KR102802818B1 - Polymers for use in electronic devices - Google Patents

Abstract

A polyamine having the chemical formula I is disclosed:
[Chemical Formula I]

In formula I, Q ¹ is H, R ¹ , or R ⁹ ; Q ² is H, R ² , or R ⁹ ; Q ³ is R ³ or R ⁹ ; Q ⁴ is R ⁴ or R ⁹ ; Q ⁵ is R ⁷ or R ⁹ ; R ¹ and R ² are the same or different at each occurrence and are F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, siloxy, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, or unsubstituted or substituted aryloxy; R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same or different and are H, F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, siloxy, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, or unsubstituted or substituted aryloxy; R ⁸ is alkyl, silyl, unsubstituted or substituted hydrocarbon aryl, or unsubstituted or substituted heteroaryl; R ⁹ is the same or different at each occurrence and is NH ₂ or ArNH ₂ ; Ar is the same or different at each occurrence and is unsubstituted or substituted C _6-18 hydrocarbon aryl; a and b are the same or different and are integers from 0 to 3. In Formula I, at least two of Q ¹ to Q ⁵ are R ⁹ .

Description

Polymers for use in electronic devices

Claiming Benefit of Prior Application

This application claims the benefit of U.S. Provisional Application No. 62/715,889, filed August 8, 2018, which is incorporated herein by reference in its entirety.

Technical field

The present invention relates to a novel polymer compound. The present invention also relates to a process for producing such a polymer compound, and to an electronic device having at least one layer comprising such a material.

Materials for use in electronic applications often have stringent requirements in terms of their structural, optical, thermal, electrical, and other properties. As the number of commercial electronic applications continues to increase, innovative materials with new and/or improved properties in the breadth and specificity of the required properties are required. Polyimides represent a class of polymer compounds that have been widely used in a variety of electronic applications. Polyimides can serve as flexible glass replacements in electronic display devices when they have the right properties. These materials can function as components of liquid crystal displays ("LCDs") where moderate power consumption, light weight, and layer flatness are important properties for efficient use. Other applications in electronic display devices where these parameters are important include device substrates, substrates for color filter sheets, cover films, touch screen panels, etc.

Many of these components are also important in the construction and operation of organic electronic devices, including organic light-emitting diodes ("OLEDs"). OLEDs are promising for many display applications because of their high power conversion efficiency and their wide range of end-use applications. The use of OLEDs is increasing in mobile phones, tablet devices, portable/notebook computers, and other commercial products. In addition to low power consumption, these applications require displays that are information-rich, full-color, and have fast video rate response times.

Polyimide films generally have sufficient thermal stability, high glass transition temperature, and mechanical toughness to be considered for these applications. Additionally, polyimides generally do not produce haze when subjected to repeated bending, and are therefore often preferred over other transparent substrates such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) for flexible display applications.

Polyimides are generally rigid, highly aromatic materials, and when the film/coating is formed, the polymer chains tend to orient in the plane of the film/coating. This results in a difference in refractive index between the parallel and perpendicular directions of the film (birefringence), which creates optical phase retardation that can negatively affect display performance. New monomers with novel structural features could potentially lead to polyimides with improved properties for specific applications.

There is a continuing demand for polymeric materials suitable for use in electronic devices.

A polyamine having the chemical formula I is provided:

[Chemical Formula I]

Here,

Q ¹ is selected from the group consisting of H, R ¹ , and R ⁹ ;

Q ² is selected from the group consisting of H, R ² , and R ⁹ ;

Q ³ is selected from the group consisting of R ³ and R ⁹ ;

Q ⁴ is selected from the group consisting of R ⁴ and R ⁹ ;

Q ⁵ is selected from the group consisting of R ⁷ and R ⁹ ;

R ¹ and R ² are the same or different in each case and are selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, siloxy, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, and unsubstituted or substituted aryloxy;

R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same or different and are selected from the group consisting of H, F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, siloxy, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, and unsubstituted or substituted aryloxy;

R ⁸ is selected from the group consisting of alkyl, silyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl;

R ⁹ is the same or different in each case and is selected from the group consisting of NH ₂ and ArNH ₂ ;

Ar is the same or different in each case and is an unsubstituted or substituted C _6-18 hydrocarbon aryl;

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

However, at least two of Q ¹ to Q ⁵ are R ⁹ .

Additionally provided is a polyamic acid having a repeating unit of chemical formula II:

[Chemical Formula II]

Here,

R ^a is the same or different in each case and represents one or more tetracarboxylic acid component residues;

R ^b is the same or different in each case and represents one or more aromatic diamine residues;

From 10 to 100 mol % of R ^b are diamine residues from one or more diamines having formula I.

A composition is further provided comprising (a) a polyamic acid having a repeating unit of chemical formula II and (b) a high boiling point aprotic solvent.

Additionally provided is a polyimide wherein the repeating unit has the structure of chemical formula III:

[Chemical Formula III]

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

A polyimide film comprising a polyimide having a repeating unit of chemical formula III is additionally provided.

One or more methods for producing a polyimide film are further provided, wherein the polyimide has repeating units of formula III.

Additionally provided is a flexible glass substitute in electronic devices, the flexible glass substitute being a polyimide film comprising a polyimide having repeating units of the chemical formula III.

An electronic device is further provided having at least one layer comprising a polyimide film comprising a polyimide having repeating units of chemical formula III.

As an organic electronic device, such as an OLED, an organic electronic device comprising the flexible glass substitute disclosed herein is further provided.

The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, which is defined in the appended claims.

To enhance understanding of the concepts presented herein, embodiments are illustrated in the accompanying drawings.
Figure 1 includes an illustration of an example of a polyimide film that can act as a flexible glass substitute.
FIG. 2 includes an illustration of an example of an electronic device including a flexible glass substitute.
Those skilled in the art will appreciate that objects in the drawings are depicted simply and clearly and are not necessarily drawn to scale. For example, the dimensions of some objects in the drawings may be exaggerated relative to other objects to help improve understanding of the embodiment.

As described in detail below, a polyamine having the chemical formula I is provided.

As described in detail below, a polyamic acid having repeating units of chemical formula II is further provided.

A composition is further provided comprising (a) a polyamic acid having a repeating unit of chemical formula II and (b) a high boiling point aprotic solvent.

Further provided is a polyimide having repeating units having a structure of chemical formula III, as described in detail below.

One or more methods for producing a polyimide film are further provided, wherein the polyimide has repeating units of formula III.

Additionally provided is a flexible glass substitute in electronic devices, the flexible glass substitute being a polyimide film comprising a polyimide having repeating units of the chemical formula III.

An electronic device is further provided having at least one layer comprising a polyimide film comprising a polyimide having repeating units of chemical formula III.

As an organic electronic device, such as an OLED, an organic electronic device comprising the flexible glass substitute disclosed herein is further provided.

Many aspects and embodiments have been described above, which are merely illustrative and not limiting. After reading this specification, those skilled in the art will appreciate that other aspects and embodiments are possible without departing from the scope of the present invention.

Other features and advantages of any one or more of the embodiments will become apparent from the following detailed description and claims. The detailed description first covers definitions and explanations of terms, then the polyamine having the formula I, the polyamic acid, the polyimide, the process for making the polyimide film, the electronic device, and finally the examples.

1. Definition and explanation of terms

Before going into the details of the embodiments described below, some terms are defined or explained.

As used in "Definitions and Clarifications of Terms", R, R ^a , R ^b , R', R", and any other variables are generic designations and may be the same as or different from those defined in the chemical formula.

The term "alignment layer" is intended to mean a layer of organic polymer within an LCD that aligns the molecules closest to each plate by rubbing the plates against the LCD glass in one preferred direction during the LCD manufacturing process.

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

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

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

The term "aryl" or "aryl group" refers to a moiety formed by removing one or more hydrogens ("H") or deuteriums ("D") from an aromatic compound. An aryl group may be a single ring (monocyclic) or may have multiple rings (bicyclic or more) that are fused or covalently bonded together. A "hydrocarbon aryl" has only carbon atoms in the aromatic ring(s). A "heteroaryl" has one or more heteroatoms in at least one aromatic ring. In some embodiments, the hydrocarbon aryl group has 6 to 60 ring carbon atoms, and in some embodiments, 6 to 30 ring carbon atoms. In some embodiments, the heteroaryl group has 4 to 50 ring carbon atoms, and in some embodiments, 4 to 30 ring carbon atoms.

