolvents are used in the liquid composition. 【0365】 In some embodiments, the liquid composition is less than 1% by weight of polyamic acid in a high-boiling aprotic solvent at a concentration of more than 99% by weight. 【0366】 In some embodiments, the liquid composition is 1-5% by weight of polyamic acid in 95-99% by weight of a high-boiling point aprotic solvent. 【0367】 In some embodiments, the liquid composition is 5-10% by weight of polyamic acid in 90-95% by weight of a high-boiling point aprotic solvent. 【0368】 In some embodiments, the liquid composition is 10-15% by weight of polyamic acid in 85-90% by weight of a high-boiling point aprotic solvent. 【0369】 In some embodiments, the liquid composition is 15-20% by weight of polyamic acid in 80-85% by weight of a high-boiling point aprotic solvent. 【0370】 In some embodiments, the liquid composition is 20-25% by weight of polyamic acid in 75-80% by weight of a high-boiling aprotic solvent. 【0371】 In some embodiments, the liquid composition is 25-30% by weight of polyamic acid in 70-75% by weight of a high-boiling aprotic solvent. 【0372】 In some embodiments, the liquid composition is 30-35% by weight of polyamic acid in 65-70% by weight of a high-boiling aprotic solvent. 【0373】 In some embodiments, the liquid composition is 35-40% by weight of polyamic acid in 60-65% by weight of a high-boiling aprotic solvent. 【0374】 In some embodiments, the liquid composition is 40-45% by weight of polyamic acid in 55-60% by weight of a high-boiling aprotic solvent. 【0375】 In some embodiments, the liquid composition is 45-50% by weight of polyamic acid in 50-55% by weight of a high-boiling point aprotic solvent. 【0376】 In some embodiments, the liquid composition is 50% by weight of polyamic acid in 50% by weight of a high-boiling point aprotic solvent. 【0377】 The polyamic acid solution may optionally further contain one of a number of additives. Such additives may be antioxidants, heat stabilizers, adhesion promoters, coupling agents (e.g., silanes), inorganic fillers, or various reinforcing agents, as long as they do not adversely affect the desired polyimide properties. 【0378】 Polyamic acid solutions can be prepared using various available methods for introducing the components (i.e., monomers and solvents). Some methods for producing polyamic acid solutions include: (a) A method in which the diamine component and the dianhydride component are mixed together beforehand, and then gradually added 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 component and the dianhydride component. (Conversely to (a) above) (c) A method in which a diamine is exclusively dissolved in a solvent, and then a dianhydride is added thereto in a ratio that allows control of the reaction rate. (d) A method in which a dianhydride component is exclusively dissolved in a solvent, and then an amine component is added thereto in a ratio that allows control of 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 method in which a polyamic acid containing an excess amine component and another polyamic acid containing an excess dianhydride component are formed in advance and then reacted with each other in a reactor, particularly in a manner that produces a non-random copolymer or a block copolymer. (g) A method in which a specific portion of the amine component and the dianhydride component is reacted first, followed by the reaction of the residual diamine component, or vice versa. (h) A method in which components are added to any part or all of a solvent in any order, either partially or as a whole, and any part or all of any component is added as a solution of part or all of the solvent. (i) A method in which one of the two anhydride components is first reacted with one of the diamine components to produce a first polyamic acid. Subsequently, the other two anhydride component is reacted with the other amine component to produce a second polyamic acid. Then, before film formation, the polyamic acids are combined by one of several methods. Generally speaking, a polyamic acid solution can be obtained from any one of the polyamic acid solution preparation methods disclosed above. 【0379】 Next, the polyamic acid solution can be filtered once or multiple times to reduce the particle content. Polyimide films resulting from such filtrates exhibit a reduced defect count and can therefore provide excellent performance in the electronic applications disclosed herein. Filtration efficiency can be evaluated by laser particle counting tests 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 commercially available and known in the art. 【0380】 In some embodiments, the polyamic acid solution is prepared and filtered to yield a particle content of less than 40 particles, as measured by a laser particle counting test. 