KR20210011497A - Polymers for use in electronic devices - Google Patents

Abstract

A polyimide film is disclosed, wherein the polyimide has a weight average molecular weight of 100,000 or more and comprises a repeating unit structure of formula (V). R ^a in formula (V) is the same or different at each occurrence and represents one or more tetracarboxylic acid moieties; R ^b is the same or different in each case and represents one or more aromatic diamine moieties, and 30-100 mol% of R ^b has the formula II or the formula III. In Formula II and Formula III, R ¹ and R ² are the same or different and are F, R _f , or OR _f ; R _f is C _1-3 perfluoroalkyl; * Indicates the point of attachment.

Description

Polymers for use in electronic devices

Claims of Prior Application

This application claims the benefit of U.S. Provisional Application No. 62/687,314, filed June 20, 2018, the entirety of which is incorporated herein by reference.

Technical field

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

Materials for use in electronic devices often have stringent requirements in terms of their structural, optical, thermal, electronic and other properties. As the number of commercial electronic devices continues to increase, there is a need for innovative materials with new and/or improved properties in the breadth and specificity of essential properties. Polyimides are a representative class of polymer compounds that have been widely used in various electronic devices. Polyimide can be used as a flexible glass substitute in electronic display devices if it has appropriate properties. Such a material can function as a component of a liquid crystal display ("LCD") where moderate power consumption, light weight, and layer flatness are important properties for efficient use. Other uses in electronic display devices that value these parameters include device substrates, substrates for color filter sheets, cover films, touch screen panels, and the like.

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

Polyimide films generally have sufficient thermal stability, high glass transition temperatures, and mechanical toughness to contemplate these applications. In addition, since polyimide generally does not generate haze when bending is repeated, it is often preferred over other transparent substrates such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) in flexible display applications.

However, the conventional amber polyimide cannot be used in some display applications such as color filters and touch screen panels where light transmission is important. In addition, polyimides are generally rigid, highly aromatic materials, and when the film/coating is formed, the polymer chains tend to be oriented on the side of the film/coating. This causes a difference in refractive index (birefringence) between the parallel direction and the vertical direction of the film, resulting in an optical phase delay that can negatively affect display performance. In order to expand the use of polyimide in the display market, there is a need for a solution for improving light transmittance, reducing amber color, and reducing birefringence causing optical phase delay while maintaining desirable properties of polyimide.

Thus, there is a continuing need for polymeric materials suitable for use in electronic devices.

As a liquid composition having a solid content of 10 wt% or more and a viscosity of about 3000 cps or more,

(a) polyamic acid having a repeating unit structure of formula (I)

[Formula I]

(In the formula,

R ^a is the same or different at each occurrence and represents one or more tetracarboxylic acid moieties;

R ^b is the same or different at each occurrence and represents one or more aromatic diamine moieties;

30-100 mol% of R ^b has Formula II or Formula III,

In the formula,

R ¹ and R ² are the same or different and are selected from the group consisting of F, R _f , and OR _f ;

R _f is C _1-3 perfluoroalkyl;

* Indicates the point of attachment;

R ¹ and R ² are both adjacent to the point of attachment) and;

(b) high boiling point aprotic solvent

A composition comprising a is provided.

Polyimide films are also provided, the polyimide having a number average molecular weight of 100,000 or more and comprising a repeating unit structure of formula V

[Formula V]

(In the formula,

R ^a is the same or different at each occurrence and represents one or more tetracarboxylic acid moieties;

R ^b is the same or different at each occurrence and represents one or more aromatic diamine moieties;

30-100 mol% of R ^b has Formula II or Formula III,

In the formula,

R ¹ and R ² are the same or different and are selected from the group consisting of F, R _f , and OR _f ;

R _f is C _1-3 perfluoroalkyl;

* Indicates the point of attachment;

Both R ¹ and R ² are adjacent to the point of attachment);

In addition, the polyimide film

Coating a substrate with a polyamic acid solution comprising at least one tetracarboxylic acid component and at least one diamine component in a high boiling point aprotic solvent;

Soft baking the coated substrate;

It is prepared according to a method comprising the step of treating the soft baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals in sequence and without repetition.