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

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

Unless otherwise stated, all groups may be substituted or unsubstituted. Optionally substituted groups, such as but not limited to alkyl or aryl, may be substituted with one or more substituents, which may be the same or different. Suitable substituents include alkyl, aryl, nitro, cyano, -N(R')(R"), halo, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, siloxy, siloxane, thioalkoxy, -S(O) ₂ -, -C(=O)-N(R')(R"), (R')(R")N-alkyl, (R')(R")N-alkoxyalkyl, (R')(R")N-alkylaryloxyalkyl, -S(O) _s -aryl (wherein s is 0 to 2), or -S(O) _s -heteroaryl (wherein s is 0 to 2). Each R' and R" is independently, optionally A substituted alkyl, cycloalkyl, or aryl group. In certain embodiments, R' and R" together with the nitrogen atom to which they are attached may form a ring system. The substituents may also be cross-linking groups.

The term "amine" is intended to mean a compound containing a basic nitrogen atom having a lone pair of electrons, a lone pair being a set of two valence electrons that are not shared with any other atom. The term "amino" refers to the functional groups -NH ₂ , -NHR , or -NR ₂ , wherein R in each instance is the same or different and may be an alkyl group or an aryl group. The term "diamine" is intended to mean a compound containing two basic nitrogen atoms having associated lone pairs of electrons. The term "polyamine" is intended to mean a compound containing two or more basic nitrogen atoms having associated lone pairs of electrons. The term "aromatic diamine" is intended to mean an aromatic compound having two amino groups. The term "aromatic polyamine" is intended to mean an aromatic compound having two or more amino groups. The term "bent diamine" is intended to mean a diamine in which the two basic nitrogen atoms and the associated lone pairs of electrons are asymmetrically arranged around the center of symmetry of the corresponding compound or functional group (e.g., m -phenylenediamine: ).

The term "aromatic diamine moiety" is intended to mean a moiety bonded to two amino groups in an aromatic diamine. The term "aromatic polyamine moiety" is intended to mean a moiety bonded to two or more amino groups in an aromatic polyamine. The term "aromatic diisocyanate moiety" is intended to mean a moiety bonded to two isocyanate groups in an aromatic diisocyanate compound. The term "aromatic polyisocyanate moiety" is intended to mean a moiety bonded to two or more isocyanate groups in an aromatic polyisocyanate compound. These are further exemplified below.

The terms “diamine moiety” and “diisocyanate moiety” are intended to mean a moiety bonded to two amino groups or two isocyanate groups, respectively, wherein the moieties are aliphatic or aromatic. The terms “polyamine moiety” and “polyisocyanate moiety” are intended to mean a moiety bonded to two or more amino groups or two or more isocyanate groups, respectively, wherein the moieties are aliphatic or aromatic.

The term “b*” is intended to refer to the b* axis in the CIELab color space, which represents the complementary color of yellow/blue. Yellow is represented by a positive b* value, and blue by a negative b* value. The measured b* values can be influenced by the solvent, particularly since the choice of solvent can affect the measured chromaticity of a material exposed to high temperature processing conditions. This can occur as a result of inherent properties of the solvent and/or properties associated with low levels of impurities contained in various solvents. A particular solvent is often pre-selected to achieve the b* value required for a particular application.

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

When referring to a layer, material, member, or structure, the term "charge transport" is intended to mean that such layer, material, member, or structure facilitates the movement of charge through the thickness of such layer, material, member, or structure with relative efficiency and with little loss of charge. Hole transport materials facilitate the movement of positive charge, and electron transport materials facilitate the movement of negative charge. Although emissive materials may also have some charge transport properties, the term "charge transport layer, charge transport material, charge transport member, or charge transport structure" is not intended to include a layer, material, member, or structure whose primary function is to emit light.

The term "compound" is intended to mean an electrically uncharged substance whose molecules contain further atoms which cannot be separated from said molecules by physical means without breaking the chemical bonds. The term is intended to include oligomers and polymers.

The term "coefficient of linear thermal expansion (CTE or α)" is intended to mean a parameter that defines how much a material expands or contracts as a function of temperature. It is expressed as the change in length per 1°C, and is usually expressed in units of μm/m/°C or ppm/°C.

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

The term "dopant" is intended to mean a material that, within a layer comprising a host material, changes the electronic property(s) of that layer, or the wavelength(s) of radiation emission, absorption, or filtering of that layer, relative to the electronic property(s) of that layer, or the wavelength(s) of radiation emission, absorption, or filtering of that layer in the absence of such material.

The term "electroactive" when referring to a layer or material is intended to refer to a layer or material that electronically facilitates the operation of a device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block charge, which may be electrons or holes, or materials that exhibit a change in concentration of electron-hole pairs when absorbing radiation or that emit radiation. Examples of inert materials include, but are not limited to, planarizing materials, insulating materials, and environmental shielding materials.

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

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

The term "glass transition temperature (or T _g )" is intended to mean the temperature at which a reversible change in the material occurs, in an amorphous polymer or in the amorphous region of a semi-crystalline polymer, i.e., an abrupt material change from a hard, glassy, or brittle state to a flexible or elastic state. Microscopically, the glass transition occurs when normally coiled, immobile polymer chains become free to rotate and move past each other. T _g can be measured using differential scanning calorimetry (DSC), thermomechanical analysis (TMA), or dynamic mechanical analysis (DMA), or other methods.

The prefix "hetero" indicates that one or more carbon atoms are replaced by another atom. In some embodiments, the heteroatoms are O, N, S, or a combination thereof.

The term "high boiling point" is intended to indicate a boiling point higher than 130°C.

The term "host material" is intended to mean a material to which a dopant is added. The host material may or may not have electronic properties(s), or the ability to emit, absorb, or filter radiation. In some embodiments, the host material is present in high concentration.

The term "isothermal weight loss" is intended to refer to a material property that is directly related to the thermal stability of the material. This is typically measured by thermogravimetric analysis (TGA) at a desired constant temperature. Materials with high thermal stability typically exhibit very low isothermal weight loss rates at the desired use or processing temperature for the required period of time, so that they can be used in applications at such temperatures without significant strength loss, gas evolution, and/or structural changes.

The term "laser particle counter test" refers to a method used to evaluate the particle content of polyamic acid and other polymer solutions by spin coating a representative sample of the test solution onto a 5" silicon wafer and soft baking/drying. The resulting film is then evaluated for particle content by a number of standard measurement techniques. Such techniques include laser particle detection and other techniques known in the art.

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

The term "matrix" is intended to mean a substrate upon which one or more layers are deposited, for example during the formation of an electronic device. Non-limiting examples include glass, silicon, etc.

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

The term "optical phase retardation (or R _TH )" is intended to mean the product of the difference between the average in-plane and out-of-plane refractive indices (i.e., birefringence) and the thickness of a film or coating. Optical phase retardation is typically measured for light of a given frequency and is reported in nanometers.

The term "organic electronic device" or sometimes "electronic device" is intended herein to mean a device comprising one or more organic semiconductor layers or materials.

The term "particle content" is intended to mean the number or quantity of insoluble particles present in a solution. The particle content may be measured for the solution itself, or for the final material (piece, film, etc.) made from such a film. A variety of optical methods can be used to evaluate this property.

The term "photoactive" refers to a material or layer that emits light when activated by an applied voltage (as in a light-emitting diode or a chemical cell), emits light after absorbing a photon (as in a down-converting phosphor device), or generates a signal in the presence or absence of an applied bias voltage in response to radiant energy (as in a photodetector or photocell).

The term "polyamic acid solution" refers to a solution of a polymer containing amic acid units having the ability to form imide groups by intramolecular cyclization.