【0381】 In some embodiments, the polyamic acid solution is prepared and filtered to yield a particle content of less than 30 particles, as measured by a laser particle counting test. 【0382】 In some embodiments, the polyamic acid solution is prepared and filtered to yield a particle content of less than 20 particles, as measured by a laser particle counting test. 【0383】 In some embodiments, the polyamic acid solution is prepared and filtered to yield a particle content of less than 10 particles, as measured by laser particle counting. 【0384】 In some embodiments, the polyamic acid solution is prepared and filtered to yield a particle content of 2 to 8 particles, as measured by laser particle counting. 【0385】 In some embodiments, the polyamic acid solution is prepared and filtered to yield a particle content of 4 to 6 particles, as measured by laser particle counting. 【0386】 Exemplary preparations of polyamic acid solutions are shown in the examples. 【0387】 5. Polyimide In some embodiments, polyimide is derived from formula III 【0388】 [ka] 【0389】 [In the formula, R a Each of these represents a residue of one or more tetracarboxylic acid components, which may or may not be the same when they appear; and R b Each of these may be identical or different when it appears, and represents one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R a However, it is a residue from one or more dianhydrides having formula I. It has a repeating unit structure. 【0390】 R in Equation II a and R b All of the above embodiments relating to the R of formula III a and R b It applies equally to [the other thing]. 【0391】 Any of the aforementioned embodiments relating to Equation I of Equation III can be combined with one or more other embodiments, insofar as they do not conflict with each other. 【0392】 In some embodiments, polyimide is expressed in formula VI 【0393】 [ka] 【0394】 [In the formula, R a1 Each of these is either identical or different when it appears, and represents one or more tetracarboxylic acid residues; and R b1 Each of these is either identical or different when it appears, and represents one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R b1 [ is a residue from one or more diamines having formula IV] It has a repeating unit structure. 【0395】 R in formula V a1 and R b1 All of the above embodiments relating to the R of formula VI a1 and R b1 It applies equally to [the other thing]. 【0396】 Any of the aforementioned embodiments relating to Equation IV of Equation VI can be combined with one or more other embodiments, insofar as they do not conflict with each other. 【0397】 In some embodiments, polyimide is a polyimide of formula IX 【0398】 [ka] 【0399】 [In the formula, R a2 Each of these is either identical or different when it appears, and represents one or more tetracarboxylic acid residues; and R b2 Each of these is either identical or different when it appears, and represents one or more aromatic diamine residues; Here, 0.001 to 100 mol% of R b2 [ is a residue from one or more diamines having formula VII] It has a repeating unit structure. 【0400】 R in Equation VIII a2 and R b2 All of the above embodiments relating to the R of formula IX a2 and R b2 It applies equally to [the other thing]. 【0401】 Any of the aforementioned embodiments relating to Equation VII of Equation IX can be combined with one or more other embodiments, insofar as they do not conflict with each other. 【0402】 Polyimides can be produced from any suitable polyimide precursor, such as polyamic acids, polyamic acid esters, polyisoimides, and polyamic acid salts. 【0403】 As described above, a polyimide film is also provided in which the polyimide has a repeating unit structure of formula III, formula VI, or formula IX. 【0404】 Polyimide films can be manufactured by coating a substrate with a polyimide precursor and then imidizing it. This can be achieved by a thermal or chemical conversion process. 【0405】 Furthermore, if the polyimide is soluble in a suitable coating solvent, it can be provided as an already imidized polymer that has been dissolved in the suitable coating solvent and coated as 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 a low photodelay. 【0407】 In some embodiments of polyimide films, the glass transition temperature (T g ) is above 300°C in the case of a polyimide film cured at a temperature above 350°C; above 370°C in some embodiments; and above 380°C in some embodiments. 【0408】 In some embodiments of the polyimide film, the optical delay is less than 120 at 550 nm; in some embodiments, less than 100; and in some embodiments, less than 90. 