A polyimide film is also provided, the polyimide having a weight average molecular weight of 100,000 or more and comprising a repeating unit structure of formula V

[Formula V]

(In the formula,

R ^a is the same or different at each occurrence and represents one or more tetracarboxylic acid moieties;

R ^b is the same or different at each occurrence and represents one or more aromatic diamine moieties;

30-100 mol% of R ^b has Formula II or Formula III,

In the formula,

R ¹ and R ² are the same or different and are selected from the group consisting of F, R _f , and OR _f ;

R _f is C _1-3 perfluoroalkyl;

* Indicates the point of attachment;

Both R ¹ and R ² are adjacent to the point of attachment);

In addition, the polyimide film

Coating a substrate with a polyamic acid solution comprising at least one tetracarboxylic acid component and at least one diamine component in a high boiling point aprotic solvent;

Soft baking the coated substrate;

It is prepared according to a method comprising the step of treating the soft baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals in sequence and without repetition.

As a flexible glass substitute in an electronic device, a flexible glass substitute is also provided, which is the polyimide film.

Also provided is an electronic device having at least one layer comprising the polyimide film.

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

The foregoing general description and the following detailed description are illustrative and illustrative only, and do not limit the invention as defined in the appended claims.

In order to enhance the understanding of the concepts presented herein, embodiments are illustrated in the accompanying drawings.
1 includes an illustration of an example of a polyimide film that can act as a flexible glass substitute.
2 includes an illustration of an example of an electronic device including a flexible glass substitute.
Those skilled in the art will understand that the objects in the drawings have been drawn for conciseness and clarity and are not necessarily drawn to scale. For example, in the drawings, dimensions of some objects may be exaggerated compared to other objects in order to increase understanding of implementation.

As described in detail below, a polyamic acid having formula (I) is provided.

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

As described in detail below, polyimides are also provided in which the repeating units have the structure of formula IV.

Also provided is one or more methods for making polyimide films having repeating units of formula IV.

As a flexible glass substitute in an electronic device, a flexible glass substitute is also provided, which is a polyimide film having repeating units of formula IV.

Also provided is an electronic device having at least one layer comprising a polyimide film having repeating units of formula IV.

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

Although many aspects and embodiments have been described above, they are merely illustrative and not limiting. After reading this specification, those skilled in the art will understand that other aspects and implementations are possible without departing from the scope of the invention.

Other features and advantages of any one or more embodiments will become apparent from the following detailed description and claims. The detailed description first deals with the definition and description of terms, then deals with a liquid composition, a polyimide, a method of manufacturing a polyimide film, an electronic device, and finally deals with examples.

1. Definition and explanation of terms

Before addressing the embodiments described below in detail, some terms are defined or described.

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

The term “alignment layer” refers to a layer of organic polymer in an LCD that aligns molecules closest to each plate by rubbing the plate against the LCD glass in one preferred direction during the liquid crystal device (LCD) manufacturing process.

The term "alkyl" as used herein includes branched and straight chain saturated aliphatic hydrocarbon groups. Unless otherwise specified, the term is also intended to include cyclic groups. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, isobutyl, secondary butyl, tertiary 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, alkyl groups can be single, double, and triple 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, alkyl groups have 1 to 20 carbon atoms. In other embodiments, the alkyl group has 1 to 6 carbon atoms. This term includes heteroalkyl groups. Heteroalkyl groups may have 1 to 20 carbon atoms.

The term “aprotic” refers to a class of solvents that lack acidic hydrogen atoms and thus cannot act as hydrogen donors. Typical aprotic solvents include alkanes, carbon tetrachloride (CCl4), benzene, dimethyl formamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and the like.

The term "aromatic compound" is intended to mean an organic compound comprising at least one unsaturated cyclic group having 4n+2 delocalized π electrons. The term includes both aromatic compounds having only carbon atoms and hydrogen atoms, and heteroaromatic compounds in which at least one of the carbon atoms in the cyclic group is substituted with 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 hydrogen ("H") or deuterium ("D") from an aromatic compound. The aryl group may be a single ring (monocyclic), or may have multiple rings (bicyclic or more) condensed or covalently bonded to each other. “Hydrocarbon aryl” has only carbon atoms in the aromatic ring(s). “Heteroaryl” has one or more heteroatoms within at least one aromatic ring. In some embodiments, hydrocarbon aryl groups have 6 to 60 ring carbon atoms, and in some embodiments 6 to 30 ring carbon atoms. In some embodiments, heteroaryl groups have 4-50 ring carbon atoms, and in some embodiments 4-30 ring carbon atoms.