The term “polyanhydride” refers to a compound having two or more acid anhydride groups. The term “polyanhydride moiety” is intended to mean a moiety bonded to two or more anhydride groups. This is further exemplified below.

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

The term "satisfactory" with respect to a property or characteristic of a material is intended to mean that the property or characteristic satisfies all requirements/needs for the material being used. For example, an isothermal weight loss of less than 1% at 350° C. for 3 hours in nitrogen can be considered a non-limiting example of a "satisfactory" property with respect to the polyimide films disclosed herein.

The term "soft baking" is intended to mean a process commonly used in electronics manufacturing, which involves heating a coated material to remove the solvent and solidify the film. Soft baking is typically performed on a hot plate or in an exhaust oven at a temperature of 90°C to 110°C as a preparatory step for subsequent heat treatment of the coated layer or film.

The term "substrate" refers to a base material which may be rigid or flexible, and which may include one or more layers of one or more materials including, but not limited to, glass, polymers, metals, or ceramic materials, or combinations thereof. The substrate may or may not include electronic components, circuitry, or conductive elements.

The term "siloxane" refers to the group R ₃ SiOR ₂ Si-, wherein R, which is the same or different at each occurrence, is H, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons of the R alkyl group are replaced by Si.

The term "siloxy" refers to the group R ₃ SiO-, where R, which is the same or different at each occurrence, is H, C1-20 alkyl, fluoroalkyl, or aryl.

The term "silyl" refers to a R ₃ Si- group, wherein R, which is the same or different at each occurrence, is H, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons of the R alkyl group are replaced with Si.

The term "spin coating" is intended to refer to a process used to deposit a uniform thin film on a flat substrate. Typically, a small amount of coating material is applied to the center of a substrate that is rotating at a low speed or not at all. The substrate is then rotated at a specific speed to uniformly apply the coating material by centrifugal force.

The term “spiro group” refers to a group having a bicyclic organic moiety in which two rings have a single atom in common. The rings may be substantially different or identical and may form part of another ring system. The common atom has two bonds in each ring and is called a spiro atom. In some embodiments, the spiro atom is selected from the group consisting of C and Si.

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

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

The term "tetracarboxylic acid moiety" is intended to mean a moiety bonded to four carboxyl groups within a tetracarboxylic acid moiety. This is further exemplified below.

The term "transmittance" refers to the percentage of light of a given wavelength incident on a film that passes through the film and can be detected on the other side. Measurement of light transmittance in the visible region (380 nm to 800 nm) is particularly useful for characterizing film chromaticity characteristics, which are most important for understanding the in-use properties of the polyimide films disclosed herein.

The term "yellowness index (or YI)" refers to the degree of yellowness relative to a standard. A positive YI value indicates the presence and degree of yellowness. Materials with a negative YI have a bluish tinge. It should also be noted that YI can be solvent dependent, especially for polymerization and/or curing processes performed at high temperatures. For example, the degree of color introduced using DMAC as a solvent may be different than that introduced using NMP as a solvent. This can occur as a result of inherent properties of the solvent and/or properties associated with low levels of impurities contained in various solvents. Specific solvents are often pre-selected to achieve the YI value required for a particular application.

In a structure where the substituent bond penetrates one or more rings as shown below,

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

When used to refer to layers within a device, the phrase "adjacent to" does not necessarily mean that one layer is immediately next to another layer. 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 that are connected by a bond). Exemplary adjacent R groups are exemplified below:

In this specification, unless expressly stated otherwise or the context of usage indicates otherwise, when an embodiment of the present subject matter is stated or described as comprising, incorporating, containing, having, consisting of, or consisting of or consisting of a particular feature or element, one or more of the features or elements other than those expressly stated or described may be present in the embodiment. An alternative embodiment of the disclosed subject matter is described as consisting essentially of the particular feature or element, wherein no feature or element is present in such embodiment that materially changes the operation or distinguishing characteristics of the embodiment. A further alternative embodiment of the disclosed subject matter is described as consisting of the particular feature or element, wherein only the specifically stated or described feature or element is present in such embodiment or a non-substantial variation thereof.

Moreover, unless explicitly stated to the contrary, "or" means an inclusive 'or', not an exclusive 'or'. For example, the condition A 'or' B is satisfied by any of the following: A is true (or exists) and B is false (or nonexistent), A is false (or nonexistent) and B is true (or exists), and both A and B are true (or existent).

In addition, singular nouns are used to describe elements and components described herein. This is done merely for convenience and to provide a general sense of the scope of the invention. This description should be read to include one or at least one, and the singular includes the plural unless it is clearly meant to be singular.

The group numbers corresponding to the columns in the periodic table of elements use the "New Notation" conventions found in the CRC Handbook of Chemistry and Physics , 81 ^st Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

Where not described herein, many details of specific materials, processing operations, and circuitry are conventional and can be found in textbooks and other materials in the fields of organic light emitting diode displays, photodetectors, photovoltaics, and semiconductor component technologies.

2. Polyamine having chemical formula I

The polyamine described herein has the formula I:

[Chemical Formula I]

Here,

Q ¹ is selected from the group consisting of H, R ¹ , and R ⁹ ;

Q ² is selected from the group consisting of H, R ² , and R ⁹ ;

Q ³ is selected from the group consisting of R ³ and R ⁹ ;

Q ⁴ is selected from the group consisting of R ⁴ and R ⁹ ;

Q ⁵ is selected from the group consisting of R ⁷ and R ⁹ ;

R ¹ and R ² are the same or different in each case and are selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, siloxy, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, and unsubstituted or substituted aryloxy;

R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same or different and are selected from the group consisting of H, F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, siloxy, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, and unsubstituted or substituted aryloxy;

R ⁸ is selected from the group consisting of alkyl, silyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl;

R ⁹ is the same or different in each case and is selected from the group consisting of NH ₂ and ArNH ₂ ;

Ar is the same or different in each case and is an unsubstituted or substituted C _6-18 hydrocarbon aryl;

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

However, at least two of Q ¹ to Q ⁵ are R ⁹ .

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

All of the embodiments described above for Q ¹ in Chemical Formula I equally apply to Q ² , Q ³ , Q ⁴ , and Q ⁵ in Chemical Formula I.

In some embodiments of formula I, a is 0.

In some embodiments of formula I, a is 1.

In some embodiments of formula I, a is 2.

In some embodiments of formula I, a is 3.

In some embodiments of formula I, a is greater than 0.

In some embodiments of formula I, a is greater than 0 and at least one R ¹ is F.

In some embodiments of formula I, a is greater than 0 and at least one R ¹ is CN.

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

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

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

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

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

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

In some embodiments of formula I, a is greater than 0 and at least one R ¹ is SiH ₃ .

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

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

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

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

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

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

In some embodiments of formula I, b is 0.

In some embodiments of formula I, b is 1.

In some embodiments of formula I, b is 2.

In some embodiments of formula I, b is 3.

In some embodiments of formula I, b is greater than 0.

In some embodiments of formula I, b is greater than 0 and at least one R ² is F.

In some embodiments of formula I, b is greater than 0 and at least one R ² is CN.

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

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

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

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

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

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

In some embodiments of formula I, b is greater than 0 and at least one R ² is SiH ₃ .

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

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

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

In some embodiments of formula I, b is greater than 0 and at least one R ² is unsubstituted or substituted C _3-30 heteroaryl; in some embodiments, unsubstituted or substituted C _3-18 heteroaryl; in some embodiments, is unsubstituted.

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

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

In some embodiments of formula I, R ⁵ is R ⁶ .

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of formula I, R ⁵ is unsubstituted or substituted C _6-30 hydrocarbon aryl; in some embodiments, C _6-18 hydrocarbon aryl; and in some embodiments, is unsubstituted.

In some embodiments of formula I, R ⁵ is unsubstituted or substituted C _3-30 heteroaryl; in some embodiments, C _3-18 heteroaryl; and in some embodiments, is unsubstituted.

In some embodiments of formula I, R ⁵ is unsubstituted or substituted C _6-30 hydrocarbon aryloxy; in some embodiments, C _6-18 hydrocarbon aryloxy; and in some embodiments, is unsubstituted.