【0409】 In some embodiments of the polyimide film, the in-plane thermal expansion coefficient (CTE) is less than 45 ppm / °C at 50°C to 200°C in the first measurement; less than 30 ppm / °C in some embodiments; less than 20 ppm / °C in some embodiments; and less than 15 ppm / °C in some embodiments. 【0410】 In some embodiments of the polyimide film, the in-plane thermal expansion coefficient (CTE) is less than 75 ppm / °C at 50°C to 200°C in the second measurement; in some embodiments, it is 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; and 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; and 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 cloudiness value is less than 1.0%; in some embodiments, it is less than 0.5%. 【0415】 In some embodiments of the polyimide film, b * It is less than 7.5; in some embodiments, it is less than 5.0. 【0416】 In some embodiments of the polyimide film, YI is less than 12; in some embodiments, it is less than 10. 【0417】 In some embodiments of the polyimide film, the transmittance at 400 nm is greater than 40%; in some embodiments, it is greater than 50%. 【0418】 In some embodiments of the polyimide film, the transmittance at 430 nm is greater than 60%; in some embodiments, it is greater than 70%. 【0419】 In some embodiments of the polyimide film, the transmittance at 450 nm is greater than 70%; in some embodiments, it is greater than 80%. 【0420】 In some embodiments of the polyimide film, the transmittance at 550 nm is greater than 70%; in some embodiments, it is greater than 80%. 【0421】 In some embodiments of the polyimide film, the transmittance at 750 nm is greater than 70%; in some embodiments, it is greater than 80%. 【0422】 Any of the above embodiments relating to the polyimide film can be combined with one or more other embodiments, insofar as they do not conflict with each other. 【0423】 6. Method for preparing polyimide film Generally, polyimide films can be prepared from polyimide precursors by chemical or thermal conversion. In some embodiments, the film is prepared from a corresponding polyamic acid solution by a chemical or thermal conversion process. The polyimide films disclosed herein are prepared by a thermal conversion process, particularly when used as a flexible substitute for glass in electronic devices. 【0424】 Generally, polyimide films can be prepared from the corresponding polyamic acid solution by chemical or thermal conversion processes. The polyimide films disclosed herein, particularly when used as flexible substitutes for glass in electronic devices, are prepared by thermal conversion or modified thermal conversion processes, rather than by chemical conversion processes. 【0425】 The chemical conversion process is described in (Patent Document 1) and (Patent Document 2), which are incorporated in their entirety by reference. In such a process, conversion chemicals are added to a polyamic acid solution. Conversion chemicals found 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 a slightly molar excess of the amount of amide 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. Generally, an equivalent amount of tertiary amine catalyst is used. 【0426】 The thermal conversion process may or may not use a conversion chemical (i.e., a catalyst) to convert the polyamic acid cast solution to polyimide. When a conversion 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 for both drying the solvent film and carrying out the imidation reaction. Generally, thermal conversion processes with or without a conversion catalyst are used to prepare the polyimide films disclosed herein. 【0427】 Specific method parameters are selected in advance, taking into account that film composition is not the only factor producing the properties of interest. Rather, the curing temperature and temperature gradient profile also play an important role in achieving the most desired properties for the intended use disclosed herein. The polyamic acid must be imidized at the highest temperature, or higher than, the temperature of any subsequent processing step (e.g., welding of inorganic or other layers required to produce a functional display), but lower than the temperature at which significant thermal decomposition / discoloration of the polyimide occurs. It should also be noted 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 of 300°C to 320°C are typically used when subsequent processing temperatures exceeding 300°C are required. Selecting the appropriate curing temperature allows for a well-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. Extremely low oxygen levels allow for the use of the highest curing temperatures without significant decomposition / discoloration of the polymer. Catalysts accelerating the imidization process are effective in achieving higher levels of imidization at curing temperatures of approximately 200°C to 300°C. This technique allows for flexible devices to utilize the T of polyimide. g If prepared using a curing temperature below a certain limit, it may be used optionally. 