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

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

Unless otherwise specified, all groups may or may not be substituted. 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 are alkyl, aryl, nitro, cyano, -N(R')(R"), halo, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryl Oxy, 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 (s=0-2), or -S(O) _s -heteroaryl (s=0-2). Each of R'and R" is independently, optionally substituted alkyl, cycloalkyl, Or an aryl group. In certain embodiments, R′ and R”, together with the nitrogen atom bonded to them, may form a ring system. The substituent may be a bridging group.

The term "amine" refers to a compound containing a basic nitrogen atom having a lone pair of electrons. The term “amino” refers to the functional group -NH ₂ , -NHR, or -NR ₂ , where R is the same or different in each case and may be an alkyl group or an aryl group. The term "diamine" is intended to mean a compound containing two basic nitrogen atoms with an associated lone pair of electrons. The term "aromatic diamine" is intended to mean an aromatic compound having two amino groups. The term "bent diamine" is intended to mean a diamine in which two basic nitrogen atoms and an associated lone pair of electrons are arranged asymmetrically with respect to the center of symmetry of the compound or functional group in question (eg m -phenylenediamine below).

The term "aromatic diamine moiety" is intended to mean a moiety bonded to the two amino groups of an aromatic diamine. The term “aromatic diisocyanate moiety” is intended to mean a moiety bonded to two isocyanate groups of an aromatic diisocyanate compound. Additional examples of this are as follows.

The terms “diamine moiety” and “diisocyanate moiety” refer to a moiety bonded to two amino groups or two isocyanate groups, respectively, and the moiety may be aromatic or aliphatic.

The term "b*" refers to the b* axis in the CIELab color space representing the yellow/blue alternative color. Yellow is represented by a positive b* value, and blue is represented by a negative b* value. The measured b* value can be influenced by the solvent, especially since the choice of solvent can affect the chromaticity measured in materials exposed to high temperature processing conditions. This can occur as a result of the inherent properties of the solvent and/or the properties associated with the low levels of impurities contained in the various solvents. Certain solvents are usually preselected to achieve the desired b* value for a particular application.

The term “birefringence” refers to the difference in refractive index in different directions in a polymer film or coating. This term generally refers to the difference between the refractive index of the x-axis or y-axis (in-plane) and the refractive index of the z-axis (out-of-plane).

When referring to a layer, material, member, or structure, the term “charge transport” means that such a layer, material, member or structure is It means that it facilitates the transfer of electric charges. The hole transport material facilitates the transfer of positive charges, and the electron transport material facilitates the transfer of negative charges. Light-emitting materials may also have some charge transport properties, but the term "charge transport layer, charge transport material, charge transport member, or charge transport structure" does not include a layer, material, member or structure whose primary function is light emission. .

The term "compound" refers to an electrically uncharged substance consisting of molecules that further contain atoms that cannot be separated from the molecule by physical means without breaking a chemical bond. This term includes oligomers and polymers.

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

α = (ΔL / L ₀ ) / ΔT

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

The term “dopant” refers to the electronic property(s) of that layer, or the target wavelength(s) of radiation emission, absorption, or filtering, within a layer comprising a host material, the electronic properties of a layer in which such material is not present ( S), or a material that changes relative to the wavelength(s) of radiation emission, absorption, or filtering.

The term “electroactive” when referring to a layer or material refers to a layer or material that electronically facilitates the operation of the device. Examples of electroactive materials include, but are 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 or emit radiation upon absorption of radiation. It doesn't work. Examples of inactive materials include, but are not limited to, planarizing materials, insulating materials, and environmental shielding materials.

The term “tensile elongation” or “tensile strain” is meant to mean the percentage of length increase that occurs before the material breaks upon application of tensile stress. This can be measured, for example, by ASTM method D882.