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

All embodiments described above for R ⁵ in formula I apply equally to R ⁶ in formula I.

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

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

In some embodiments of formula I, R ⁸ is unsubstituted or substituted C _6-30 hydrocarbon aryl; in some embodiments, C _6-18 hydrocarbon aryl; and in some embodiments, is unsubstituted.

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

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

In some embodiments of formula I, two R ⁹ groups are present and are identical.

In some embodiments of formula I, two R ⁹ groups are present and are different.

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

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

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

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

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

In some embodiments of formula I, at least one R ⁹ is ArNH ₂ , wherein:

Ar has the chemical formula a:

[chemical formula a]

Here,

R ¹⁰ and R ¹¹ are the same or different in each occurrence and are selected from the group consisting of F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy, wherein adjacent R ¹⁰ and/or R ¹¹ groups may be joined together to form a fused ring;

p and q are the same or different and are integers from 0 to 4;

s is an integer from 0 to 3;

* Indicates an attachment point.

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

In some embodiments of formula I, the polyamine has formula IA:

[Chemical Formula IA]

Here, R ¹ to R ⁹ , a, and b are as defined in Formula I. All embodiments described above for R ¹ to R ⁹ , a, and b in Formula I apply equally to R ¹ to R ⁹ , a, and b in Formula IA.

In some embodiments of formula I, the polyamine has formula IB:

[Chemical Formula IB]

Here, R ¹ , R ² , R ⁵ to R ⁹ , a, and b are as defined in Formula I. All embodiments described above for R ¹ , R ² , R ⁵ to R ⁹ , a, and b in Formula I apply equally to R ¹ , R ² , R ⁵ to R ⁹ , a, and b in Formula IB.

In some embodiments of formula I, the polyamine has the formula IC:

[Chemical Formula IC]

Here, R ¹ to R ⁶ , R ⁸ , R ⁹ , a, and b are as defined in Formula I. All of the embodiments described above for R ¹ to R ⁶ , R ⁸ , R ⁹ , a, and b in Formula I apply equally to R ¹ to R ⁶ , R ⁸ , R ⁹ , a, and b in Formula IC.

The new compounds can be prepared using any technique that produces a C—C or C—N bond. A variety of such techniques are known, including Suzuki, Yamamoto, Stille, Negishi, and metal-catalyzed C—N couplings, as well as metal-catalyzed and oxidative direct arylations, and Diels-Alder cycloaddition. Exemplary preparations are provided in the Examples.

One synthetic reaction scheme is shown below.

In the above reaction formula, “Bpin” represents boron pinacolate.

Any of the above embodiments for Formula I may be combined with one or more other embodiments, provided they are not mutually exclusive. For example, an embodiment wherein Q ¹ and Q ² are R ⁷ may be combined with at least one of an embodiment wherein R ⁷ is NH ₂ , an embodiment wherein a is 0, and an embodiment wherein b is 0. Those skilled in the art will understand which embodiments are mutually exclusive and will therefore readily be able to determine combinations of embodiments contemplated by the present application.

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

Compound 1

Compound 2

Compound 3

Compound 4

Compound 5

Compound 6

3. Polyamic acid

The polyamic acid described herein is a reaction product of one or more polyanhydrides and one or more polyamines, wherein 10 to 100 mol % of the one or more polyamines have the formula I.

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

In some embodiments of the polyamic acid, two different polyamines having formula I are reacted.

In some embodiments of the polyamic acid, three different polyamines having formula I are reacted.

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

In some embodiments of the polyamic acid, 20 to 100 mol %; in some embodiments, 30 to 100 mol %; in some embodiments, 40 to 100 mol %; in some embodiments, 50 to 100 mol %; in some embodiments, 60 to 100 mol %; in some embodiments, 70 to 100 mol %; in some embodiments, 80 to 100 mol %; in some embodiments, 90 to 100 mol %; in some embodiments, 100 % of the one or more polyamines have Formula I.

In some embodiments of the polyamic acid, at least one additional polyamine is reacted with the polyamine(s) having formula I.

In some embodiments of the polyamic acid, an additional polyamine is reacted with the polyamine(s) having formula I.

In some embodiments of the polyamic acid, two additional polyamines are reacted with the polyamine(s) having formula I.

In some embodiments of the polyamic acid, three additional polyamines are reacted with the polyamine(s) having formula I.

In some embodiments of the polyamic acid, four additional polyamines are reacted with the polyamine(s) having formula I.

In some embodiments of the polyamic acid, the polyamic acid has a repeating unit structure of formula II:

[Chemical Formula II]

Here,

R ^a is the same or different in each case and represents one or more tetracarboxylic acid residues;

R ^b is the same or different in each case and represents one or more diamine residues;

From 10 to 100 mol % of R ^b are residues from one or more diamines having formula I.

In some embodiments of formula II, R ^a represents a single tetracarboxylic acid moiety.

In some embodiments of formula II, R ^a represents two different tetracarboxylic acid moieties.

In some embodiments of formula II, R ^a represents three different tetracarboxylic acid moieties.

In some embodiments of formula II, R ^a represents four different tetracarboxylic acid moieties.

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

Examples of suitable aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4'-hexafluoroiso-propylidenebisphthalic polyanhydride (6FDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4'-bisphenol-A dianhydride (BPADA), hydroquinone diphthalic anhydride (HQDEA), ethylene glycol bis(trimellitic anhydride) (TMEG-100), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (DTDA); 4,4'-bisphenol A dianhydride (BPADA); and the like, and combinations thereof. These aromatic dianhydrides can be optionally substituted with groups known in the art, including alkyl, aryl, nitro, cyano, -N(R')(R ^" ), halo, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, siloxy, siloxane, thioalkoxy, -S(O) ₂ -, -C(=O)-N(R')(R"), (R')(R")N-alkyl, (R')(R")N-alkoxyalkyl, (R')(R")N-alkylaryloxyalkyl, -S(O) _s -aryl (wherein s is 0 to 2), or -S(O) _s -heteroaryl (wherein s is 0 to 2). may be. Each of R' and R" is independently an optionally substituted alkyl, cycloalkyl, or aryl group. In certain embodiments, R' and R" may form a ring system together with the nitrogen atom to which they are attached. The substituents may also be cross-linking groups.

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

In some embodiments of formula II, R ^a represents a PMDA moiety.

In some embodiments of formula II, R ^a represents a BPDA moiety.

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

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

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

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

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

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

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

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

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

In formula II, 10 to 100 mol % of R ^b represents a diamine residue from one or more diamines having formula I as shown above.

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

In some embodiments of formula II, 10 to 100 mol % of R ^b represent diamine residues from two different diamines, both having formula I as shown above.

In some embodiments of formula II, 10 to 100 mol % of R ^b represent diamine residues from three different diamines, all having formula I as shown above.

In some embodiments of formula II, 10 to 100 mol % of R ^b represent diamine residues from at least four different diamines, all of which have formula I as shown above.

In some embodiments of formula II, 20 to 100 mol % of R ^b are residues from one or more diamines having formula I; in some embodiments, 30 to 100 mol %; in some embodiments, 40 to 100 mol %; in some embodiments, 50 to 100 mol %; in some embodiments, 60 to 100 mol %; in some embodiments, 70 to 100 mol %; in some embodiments, 80 to 100 mol %; in some embodiments, 90 to 100 mol %; in some embodiments, 100 %.

Any of the above embodiments for Formula I in Formula II may be combined with one or more other embodiments, provided they are not mutually exclusive.

In some embodiments of formula II, R ^b represents a diamine moiety from one or more diamines having formula I and at least one additional diamine moiety.

In some embodiments of formula II, R ^b represents a diamine moiety from one or more diamines having formula I and one additional diamine moiety.

In some embodiments of formula II, R ^b represents a diamine moiety from one or more diamines having formula I and two additional diamine moieties.

In some embodiments of formula II, R ^b represents a diamine moiety from one or more diamines having formula I and three additional diamine moieties.

In some embodiments of formula II, the one or more additional diamine moieties are moieties from one or more additional aromatic diamines.