【0429】 The amount of time spent in each potential curing step is an even more important process consideration. Generally, the time used for curing at the highest temperature should be kept to a minimum. For curing at 320°C, for example, the curing time may be up to about 1 hour or under an inert atmosphere; however, at higher curing temperatures, it is desirable to shorten this time to avoid thermal decomposition. Generally speaking, the higher the temperature, the shorter the time. Those skilled in the art will recognize the balance of temperature and time needed to optimize the properties of 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 heat conversion process, the polyamic acid solution is coated onto a substrate such that the soft bake thickness of the resulting film is 10 to 50 μm. 【0432】 In some embodiments of the heat conversion process, the coated substrate is soft-baked on a hot plate in proximity mode, where nitrogen gas is used to hold the coated substrate just above the hot plate. 【0433】 In some embodiments of the heat conversion process, the coated substrate is soft-baked on a hot plate in full-contact mode, where the coated substrate is in direct contact with the hot plate surface. 【0434】 In some embodiments of the heat conversion process, the coated substrate is soft-baked on a hot plate using a combination of proximity mode and full-contact mode. 【0435】 In some embodiments of the heat conversion process, the coated substrate is soft-baked using a hot plate set to 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 pre-selected temperatures over 2 to 10 pre-selected time intervals, the latter of which may be the same or different. 【0438】 In some embodiments of the heat conversion process, the pre-selected temperature is in the range of 80 to 450°C. 【0439】 In some embodiments of the heat conversion process, one or more of the pre-selected time intervals are 2 minutes. 【0440】 In some embodiments of the heat conversion process, one or more of the pre-selected time intervals are 5 minutes. 【0441】 In some embodiments of the heat conversion process, one or more of the pre-selected time intervals are 10 minutes. 【0442】 In some embodiments of the heat conversion process, one or more of the pre-selected time intervals are 15 minutes. 【0443】 In some embodiments of the heat conversion process, one or more of the pre-selected time intervals are greater than 15 minutes. 【0444】 In some embodiments of the heat conversion process, one or more of the pre-selected time intervals are between 2 minutes and 60 minutes. 【0445】 In some embodiments of the heat conversion process, one or more of the pre-selected time intervals are between 2 minutes and 120 minutes. 【0446】 In some embodiments of the thermal conversion process, a method for 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 processing the soft-baked coated substrate at a plurality of pre-selected temperatures over a plurality of pre-selected time intervals, thereby enabling the polyimide film to exhibit properties satisfactory for use in electronic applications such as those disclosed herein. 【0447】 In some embodiments of the thermal conversion process, a method for preparing a polyimide film comprises the following steps: coating a substrate with the polyamic acid solution described above; soft-baking the coated substrate; and processing the soft-baked coated substrate at a plurality of pre-selected temperatures over a plurality of pre-selected time intervals, thereby enabling the polyimide film to exhibit properties satisfactory for use in electronic applications as disclosed herein. 【0448】 In some embodiments of the thermal conversion process, a method for preparing a polyimide film essentially comprises the following steps in order: coating a substrate with the polyamic acid solution described above; soft-baking the coated substrate; and processing the soft-baked coated substrate at a plurality of pre-selected temperatures over a plurality of pre-selected time intervals, thereby enabling the polyimide film to exhibit properties satisfactory for use in electronic applications such as those disclosed herein. 【0449】 Typically, the polyamic acid solution / polyimide disclosed herein is coated / cured onto a support glass substrate to facilitate processing throughout the rest of the display manufacturing process. At some point in the process, as determined by the display manufacturer, the polyimide coating is removed from the support glass substrate by a mechanical or laser lift-off process. These processes separate the polyimide from the glass as a film with a fused display layer, enabling a flexible format. Often, this polyimide film with a vapor-deposited layer is then bonded to a thicker, but still flexible, plastic film to provide a support for the subsequent fabrication of the display. 