The prefix "fluoro" denotes that one or more hydrogens in a group have been replaced by fluorine.

The term “glass transition temperature (or T _g )” refers to a reversible change in the amorphous region of an amorphous polymer or semi-crystalline polymer, ie a sudden change in material from a hard, vitreous, or brittle state to a flexible or elastic state. It means temperature. Microscopically, the glass transition occurs when the normally wound, immobile polymer chains rotate freely and can move past each other. T _g can be measured using differential scanning calorimetry (DSC), thermodynamic analysis (TMA), or kinetic analysis (DMA), or other methods.

The prefix “hetero” indicates that one or more carbon atoms have been replaced by another atom. In some embodiments, the heteroatom is O, N, S, or combinations thereof.

The term “high boiling point” refers to a boiling point higher than 130°C.

The term “host material” refers to a material to which a dopant is added. The host material may or may not have electronic property(s) or the ability to emit, absorb, or filter radiation. In some embodiments, the host material is present in a higher concentration.

The term "isothermal weight loss" is meant to mean a property of a material that is directly related to the thermal stability of the material. This is generally measured via thermogravimetric analysis (TGA) at the desired constant temperature. Materials with high thermal stability generally exhibit very low isothermal weight loss rates for target times at the required use or processing temperature, and can therefore be applied at these temperatures without significant loss of strength, outgassing, and/or structural changes.

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

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

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

The term “optical phase delay (or R _TH )” refers to the product of the difference between the average in-plane and out-of-plane refractive indices (ie, birefringence) and the thickness of the film or coating. Optical phase delay is generally measured for light at a certain frequency, and the units are reported in nanometers.

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

The term "particle content" is meant to mean the number or number of insoluble particles present in a solution. The particle content can be measured for the solution itself, or it can be measured for the final material (fragment, film, etc.) made from such a film. Various optical methods can be used to evaluate these properties.

The term "photoactive" means that it emits light when activated by an applied voltage (as in a light-emitting diode or a chemical cell), absorbs a photon (as in a downconverting phosphorescent device) and then emits light, or (as in a photodetector or photovoltaic cell) ) Refers to a material or layer that generates a signal in the presence or absence of an applied bias voltage in response to radiant energy.

The term “polyamic acid solution” refers to a solution of a polymer containing amic acid units capable of forming imide groups by intramolecular cyclization.

The term “polyimide” refers to a condensation polymer resulting from the reaction of at least one difunctional carboxylic acid component with at least one primary diamine or diisocyanate. They contain the imide structure -CO-NR-CO- as linear or heterocyclic units along the backbone of the polymer backbone.

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

The term "soft baking" is a process generally used in the manufacture of electronic devices, and refers to a process of heating a coated material to remove a solvent and solidify a film. Soft baking is a preparatory step for the subsequent heat treatment of the coated layer or film and is generally carried out in a hot plate or vented oven at a temperature of 90°C to 110°C.

The term “substrate” is a substrate that may be rigid or flexible, which may include one or more layers of one or more materials, which may include, but are not limited to, glass, polymer, metal or ceramic materials, or combinations thereof. Refers to the substrate. The substrate may or may not include electronic devices, circuits, or conductive members.

The term “siloxane” refers to the group R ₃ SiOR ₂ Si-, where R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons of the R alkyl group are substituted with Si.

The term “siloxy” refers to the group R ₃ SiO-, where R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl. The term “silyl” refers to the group R ₃ Si-, where R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons of the R alkyl group are substituted with Si.

The term “spin coating” is intended to mean 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 rotates at low speed or does not rotate at all. Then, the substrate is rotated at a specific speed in order to uniformly apply the coating material by centrifugal force.

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 films are evaluated for particle content by several standard measurement techniques, including laser particle detection and other techniques known in the art.

The term "tensile modulus" is meant to mean a measure of the stiffness of a solid material, defining the initial relationship between stress (force per unit area) and strain (proportional strain) in a film-like material. A commonly used unit is Giga Pascal (GPa).