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

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

In some embodiments of formula II, the moiety derived from the anhydride monomer is present as an end-capping group.

In some embodiments, the anhydride monomer is selected from the group consisting of phthalic anhydride and derivatives thereof.

In some embodiments, the anhydride is present in an amount of less than 5 mol % of the total tetracarboxylic acid composition.

In some embodiments of formula II, a moiety derived from a monoamine monomer is present as an end-capping group.

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

In some embodiments, the monoamine is present in an amount of less than 5 mol % of the total amine composition.

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

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

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

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

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

In some embodiments, the polyamic acid has a weight average molecular weight (M _W ) of 100,000 to 400,000 based on gel permeation chromatography using polystyrene standards.

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

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

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

Any of the above embodiments for polyamic acid may be combined with one or more other embodiments, provided they are not mutually exclusive.

The overall polyamic acid composition can be expressed using notations commonly used in the art. For example, a polyamic acid having a tetracarboxylic acid component of 100% ODPA and a diamine component of 90 mol% bis-P and 10 mol% TFMB would be expressed as:

ODPA//BIS-P/TFMB 100//90/10.

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

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

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

In some embodiments, the high boiling point aprotic solvent has a boiling point greater than or equal to 200°C.

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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The polyamic acid solution may optionally further contain any 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.

Polyamic acid solutions can be prepared using a variety of available methods involving the introduction of the components (i.e., monomers and solvents). Some methods of preparing polyamic acid solutions include the following:

(a) A method of mixing a polyamine component and a polyanhydride component together in advance and then adding the mixture to a solvent little by little while stirring.

(b) A method of adding a solvent to a stirred mixture of a polyamine component and a polyanhydride component (opposite to (a) above).

(c) A method of dissolving only polyamine in a solvent and then adding polyanhydride thereto in a proportion that allows the reaction rate to be controlled.

(d) a method of dissolving only the polyanhydride component in a solvent and then adding an amine component thereto in a proportion so as to control the reaction rate;

(e) A method of dissolving the component and the polyanhydride component individually in a solvent and then mixing these solutions in a reactor.

(f) a method of forming a polyamic acid having an excess polyamine component and another polyamic acid having an excess polyanhydride component in advance and then reacting them with each other in a reactor, particularly in a manner to produce a non-random copolymer or a block copolymer;

(g) a method of first reacting a specific portion of the polyamine component with the polyanhydride component and then reacting it with the remaining polyamine component, or vice versa;

(h) a method of adding the components partially or wholly to part or all of a solvent in any order (and part or all of any component may be added as a solution to part or all of the solvent);

(i) a method of first reacting one of the polyanhydride components with one of the polyamine components to provide a first polyamic acid, then reacting another polyanhydride component with another polyamine component to provide a second polyamic acid, and then combining the polyamic acids in any one of a number of ways prior to film formation.

In general, the polyamic acid solution can be obtained from any one of the polyamic acid solution preparation methods disclosed above.

The polyamic acid solution can then be filtered one or more times to reduce the particle content. Polyimide films produced from such filtered solutions can exhibit superior performance in the electronic applications disclosed herein by exhibiting a reduced number of defects. Evaluation of the filtration efficiency can be performed by laser particle counter testing in which a representative sample of the polyamic acid solution is cast onto a 5" silicon wafer. After soft baking/drying, the film is evaluated for particle content by a number of laser particle counting techniques on equipment that is commercially available and known in the art.

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

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

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

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

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

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

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

4. Polyimide

A polyimide is provided which is produced from the imidization of the polyamic acid described above. “Imidization” means intramolecular cyclization of an amic acid to form an imide group. In some embodiments, thermal imidization is used. In some embodiments, chemical imidization is used. In some embodiments, a combination of thermal imidization and chemical imidization is used.

In some embodiments, the polyimide has a repeating unit structure of formula III:

[Chemical Formula III]

Here,

R ^a is the same or different in each case and represents one or more tetracarboxylic acid component residues;

R ^b is the same or different in each case and represents one or more aromatic diamine residues;

From 10 to 100 mol % of R ^b are residues from one or more diamines having formula I.

All embodiments described above for R ^a and R ^b in formula II are equally applicable to R ^a and R ^b in formula III.

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

The polyimide can be prepared from any suitable polyimide precursor, such as polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid salt.

As described above, a polyimide film is also provided in which the polyimide has a repeating unit structure of chemical formula III.

Polyimide films can be manufactured by coating a polyimide precursor on a substrate and subsequently imidizing it. This can be accomplished by a thermal conversion process or a chemical conversion process.

Additionally, if the polyimide is soluble in a suitable coating solvent, the polyimide may be provided as an already imidized polymer dissolved in a suitable coating solvent and coated as the polyimide.

In some embodiments, a polyimide film comprising a polyimide having repeating units of formula III has both a high glass transition temperature and a low coefficient of thermal expansion (CTE).

In some embodiments of the polyimide film, the glass transition temperature (T _g ) is greater than 300° C., in some embodiments, greater than 350° C., and in some embodiments, greater than 375° C. for the polyimide film cured at a temperature greater than 325° C.

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

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

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.

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

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

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

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

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

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

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

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

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

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

Any of the above embodiments for polyimide film may be combined with one or more other embodiments, provided they are not mutually exclusive.

5. Method for manufacturing polyimide film

In general, the polyimide film can be prepared from a polyimide precursor by a chemical or thermal conversion process. 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, particularly when used as flexible glass replacements in electronic devices, are prepared by a thermal conversion process.

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

Chemical conversion processes are described in U.S. Patent Nos. 5,166,308 and 5,298,331, which are incorporated by reference in their entireties. In such processes, conversion chemicals are added to a polyamic acid solution. Conversion chemicals that have been found to be useful in the present invention include, but are not limited to, (i) one or more dehydrating agents, such as aliphatic acid anhydrides (such as acetic anhydride) and acid anhydrides; and (ii) one or more catalysts, such as aliphatic tertiary amines (such as triethylamine), tertiary amines (such as dimethylaniline), and heterocyclic tertiary amines (such as pyridine, picoline, isoquinoline, etc.). The anhydride dehydrating material is typically used in a molar excess relative to the amount of amide acid groups present in the polyamic acid solution. The amount of acetic anhydride used is typically from 2.0 to 3.0 moles per equivalent of polyamic acid. Typically, a similar amount of tertiary amine catalyst is used.

The thermal conversion process may or may not use a conversion chemical (i.e., a catalyst) to convert the polyamic acid casting solution to a 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 to dry the solvent from the film and effect the imidization reaction. A thermal conversion process is typically used to produce the polyimide films disclosed herein, with or without a conversion catalyst.

Specific process parameters are pre-selected considering that it is not only the film composition that yields the properties of interest. Rather, the curing temperature and temperature-ramp profile also play an important role in achieving the most desirable properties for the intended applications disclosed herein. The polyamic acid should be imidized at a temperature above the highest temperature of any subsequent processing step (e.g., deposition of inorganic or other layer(s) required to fabricate a functional display), but below the temperature at which significant thermal degradation/discoloration of the polyimide occurs. It should also be noted that an inert atmosphere is generally preferred, and is particularly preferred when higher processing temperatures are used for imidization.

For the polyamic acids/polyimides disclosed herein, temperatures of 300°C to 320°C are typically used when post-processing temperatures exceeding 300°C are required. Selecting an appropriate curing temperature will produce a fully cured polyimide having an optimal balance of thermal and mechanical properties. Because of these very high temperatures, an inert atmosphere is required. Typically, oxygen levels of less than 100 ppm should be used within the oven. At very low oxygen levels, the highest cure temperatures can be used without significant degradation/discoloration of the polymer. Catalysts that promote the imidization process are effective in achieving higher levels of imidization at cure temperatures of about 200°C to 300°C. This approach may be used selectively when the flexible device is fabricated with an upper cure temperature that is below the T _g of the polyimide.