【0450】 A modification thermal conversion process is also provided in which the conversion catalyst causes the imidation reaction at a lower temperature than is generally possible in the absence of such a conversion catalyst. 【0451】 In some embodiments, the polyamic acid solution is converted into a polyimide film by a modification thermal conversion process. 【0452】 In some embodiments of the modification thermal conversion process, the polyamic acid solution further comprises a conversion catalyst. 【0453】 In some embodiments of the modification 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 modification heat conversion process, a 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 modification heat conversion process, the coated substrate is soft-baked on a hot plate in proximity mode, where nitrogen gas is used to hold the coated substrate directly above the hot plate. 【0456】 In some embodiments of the modification heat conversion process, the coated substrate is soft-baked on a hot plate in full-contact mode, where the coated substrate is in direct contact with the surface of the hot plate. 【0457】 In some embodiments of the modification heat conversion process, the coated substrate is soft-baked on a hot plate using a combination of proximity mode and full-contact mode. 【0458】 In some embodiments of the modification heat conversion process, the coated substrate is soft-baked using a hot plate set to 80-150°C. 【0459】 In some embodiments of the modification thermal conversion process, the coated substrate is soft-baked for a total time of 2 to 10 minutes. 【0460】 In some embodiments of the modification thermal conversion process, a soft-baked coating substrate is subsequently cured at 2 to 10 pre-selected temperatures over 2 to 10 pre-selected time intervals, the latter of which may be the same or different. 【0461】 In some embodiments of the modification heat conversion process, the pre-selected temperature is 80 to over 300°C. 【0462】 In some embodiments of the modification heat conversion process, one or more of the pre-selected time intervals are between 2 minutes and 120 minutes. 【0463】 In some embodiments of the modification thermal conversion process, a method for preparing a polyimide film comprises the following steps in order: coating a substrate with a polyamic acid solution containing the above-mentioned conversion chemicals; soft-baking the coated substrate; and processing the soft-baked coated substrate at a plurality of pre-selected temperatures over a plurality of pre-selected time intervals, thereby enabling the polyimide film to exhibit properties satisfactory for use in electronics applications as disclosed herein. 【0464】 In some embodiments of the modification thermal conversion process, a method for preparing a polyimide film comprises the following steps: coating a substrate with a polyamic acid solution containing the above-mentioned conversion chemicals; soft-baking the coated substrate; and processing the soft-baked coated substrate at a plurality of pre-selected temperatures over a plurality of pre-selected time intervals, thereby enabling the polyimide film to exhibit properties satisfactory for use in electronic applications as disclosed herein. 【0465】 In some embodiments of the modification thermal conversion process, a method for preparing a polyimide film essentially comprises the following steps in order: coating a substrate with a polyamic acid solution containing the above-mentioned conversion chemicals; soft-baking the coated substrate; and processing the soft-baked coated substrate at a plurality of pre-selected temperatures over a plurality of pre-selected time intervals, thereby enabling the polyimide film to exhibit properties satisfactory for use in electronic applications such as those disclosed herein. 【0466】 7. Electronic devices The polyimide films disclosed herein may be suitable for use in several layers within 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, and cover films. The specific material properties required for each application are unique and can be addressed by appropriate compositions and processing conditions for the polyimide films disclosed herein. 【0467】 In some embodiments, as already described in detail, the flexible substitute for glass in electronic devices is a polyimide film having repeating units of formula III, formula VI, or formula IX. 