The term "tetracarboxylic acid component" is intended to mean at least one of tetracarboxylic acid, tetracarboxylic acid monoanhydride, tetracarboxylic dianhydride, tetracarboxylic acid monoester, and tetracarboxylic acid diester.

The term "tetracarboxylic acid component moiety" is intended to mean a moiety bonded to the four carboxyl groups of the tetracarboxylic acid component. Additional examples of this are as follows.

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

The term "yellowing degree (or YI)" means the degree of yellowing relative to the standard. Positive YI values indicate the presence and grade of yellow. Materials with negative YI are bluish. It should also be noted that YI can be solvent dependent, especially for polymerization and/or curing processes carried out at high temperatures. For example, the grade of color introduced using DMAC as a solvent may differ from that introduced using NMP as a solvent. This can occur as a result of the inherent properties of the solvent and/or the properties associated with the low levels of impurities contained in the various solvents. Certain solvents are usually preselected to achieve the desired YI values for a particular application.

In a structure in which a substituent bond passes through one or more rings as shown below,

It is meant that the substituent R may be bonded at any effective position on one or more rings.

The phrase "adjacent to" when referring to a layer in a device does not necessarily mean that one layer is immediately next to another. On the other hand, the phrase "adjacent R group" is used to refer to an R group adjacent to each other in the formula (ie, an R group on an atom connected by a bond). Exemplary adjacent R groups are as follows.

In this specification, unless expressly stated otherwise or indicated to the contrary in the context of usage, embodiments of the subject matter include, contain, contain, have, consist of, or consist of, or consist of certain features or elements. When stated or described as being, one or more features or elements other than those explicitly mentioned or described may be present in an implementation. Alternative embodiments of the disclosed subject matter are described as consisting essentially of specific features or elements, in which there are no features or elements that substantially alter the principle of operation or distinct features of the embodiments. Another alternative embodiment of the disclosed subject matter is described as consisting of specific features or elements, in which only those features or elements specifically mentioned or described are present in such embodiments or non-substantial variations thereof.

Further, unless expressly stated otherwise, "or" means an inclusive OR, not an exclusive OR. For example, condition A or B is satisfied by any of the following: A is true (or exists), B is false (or does not exist), A is false (or does not exist), and B is true (or is), And both A and B are true (or present).

In addition, singular nouns are used to describe the elements and components described herein. This is for convenience only and is to provide a general meaning of the scope of the present invention. Such descriptions are to be construed to include one or at least one, and the singular includes the plural unless it is clear that it excludes the plural.

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

Unless defined otherwise, 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 may 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 specific passages are cited. In case of conflict, the present specification, including definitions, will control. Further, the materials, methods, and examples are illustrative only and are not intended to be limiting.

To the extent not described herein, many details of specific materials, processing operations and circuits are conventional and can be found in textbooks and other materials in the field of organic light emitting diode displays, photodetectors, photovoltaic and semiconductor member technologies.

2. Liquid composition

There is provided a liquid composition having a solid content of 10 wt% or more and a viscosity of about 3,000 cps (cps = centipoise), the composition comprising

(a) polyamic acid having a repeating unit structure of formula (I)

[Formula I]

(In the formula,

R ^a is the same or different at each occurrence and represents one or more tetracarboxylic acid moieties;

R ^b is the same or different at each occurrence and represents one or more aromatic diamine moieties;

30-100 mol% of R ^b has Formula II or Formula III,

In the formula,

R ¹ and R ² are the same or different and are selected from the group consisting of F, R _f , and OR _f ;

R _f is C _1-3 perfluoroalkyl;

* Indicates the point of attachment;

R ¹ and R ² are both adjacent to the point of attachment) and;

(b) a high boiling point aprotic solvent.

The liquid composition is also referred to herein as a “polyamic acid solution”.

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

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

In some embodiments of formula I, R ^a represents one tetracarboxylic acid moiety.

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

In some embodiments of formula I, R ^a represents 3 tetracarboxylic acid moieties.

In some embodiments of formula I, R ^a represents 4 tetracarboxylic acid moieties.