The amount of time for each potential cure step is also an important process consideration. In general, the time used for the highest temperature cure should be kept to a minimum. For example, for a 320°C cure, the cure time may be up to one hour under an inert atmosphere, but at higher cure temperatures this time should be shortened to avoid thermal degradation. In general, the higher the temperature, the shorter the time should be. Those skilled in the art will recognize the balance between temperature and time to optimize the properties of the polyimide for a particular end use.

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

In some embodiments of the thermal conversion process, the polyamic acid solution is coated onto the matrix such that the soft baked thickness of the resulting film is less than 50 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is coated onto the matrix such that the soft baked thickness of the resulting film is less than 40 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is coated onto the matrix such that the soft baked thickness of the resulting film is less than 30 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is coated onto the matrix such that the soft baked thickness of the resulting film is less than 20 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is coated onto the matrix such that the resulting film has a soft baked thickness of 10 μm to 20 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is coated onto the matrix such that the resulting film has a soft baked thickness of 15 μm to 20 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is coated onto the matrix such that the resulting film has a soft baked thickness of 18 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is coated onto the matrix such that the soft baked thickness of the resulting film is less than 10 μm.

In some embodiments of the thermal conversion process, the coated matrix is soft baked on a hotplate in proximity mode, with nitrogen gas used to maintain the coated matrix directly above the hotplate.

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

In some embodiments of the thermal conversion process, the coated matrix is soft baked on a hotplate using a combination of proximity mode and full contact mode.

In some embodiments of the thermal conversion process, the coated matrix is soft baked using a hot plate set at 80° C.

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

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

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

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

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

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

In some embodiments of the thermal conversion process, the coated matrix is soft baked for a total time of greater than 10 minutes.

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

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

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

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

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

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

In some embodiments of the thermal conversion process, the soft baked coated matrix is subsequently cured at two preselected temperatures for two preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated matrix is subsequently cured at three preselected temperatures for three preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated matrix is subsequently cured at four preselected temperatures for four preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated matrix is subsequently cured at five preselected temperatures for five preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated matrix is subsequently cured at six preselected temperatures for six preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated matrix is subsequently cured at seven preselected temperatures for seven preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated matrix is subsequently cured at eight preselected temperatures for eight preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated matrix is subsequently cured at nine preselected temperatures for nine preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated matrix is subsequently cured at ten preselected temperatures for ten preselected time intervals, wherein the preselected time intervals can be the same or different.

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

In some embodiments of the thermal conversion process, the preselected temperature is 100°C.

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

In some embodiments of the thermal conversion process, the preselected temperature is 150°C.

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

In some embodiments of the thermal conversion process, the preselected temperature is 200°C.

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

In some embodiments of the thermal conversion process, the preselected temperature is 250°C.

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

In some embodiments of the thermal conversion process, the preselected temperature is 300°C.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 300°C.

In some embodiments of the thermal conversion process, the preselected temperature is 350°C.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 350°C.

In some embodiments of the thermal conversion process, the preselected temperature is 400°C.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 400°C.

In some embodiments of the thermal conversion process, the preselected temperature is 450°C.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 450°C.

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 2 minutes.

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 5 minutes.

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 10 minutes.

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

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 20 minutes.

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 25 minutes.

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 30 minutes.

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 35 minutes.

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 40 minutes.

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

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 50 minutes.

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 55 minutes.

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 60 minutes.

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

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

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

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

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

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

In some embodiments of the thermal conversion process, the method for making a polyimide film essentially consists of the steps of, in sequence, coating the polyamic acid solution described above onto a matrix; soft baking the coated matrix; and treating the soft-baked coated matrix at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic device applications as disclosed herein.

Typically, the polyamic acid solution/polyimide disclosed herein is coated/cured onto a supporting glass substrate to facilitate processing through the remaining display manufacturing processes. At some point in the process, as determined by the display manufacturer, the polyimide coating is lifted off from the supporting glass substrate by a mechanical or laser lift off process. This process separates the polyimide from the glass as a film onto which the display layers are deposited, thereby enabling a flexible configuration. Typically, this polyimide film with the deposited layers is then bonded to a thicker, but still flexible, plastic film to provide support for subsequent manufacturing of the display.

A modified thermal conversion process is also provided in which the imidization reaction occurs at a temperature lower than that at which the imidization reaction would normally occur in the absence of such a conversion catalyst.

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

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains a conversion catalyst selected from the group consisting of tertiary amines.

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

In some embodiments of the modified thermal conversion process, the conversion catalyst is present in an amount of less than 5 wt % of the polyamic acid solution.

In some embodiments of the modified thermal conversion process, the conversion catalyst is present in an amount of less than 3 wt % of the polyamic acid solution.

In some embodiments of the modified thermal conversion process, the conversion catalyst is present in an amount of less than 1 wt % of the polyamic acid solution.

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

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains tributylamine as a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains dimethylethanolamine as a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains isoquinoline as a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains 1,2-dimethylimidazole as a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains 3,5-dimethylpyridine as a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains 5-methylbenzimidazole as a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains N-methylimidazole as a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains 2-methylimidazole as a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains 2-ethyl-4-imidazole as a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains 3,4-dimethylpyridine as a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution additionally contains 2,5-dimethylpyridine as a conversion catalyst.

In some embodiments of the modified thermal conversion process, the polyamic acid solution is coated onto the matrix such that the soft baked thickness of the resulting film is less than 50 μm.

In some embodiments of the modified thermal conversion process, the polyamic acid solution is coated onto the matrix such that the soft baked thickness of the resulting film is less than 40 μm.

In some embodiments of the modified thermal conversion process, the polyamic acid solution is coated onto the matrix such that the soft baked thickness of the resulting film is less than 30 μm.

In some embodiments of the modified thermal conversion process, the polyamic acid solution is coated onto the matrix such that the soft baked thickness of the resulting film is less than 20 μm.

In some embodiments of the modified thermal conversion process, the polyamic acid solution is coated onto the matrix such that the resulting film has a soft baked thickness of 10 μm to 20 μm.

In some embodiments of the modified thermal conversion process, the polyamic acid solution is coated onto the matrix such that the resulting film has a soft baked thickness of 15 μm to 20 μm.

In some embodiments of the modified thermal conversion process, the polyamic acid solution is coated onto the matrix such that the resulting film has a soft baked thickness of 18 μm.

In some embodiments of the modified thermal conversion process, the polyamic acid solution is coated onto the matrix such that the soft baked thickness of the resulting film is less than 10 μm.

In some embodiments of the modified thermal conversion process, the coated matrix is soft baked on a hotplate in proximity mode, with nitrogen gas used to maintain the coated matrix directly above the hotplate.

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

In some embodiments of the modified thermal conversion process, the coated matrix is soft baked on a hotplate using a combination of proximity mode and full contact mode.

In some embodiments of the modified thermal conversion process, the coated matrix is soft baked using a hot plate set at 80° C.

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

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

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

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

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

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

In some embodiments of the modified thermal conversion process, the coated matrix is soft baked for a total time of greater than 10 minutes.

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

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

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

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

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

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

In some embodiments of the modified thermal conversion process, the soft baked coated matrix is subsequently cured at two preselected temperatures for two preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated matrix is subsequently cured at three preselected temperatures for three preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated matrix is subsequently cured at four preselected temperatures for four preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated matrix is subsequently cured at five preselected temperatures for five preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated matrix is subsequently cured at six preselected temperatures for six preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated matrix is subsequently cured at seven preselected temperatures for seven preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated matrix is subsequently cured at eight preselected temperatures for eight preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated matrix is subsequently cured at nine preselected temperatures for nine preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated matrix is subsequently cured at ten preselected temperatures for ten preselected time intervals, wherein the preselected time intervals can be the same or different.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 80°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 100°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 100°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 150°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 150°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 200°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 200°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 220°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 220°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 230°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 230°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 240°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 240°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 250°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 250°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 260°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 260°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 270°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 270°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 280°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 280°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 290°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is greater than 290°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 300°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is less than 300°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is less than 290°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is less than 280°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is less than 270°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is less than 260°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is less than 250°C.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 2 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 5 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 10 minutes.