【0468】 Organic electronic devices that may benefit from having one or more layers comprising at least one of the compounds 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 by electronic processes (e.g., photodetectors, photoconductive cells, photoresistors, photoswitches, phototransistors, photocells, infrared detectors, biosensors), (3) devices that convert radiation into electrical energy (e.g., photovoltaic devices or solar cells), (4) devices that convert light of one wavelength into light of a longer wavelength (e.g., down-converting phosphorescent devices), and (5) devices that include one or more electronic components comprising 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】 Figure 1 shows one example of a polyimide film that can act as a flexible substitute for glass as described herein. The flexible film 100 may have the properties described in embodiments of this disclosure. In some embodiments, the polyimide film that can act as a flexible substitute for glass is included in an electronic device. Figure 2 shows an electronic device 200 that is an organic electronic device. The device 200 has a substrate 100, an anode layer 110 and a second electrical contact layer, a cathode layer 130 and a photoactive layer 120 between them. Optionally, further layers may be present. A layer adjacent to the anode layer may be a hole injection layer (not shown), sometimes called a buffer layer. A layer adjacent to the hole injection layer may be a hole transport layer (not shown) containing a hole transport material. A layer adjacent to the cathode layer may be an electron transport layer (not shown) containing an electron transport material. As an option, the device may use one or more additional hole injection 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. The layers 110-130 are referred to individually and collectively as the organic active layer. Additional layers, which 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 film disclosed herein in addition to the substrate 100. 【0470】 Different layers will be further discussed herein with reference to Figure 2. However, this discussion applies equally to other configurations. 【0471】 In some embodiments, different layers have thicknesses in the following ranges: substrate 100, 5-100 microns; anode 110, 500-5,000 Å, 1,000-2,000 Å in some embodiments; hole injection layer (not shown), 50-2,000 Å, 200-1,000 Å in some embodiments; hole transport layer (not shown), 50-3,000 Å, 200-2,000 Å in some embodiments; photoactive layer 120, 10-2,000 Å, 100-1,000 Å in some embodiments; electron transport layer (not shown), 50-2,000 Å, 100-1,000 Å in some embodiments; cathode 130, 200-10,000 Å, 300-5,000 Å in some embodiments. The desired ratio of layer thicknesses depends on the exact properties of the materials used. 【0472】 In some embodiments, the organic electronic device (OLED) includes a flexible alternative to the glass disclosed herein. 【0473】 In some embodiments, the organic electronic device includes a substrate, an anode, a cathode, and a photoactive layer between them, 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, and cathode. 【0475】 Methods and materials similar to or equivalent to those described herein may be used in carrying out or testing the present invention, but preferred methods and materials are described below. Furthermore, the materials, methods and examples are illustrative and not intended to be limiting. All publications, patent applications, patents and other references mentioned herein are incorporated herein by reference in their entirety. [Examples] 【0476】 The concepts described herein are further illustrated in the following embodiments, which do not limit the scope of the invention as defined in the claims. 【0477】 Synthesis Example 1 This example illustrates the preparation of compound IV-3, which is 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 acid 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 with NMP (100 ml) at 180°C under a nitrogen atmosphere for 5 hours. The reaction mixture was cooled, diluted with water, and 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 that elutes with chloroform. After removing the chloroform to the minimum amount using a rotary evaporator, methanol was added. The precipitate collected by filtration was dried to obtain 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 under reflux for 4 hours. The reaction mixture was cooled, diluted with water (100 ml), and the crude product was recovered by filtration and washed with a methanol:water (1:1) mixture. The crude product was dissolved in acetonitrile and passed through a filter packed with silica gel and basic alumina that elutes with acetonitrile. Acetonitrile was removed to the minimum amount, and compound 4, to be used in the next step, was obtained 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), Cl2Pd (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 hour. The reaction mixture was cooled, the product was filtered, washed with toluene and water, and dried to obtain 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, Fluorizyl, and basic alumina that elute tetrahydrofuran. After removing the tetrahydrofuran by distillation, the residue was repeatedly crystallized from a mixture of tetrahydrofuran and hexane to obtain a product with a purity exceeding 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 a 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), and compound I-2. 