In some embodiments of formula I, R ^a represents one or more tetracarboxylic acid 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 dianhydride (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, but are not limited thereto. These aromatic dianhydrides are alkyl, aryl, nitro, cyano, -N(R')(R ^" ), halo, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, hetero Aryloxy, 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 (s=0-2), or -S(O) _s -heteroaryl (s=0-2), etc. may be optionally substituted with groups known in the art. Each of R'and R" is independently independent As an optionally substituted alkyl, cycloalkyl, or aryl group. In certain embodiments, R′ and R”, together with the nitrogen atom bonded to them, may form a ring system. The substituent may be a bridging group.

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

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

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

In some embodiments of formula I, R ^a represents a 6FDA moiety.

In some embodiments of formula I, R ^a represents a BTDA moiety.

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

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

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

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

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

In some embodiments of formula I, R ^a represents 6FDA residues and BTDA residues.

In Formula I, 30-100 mol% of R ^b represents a diamine residue having Formula II or Formula III. In some embodiments of Formula I, 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 90-100 mol%, in some embodiments 100 mol%) of R ^b has Formula II.

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

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

In some embodiments of Formula II, R ¹ is C _1-3 perfluoroalkyl, and in some embodiments trifluoromethoxy.

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

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

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

All the above-described embodiments for R ¹ and R ² in Formula II apply equally to R ¹ and R ² in Formula III.

In some embodiments of formula I, R ^b represents a moiety from a diamine selected from the group consisting of compounds IV-A to IV-F above.

Diamine can be prepared as shown in the scheme below.

(One)

(2)

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

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

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

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

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-trimethylbenzene (DAM), 3,3',5,5'-tetramethylbenzidine (3355TMB), 2,2'-bis(trifluoromethyl) benzidine (22TFMB or TFMB), 2,2-bis[4-(4 -Aminophenoxy)phenyl]propane (BAPP), 4,4'-methylene 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 (anthranylic 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), 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-trifluoromethyl phenoxy) biphenyl (6BFBAPB), 3,3'5,5'-tetramethyl-4,4'-diamino diphenylmethane (TMMDA), and the like, and combinations thereof.

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

In some embodiments of Formula I, moieties resulting from monoanhydride monomers exist as end-capping groups.

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

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

In some embodiments of Formula I, moieties resulting from monoamine monomers exist as end-capping groups.

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

In some embodiments, the monoamine is present in an amount of 5 mol% or less 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.

Unless mutually exclusive, any of the above embodiments of the polyamic acid can be combined with one or more other embodiments. For example, embodiments in which R ^a represents ^a PMDA moiety can be combined with embodiments in which R ^b has formula II.

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

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

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

In some embodiments, the high boiling 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 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, two or more of the above identified high boiling point aprotic solvents are used in the liquid composition.

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

The polyamic acid solution may optionally further contain any one of a number of additives. These additives may be antioxidants, heat stabilizers, adhesion promoters, coupling agents (eg, 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 methods available in connection with the introduction of components (ie, monomers and solvents). Some methods of preparing the polyamic acid solution include the following methods.

(a) After mixing the diamine component and the dianhydride component together in advance, the mixture is gradually added to the solvent while stirring.

(b) A method of adding a solvent to the stirred mixture of diamine and dianhydride component (as opposed to (a) above).

(c) After dissolving only diamine in a solvent, a method of adding a dianhydride in a ratio capable of controlling the reaction rate.

(d) After dissolving only the dianhydride component in a solvent, the amine component is added in a ratio capable of controlling the reaction rate.

(e) A method of separately dissolving a diamine component and a dianhydride component in a solvent, and then mixing these solutions in a reactor.

(f) A method in which a polyamic acid having an excess amine component and another polyamic acid having an excess dianhydride component are formed in advance, and then reacted with each other in a reactor, particularly in a manner of producing a non-random or block copolymer.

(g) A method in which a specific part of an amine component and a dianhydride component are first reacted, and then the remaining diamine components are reacted, or vice versa.

(h) A method of adding some or all of the components to some or all of the solvent in any order (some or all of the optional components may be added as a solution to some or all of the solvent).

(i) one of the dianhydride components is first reacted with one of the diamine components to give a first polyamic acid, and then the other dianhydride component is reacted with another amine component to give a second polyamic acid, and then a film A method of compounding the polyamic acid in any one of a number of ways prior to formation.