In some embodiments of the modified conversion process, at least one of the preselected time intervals is 15 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 20 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 25 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 30 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 35 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 40 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 45 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 50 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 55 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 60 minutes.

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

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

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

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

In some embodiments of the modified thermal conversion process, a method for making a polyimide film comprises, in sequence, the steps of: coating a polyamic acid solution as described above comprising a conversion chemical onto a matrix; soft baking the coated matrix; and treating the soft-baked coated matrix at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic device applications as disclosed herein.

In some embodiments of the modified thermal conversion process, the method for making a polyimide film comprises, in sequence, the steps of: coating a polyamic acid solution as described above comprising a conversion chemical onto a matrix; soft baking the coated matrix; and treating the soft-baked coated matrix at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic device applications as disclosed herein.

In some embodiments of the modified thermal conversion process, the method for making a polyimide film essentially consists of the steps of, in sequence, coating a polyamic acid solution as described above comprising a conversion chemical onto a matrix; soft baking the coated matrix; and treating the soft-baked coated matrix at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic device applications as disclosed herein.

6. Electronic devices

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

In some embodiments, the flexible glass replacement in the electronic device is a polyimide film comprising a polyimide having repeating units of formula III as described in detail above.

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

Organic electronic devices that may benefit from having one or more layers comprising at least one compound as described herein include, but are not limited to: (1) devices that convert electrical energy into radiation (e.g., a light emitting diode, a light emitting diode display, a lighting device, a luminaire, or a diode laser); (2) devices that detect a signal via an electronic process (e.g., a photodetector, a photoconductive cell, a photoresistor, a photoswitch, a phototransistor, a phototube, an IR detector, a biosensor); (3) devices that convert radiation into electrical energy (e.g., a photovoltaic device or a solar cell); (4) devices that convert light of one wavelength into light of a longer wavelength (e.g., a downconverting phosphorescent device); and (5) devices that include one or more electronic components comprising one or more organic semiconductor layers (e.g., a transistor or a diode). Other uses of the compositions according to the present invention include memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolyte capacitors, energy storage devices such as rechargeable batteries, and coating materials for electromagnetic shielding applications.

An example of a polyimide film that can function as a flexible glass replacement, as described herein, is illustrated in FIG. 1 . The flexible film (100) can have the properties described in the embodiments of the present invention. In some embodiments, the polyimide film that can function as a flexible glass replacement is incorporated into an electronic device. FIG. 2 illustrates an example where the electronic device (200) is an organic electronic device. The device (200) has a substrate (100), an anode layer (110), a cathode layer (130) that is a second electrical contact layer, and a photoactive layer (120) therebetween. Additional layers may optionally be present. Adjacent to the anode, there may be a hole injection layer (not shown), sometimes referred to as a buffer layer. Adjacent to the hole injection layer, there may be a hole transport layer (not shown) comprising a hole transport material. Adjacent to the cathode, there may be an electron transport layer (not shown) comprising an electron transport material. Optionally, the device may utilize 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 between 110 and 130 are individually and collectively referred to as organic active layers. Additional layers, which may or may not be present, include a color filter, a touch panel, and/or a cover sheet. In addition to the substrate (100), one or more of these layers may also be made of a polyimide film as disclosed herein.

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

In some embodiments, the different layers have thickness ranges as follows: substrate (100), 5 to 100 microns; anode (110), 500 to 5000 Å, in some embodiments 1000 to 2000 Å; hole injection layer (not shown), 50 to 2000 Å, in some embodiments 200 to 1000 Å; hole transport layer (not shown), 50 to 3000 Å, in some embodiments 200 to 2000 Å; photoactive layer (120), 10 to 2000 Å, in some embodiments 100 to 1000 Å; electron transport layer (not shown), 50 to 2000 Å, in some embodiments 100 to 1000 Å; Cathode (130), 200 to 10,000 Å, in some embodiments 300 to 5,000 Å. The preferred ratio of layer thicknesses will depend on the exact properties of the materials used.

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

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

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

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

The optional hole injection layer may comprise a hole injection material. The term "hole injection layer" or "hole injection material" is intended to mean an electrically conductive or semiconductive material, which may have one or more functions in an organic electronic device, including but not limited to planarizing an underlying layer, charge transport and/or charge injection properties, removing impurities such as oxygen or metal ions, and other aspects to promote or improve the performance of the organic electronic device. The hole injection material may be a polymer, an oligomer, or a small molecule, and may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture, or other composition.

The hole injection layer can be formed of a polymeric material, such as polyaniline (PANI) or polyethylenedioxythiophene (PEDOT), which is usually doped with a protonic acid. The protonic acid can be, for example, poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), etc. The hole injection layer (120) can include a charge transport compound, such as copper phthalocyanine and tetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ). In some embodiments, the hole injection layer (120) is made of a dispersion of a conducting polymer and a colloid-forming polymeric acid. Such materials are described, for example, in U.S. Patent Application Publication Nos. 2004-0102577, 2004-0127637, and 2005-0205860.

The other layer may include a hole transport material. Examples of hole transport materials for the hole transport layer are summarized in, for example, Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Both hole transport small molecules and polymers may be used. Commonly used hole transport molecules include, but are not limited to: 4,4',4"-tris(N,N-diphenyl-amino)-triphenylamine (TDATA); 4,4',4"-tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA); N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine (TPD); 4,4'-Bis(carbazol-9-yl)biphenyl (CBP); 1,3-Bis(carbazol-9-yl)benzene (mCP); 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC); N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl)biphenyl]-4,4'-diamine (ETPD); Tetrakis-(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA); α-Phenyl-4-N,N-diphenylaminostyrene (TPS); p-(Diethylamino)benzaldehyde diphenylhydrazone (DEH); Triphenylamine (TPA); Bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP); 1-Phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl] pyrazoline (PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB); N,N,N',N'-tetrakis(4-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TTB); N,N'-bis(naphthalen-1-yl)-N,N'-bis-(phenyl)benzidine (α-NPB); and porphyrin compounds such as copper phthalocyanine. Commonly used hole transport polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophene), polyaniline, and polypyrrole. It is also possible to obtain hole transport polymers by doping hole transport molecules such as those mentioned above into polymers such as polystyrene and polycarbonate. In some cases, triarylamine polymers, especially triarylamine-fluorene copolymers, are used. In some cases, the polymers and copolymers are crosslinkable. Examples of crosslinkable hole transport polymers can be found, for example, in U.S. Patent Application Publication No. 2005-0184287 and International Patent Publication No. WO 2005/052027. In some embodiments, the hole transport layer is doped with p-dopants such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10-tetracarboxylic acid-3,4,9,10-dianhydride.

Depending on the application of the device, the photoactive layer (120) may be a light-emitting layer that is activated by an applied voltage (as in a light-emitting diode or a light-emitting electrochemical cell), a layer of material that absorbs light and emits light of a longer wavelength (as in a downconverting phosphorescent device), or a layer of material that generates a signal in the presence or absence of an applied bias voltage in response to radiant energy (as in a photodetector or photovoltaic device).

In some embodiments, the photoactive layer comprises a compound comprising a luminescent compound having a photoactive material. In some embodiments, the photoactive layer further comprises a host material. Examples of host materials include, but are not limited to, chrysene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, carbazole, indolocarbazole, furan, benzofuran, dibenzofuran, benzodifuran, and metal quinolinate complexes. In some embodiments, the host material is deuterated.

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

In some embodiments, the photoactive layer comprises only (a) an electroluminescent dopant having an emission maximum between 380 nm and 750 nm, (b) a first host compound, and (c) a second host compound, without any additional materials that substantially alter the operation or distinguishing characteristics of the layer.

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

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

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

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

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

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

The optional layer may function not only to facilitate electron transport but also to act as a confinement layer to prevent exciton quenching at the layer interface. Preferably, such a layer promotes electron mobility and reduces exciton quenching.