【0483】 [ka] 【0484】 A mixture of 4-bromo-1,8-naphthalenedicarboxylic acid 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), Cl2Pd (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 hours. The reaction mixture was decanted while still hot, the precipitate was washed with water and acetone, stirred in water (30 ml) to which concentrated hydrochloric acid was added for 2 hours, filtered, and dried to obtain 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 obtain the desired product with a purity of 99.51% by HPLC. The filtrate was diluted with water (100 ml), the precipitate was recovered by filtration, acetic anhydride (10 ml) was added, and the mixture was stirred at 140°C for 2 hours. The precipitate was recovered by filtration to obtain the desired product with a purity of 99.1%. MS:MH+=607. 1 ¹H-NMR (dmso-d6): 7.92-8.04 (m) and 8.29 (d, J=8.8Hz) atropisomer (6H), 8.12 (s, 2H), 8.61-8.71 (m, 4H, atropisomer). Photoluminescence: λ=418±5 nm (in tetrahydrofuran), quantum yield -59%. 【0485】 Polymer Example 1 This example illustrates the preparation of polyamic acid using diamine compound IV-3. 【0486】 Compound IV-3 (3.733 g) from Synthesis Example 1, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (0.889 g), and N-methylpyrrolidinone (27 g) were mixed and stirred in a glass reactor at ambient temperature. Pyromelitic acid dianhydride (8 mg) was then added until the final viscosity reached 13670 cP. GPC: Mn=75827, Mw=163321, Mp=150475, Mz=272075, PDI=2.15. 【0487】 Polymer Example 2 This example illustrates the preparation of polyamic acid using diamine compound IV-3. 【0488】 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-isobenzoflangione 6FDA (36 mg), and N-methylpyrrolidinone (41 g) were mixed in a glass reactor and stirred at ambient temperature. 6FDA (36 mg) was then added in two portions until a final viscosity of 1565 cP was achieved. 【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 hot plate at 90°C, and placed in a furnace. The furnace was heated in stages under a nitrogen atmosphere to a maximum curing temperature of 375°C. The wafer was removed from the furnace, immersed in water, and manually abscissed to obtain a sample of polyimide film with a thickness of 11.6 μm. 【0491】 Using a Hunter Lab spectrophotometer, b was measured along with % transmittance (%T) over the wavelength range of 350nm to 780nm. *The yellowness index was also measured. Thermal measurements of the film were performed using a combination of thermogravimetric and thermomechanical analysis appropriate to the specific parameters reported herein. Mechanical properties were measured using Instron instruments. 【0492】 The characteristics of the film are as follows: Thickness = 11.6 μm Tg > 450℃ CTE = 2.66 ppm / ℃ Cloudiness 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 hot plate at 90°C, and placed in a furnace. The furnace was heated in stages under a nitrogen atmosphere to a maximum curing temperature of 375°C. The wafer was removed from the furnace, immersed in water, and manually abscissed to obtain a sample of polyimide film with a thickness of 10.26 μm. 【0495】 Using a Hunter Lab spectrophotometer, b was measured along with % transmittance (%T) over the wavelength range of 350nm to 780nm. * The yellowness index was also measured. Thermal measurements of the film were performed using a combination of thermogravimetric and thermomechanical analysis appropriate to the specific parameters reported herein. Mechanical properties were measured using Instron instruments. 【0496】 The characteristics of the film are as follows: Thickness = 10.26 μm Tg = 495℃ CTE = 6.2 ppm / ℃ Cloudiness value = 0.5% b * =7.32 YI = 12.85 η = 0.0954 birefringence. 【0497】 Please note that not all of the above-described tasks are necessary in the general description or examples, some of the tasks may be unnecessary, and one or more additional tasks may be performed in addition to those described. Furthermore, the order in which the tasks are listed is not necessarily the order in which they are performed. 