In some embodiments, the layer comprises another electron transport material. Examples of electron transport materials that can be used in the optional electron transport layer include metal chelate oxinoid compounds including metal quinolate derivatives, such as tris(8-hydroxyquinolato)aluminum (AlQ), bis(2-methyl-8-quinolinolato)(p-phenylphenolato)aluminum (BAlq), tetrakis-(8-hydroxyquinolato)hafnium (HfQ), and tetrakis-(8-hydroxyquinolato)zirconium (ZrQ); Azole compounds such as 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD), 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), and 1,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivatives such as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthrolines such as 4,7-diphenyl-1,10-phenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); triazines; fullerenes; and mixtures thereof. In some embodiments, the electron transport material is selected from the group consisting of metal quinolates and phenanthroline derivatives. In some embodiments, the electron transport layer further comprises an n-dopant. N-dopant materials are well known. N-dopants include, but are not limited to, Group 1 and Group 2 metals; Group 1 and Group 2 metal salts, such as LiF, CsF, and Cs ₂ CO ₃ ; Group 1 and Group 2 metal-organic compounds, such as Li quinolate; and molecular n-dopants, such as leuco dyes, metal complexes, such as W ₂ (hpp) ₄ (wherein hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido-[1,2-a]-pyrimidine), and cobaltocene, tetrathianaphthacene, bis(ethylenedithio)tetrathiafulvalene, heterocyclic radicals or diradicals, and dimers, oligomers, polymers, dispiro compounds and polycycles of heterocyclic radicals or diradicals.

An optional electron injection layer can be deposited on the electron transport layer. Examples of electron injection materials include, but are not limited to, Li-containing organometallic compounds, LiF, Li ₂ O, Li quinolate, Cs-containing organometallic compounds, CsF, Cs ₂ O, and Cs ₂ CO ₃ . Such a layer can react with the lower electron transport layer, the upper cathode, or both. When the electron injection layer is present, the amount of material deposited is typically in the range of 1 to 100 Å, and in some embodiments, 1 to 10 Å.

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

Organic electronic devices are known to have other layers. For example, between the anode (110) and the hole injection layer (not shown), there may be a layer (not shown) that controls the amount of positive charge injected and/or provides band gap matching of the layers, or functions as a protective layer. Layers known in the art, such as ultra-thin layers of copper phthalocyanine, silicon oxynitride, fluorocarbons, silanes, or metals such as Pt, may be used. Alternatively, part or all of the anode layer (110), the active layer (120), or the cathode layer (130) may be surface treated to increase the charge carrier transport efficiency. The selection of materials for each component layer is preferably determined by balancing the positive and negative charges in the emitter layer to provide a device having high electroluminescence efficiency.

It is understood that each functional layer may consist of more than one layer.

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

For liquid phase deposition methods, a suitable solvent for a particular compound or a related class of compounds can be readily determined by one skilled in the art. For some applications, it is desirable for the compound to be dissolved in a non-aqueous solvent. Such non-aqueous solvents may be relatively polar, such as C ₁ to C ₂₀ alcohols, ethers, and acid esters, or may be relatively non-polar, such as C ₁ to C ₁₂ alkanes, or aromatics, such as toluene, xylene, and trifluorotoluene. Other liquids suitable for use in preparing liquid compositions comprising the novel compounds as solutions or dispersions as described herein include, but are not limited to, chlorinated hydrocarbons (e.g., methylene chloride, chloroform, chlorobenzene), aromatic hydrocarbons (e.g., substituted and unsubstituted toluenes and xylenes, including trifluorotoluene), polar solvents (e.g., tetrahydrofuran (THP), N-methyl pyrrolidone), esters (e.g., ethyl acetate), alcohols (isopropanol), ketones (cyclopentanone), and mixtures thereof. Suitable solvents for electroluminescent materials are described, for example, in International Patent Publication No. WO 2007/145979.

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

It is understood that the efficiency of the device can be improved by optimizing other layers of the device. For example, more efficient cathodes such as Ca, Ba or LiF can be used. Novel hole transport materials and shaped substrates that reduce the operating voltage or increase the quantum efficiency are also applicable. Additional layers can also be added to match the energy levels of the various layers and facilitate electroluminescence.

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

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

Example

The concepts described herein are further illustrated in the following examples, which, however, do not limit the scope of the invention as set forth in the claims.

Example 1

This example illustrates the preparation of compound 4, a diamine having the chemical formula I.

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

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

(b) 6,14-Bis(4-amino-2-trifluoromethylphenyl)-3a,4,9,9a-tetrahydro-2-phenyl-4,9[1',2']-benzeno-1H-benz[f]isoindole-1,3(2H)-dione, compound 4.

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

Example 2

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

Diamine compound 4 (4.5 g, 6.72 mmol), BPDA (2.768 g, 9.408 mmol), PMDA (0.293 g, 1.344 mmol), TFMB (2.152 g, 6.72 mmol) and N-methylpyrrolidinone (62 g) were allowed to react at ambient temperature, after which PMDA (45 mg) was carefully added one by one. NMP was partially distilled off until a final 21 wt% polymer content and a viscosity of 27390 cP. GPC: Mn = 96941, Mw = 203561, Mp = 195824, Mz = 324327, PDI = 2.10.

Example 3

This example illustrates the production of a polyimide film wherein the polyimide has the chemical formula III.

The polyamic acid solution from Example 2 was filtered through a microfilter, spin-coated on a clean silicon wafer, soft-baked at 90° C. on a hotplate, and placed in a furnace. The furnace was purged with nitrogen and heated to a maximum temperature of 320° C. The wafer was taken out from the furnace, immersed in water, and manually delaminated to obtain a sample of the polyimide film.

A polyimide film with a thickness of 8.62 μm had the following properties:

Haze: 0.19%

T _g : 327℃

CTE (1st measurement): 34.1 ppm/℃

Birefringence (633 nm): 0.042

Tensile modulus: 4.77 GPa

Tensile strength: 198.7 MPa

Breaking Elongation: 24.6%

1% TGA loss: 415℃

Optical phase delay: 369

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

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

Benefits, other advantages, and solutions to problems have been described above with respect to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause or make any benefit, advantage, or solution more apparent are not to be construed as being a critical, essential, or essential feature of any or all of the claims.

It should be understood that certain features described herein in the context of individual embodiments for clarity may also be provided in combination in a single embodiment. Conversely, various features described in the context of a single embodiment for brevity may also be provided individually or in any subcombination. The use of the various ranges of values set forth herein are intended to be approximations, as if the word "about" were placed in front of both the minimum and maximum values within the stated ranges. In this manner, slight variations above and below the stated ranges may be used to achieve substantially the same results as the values within the ranges. Furthermore, the disclosure of these ranges is intended to be a continuous range including all values between the minimum average value and the maximum average value, including fractional values that may occur when a portion of a component of one value is mixed with a component of a different value. Furthermore, when broader and narrower ranges are disclosed, it is within the scope of the present invention to make the minimum value of one range coincide with the maximum value of the other range, and vice versa.

Claims (9)

Polyamines having chemical formula ID:
[chemical formula ID]
Polyamic acid having repeating units of chemical formula II:
[Chemical Formula II]

(Here,
R ^a represents a tetracarboxylic acid moiety residue derived from a tetracarboxylic dianhydride selected from the group consisting of pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA), 4,4'-hexafluoroiso-propylidenebisphthalic polyanhydride (6FDA), and 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA);
R ^b is a diamine residue derived from a polyamine according to claim 1). (a) a liquid composition comprising a polyamic acid according to claim 2 and (b) an aprotic solvent having a boiling point higher than 130°C. Polyimide having repeating units of chemical formula III:
[Chemical Formula III]

(Here,
R ^a represents a tetracarboxylic acid moiety residue derived from a tetracarboxylic dianhydride selected from the group consisting of pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA), 4,4'-hexafluoroiso-propylidenebisphthalic polyanhydride (6FDA), and 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA);
R ^b is a diamine residue derived from a polyamine according to claim 1). An organic electronic device having at least one layer comprising a polyimide film having repeating units of chemical formula III according to claim 4. An electronic device in accordance with claim 5, wherein the layer is used for a device component selected from the group consisting of a device substrate, a substrate for a color filter sheet, a cover film, and a touch screen panel. delete delete delete