【0498】 In this specification, the concept has been described with reference to specific embodiments. However, it will be understood by those skilled in the art that various modifications and variations can be made without departing from the scope of the invention as described in the following claims. Accordingly, this specification and the figures are illustrative and not restrictive, and all such modifications are intended to be within the scope of the invention. 【0499】 Benefits, other advantages, and solutions to problems have been described in relation to specific embodiments. However, benefits, advantages, and solutions to problems, as well as any features that may produce or enhance any benefit, advantage, or solution, shall not be construed as essential, required, or indispensable features of any or all claims. 【0500】 For clarity, it should be understood that certain features may be described herein in relation to other embodiments and may also be provided in combination in a single embodiment. Conversely, for brevity, various features described in relation to a single embodiment may also be provided individually or in any partial combination. The use of various ranges of numerical values ​​specified herein is described as approximations, such that both the minimum and maximum values ​​within the range are preceded by the word “approximately”. In this way, small fluctuations above and below the range can be used to achieve substantially the same results as the numerical values ​​within the range. Furthermore, the disclosure of these ranges is intended to be a continuous range including all values ​​between the minimum-average and maximum-average values, including decimal values ​​that may arise when some components of one value are mixed with some components of a different value. Moreover, when wider and narrower ranges are disclosed, matching the minimum value from one range with the maximum value from another is within the scope expected of the invention, and vice versa. [Explanation of Symbols] 【0501】 100 circuit boards 110 Anode Layers 120 Photoactive layer 130 Cathode Layer 200 Electronic Devices

Claims

[Claim 1] A polyamic acid, which is a polyamic acid, and formula II 【Chemistry 1】 [In the formula: R a Each of these represents one or more tetracarboxylic acid residues, which may be identical or different when they appear; and R b Each of these represents one or more aromatic diamine residues, which may or may not be the same when they appear; 0.001 to 100 mol% of R a is a residue from one or more dianhydrides having the following formula I: 【Chemistry 2】 [In the formula: Y is selected from the group consisting of alkylenes, -SiR2-, esters, -O-SiR2-O-, -SiR2-O-SiR2-, -SiR2-O-SiR2-O-SiR2-, SO2, BR3, NR3, P(O)R3, and unsubstituted or substituted heteroarylenes, and their deuterated analogs, where R is the same or different when it appears, and is H, C1-20 alkyl, fluoroalkyl, or aryl; R1 to R2 are either identical or different when they appear, 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 their deuterated analogs. R3 is selected from the group consisting of alkyl and unsubstituted or substituted carbocyclic aryls, and their deuterated analogs; a and b are either the same or different integers between 0 and 5. A polyamic acid having a repeating unit structure. [Claim 2] Polyimide, formula III 【Transformation 3】 [In the formula, R a Each of these represents one or more tetracarboxylic acid residues, which may be identical or different when they appear; and R b Each of these represents one or more aromatic diamine residues, which may or may not be the same when they appear; 0.001 to 100 mol% of R a is a residue from one or more dianhydrides having the following formula I: 【Chemistry 4】 [In the formula: Y is selected from the group consisting of alkylenes, -SiR2-, esters, -O-SiR2-O-, -SiR2-O-SiR2-, -SiR2-O-SiR2-O-SiR2-, SO2, BR3, NR3, P(O)R3, and unsubstituted or substituted heteroarylenes, and their deuterated analogs, where R is the same or different when it appears, and is H, C1-20 alkyl, fluoroalkyl, or aryl; R1 to R2 are either identical or different when they appear, 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 their deuterated analogs. R3 is selected from the group consisting of alkyl and unsubstituted or substituted carbocyclic aryls, and their deuterated analogs; a and b are either the same or different integers between 0 and 5. A polyimide having a repeating unit structure. [Claim 3] A flexible substitute for glass in an electronic device, wherein the flexible substitute for glass comprises a polyimide film having repeating units of formula III as described in claim 2. [Claim 4] An electronic device comprising a flexible substitute for glass as described in Claim 3.

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