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

The polyamic acid solution can then be filtered more than once to reduce the particle content. Polyimide films produced from such filtered solutions may exhibit a reduction in the number of defects, thereby exhibiting excellent performance in the electronic device articles disclosed herein. Evaluation of filtration efficiency can be performed by a laser particle counter test in which a representative sample of a polyamic acid solution is cast onto a 5" silicon wafer. After soft baking/drying, the film is evaluated for particle content by several laser particle counting techniques in commercially available instruments known in the art.

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

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

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

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

The total polyamic acid composition may be indicated through a notation 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 represented as follows.

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

3. Polyimide film

A polyimide film prepared from the polyamic acid solution is provided.

Polyimide has a repeating unit structure of formula V

[Formula V]

(In the formula,

R ^a is the same or different at each occurrence and represents one or more tetracarboxylic acid moieties;

R ^b is the same or different at each occurrence and represents one or more aromatic diamine moieties;

30-100 mol% of R ^b has Formula II or Formula III,

In the formula,

R ¹ and R ² are the same or different and are selected from the group consisting of F, R _f , and OR _f ;

R _f is C _1-3 perfluoroalkyl;

* Indicates the point of attachment;

Both R ¹ and R ² are adjacent to the point of attachment);

In addition, the polyimide film

Coating a substrate with a polyamic acid solution comprising at least one tetracarboxylic acid component and at least one diamine component in a high boiling point aprotic solvent;

Soft baking the coated substrate;

It is prepared according to a method comprising the step of treating the soft baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals in sequence and without repetition.

All of the foregoing embodiments for R ^a and R ^b in formula I apply equally to R ^a and R ^b in formula V.

All embodiments described above for R ¹ and R ² in the general formula II, as applied to formula (I) apply equally to R ¹ and R ² in the general formula II, as applied to formula V.

A polyimide film is prepared by coating the polyamic acid solution on a substrate and then imidizing it. This can be achieved by a thermal conversion process or a chemical conversion process. Any known coating method can be used.

Some fluorinated diamines are known to be less reactive. In order to form a polyimide film having a sufficient molecular weight with such a low reactive diamine, several polymerization steps are used. Typically, a polyamic acid solution is prepared from the low reactive diamine, the solution is coated and imidized, and the imidized product is dissolved, recoated, and reimidated. Additional dissolution, recoating, and reimidation steps are repeated several times.

Surprisingly and unexpectedly, it was found that diamines having moieties of Formula II or Formula III have better reactivity. Polyimide film with sufficient molecular weight and excellent mechanical properties by one polymerization and imidization steps. The polyamic acid solution described herein eliminates the need to repeat the steps of forming, dissolving, recoating, and reimidating the imidation product several times.

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

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

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

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

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

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

In some embodiments of the polyimide film, the coefficient of in-plane thermal expansion (CTE) is less than 45 ppm/°C at 50°C to 200°C, less than 30 ppm/°C in some embodiments, and less than 20 ppm/°C in some embodiments , In some embodiments less than 15 ppm/°C, in some embodiments 0 ppm/°C to 15 ppm/°C, and in some embodiments 0 ppm/°C to 10 ppm/°C.

In some embodiments of the polyimide film, the glass transition temperature (T _g ) is higher than 250° C. for polyimide films cured at temperatures higher than 300° C., in some embodiments higher than 300° C., and in some embodiments 350° C. Higher than

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 between 1.5 GPa and 15.0 GPa, and in some embodiments between 1.5 GPa and 12.0 GPa.

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

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

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

In some embodiments of the polyimide film, the haze is less than 1.0% and 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, and in some embodiments less than 3.0. In some embodiments of the polyimide film, YI is less than 12, in some embodiments less than 10, and in some embodiments less than 5.

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

In some embodiments of the polyimide film, the transmittance at 430 nm is higher than 60%, and in some embodiments higher than 70%.

In some embodiments of the polyimide film, the transmittance at 450 nm is higher than 70%, and in some embodiments higher than 80%.

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

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

Unless mutually exclusive, any of the above embodiments of the polyimide film may be combined with one or more other embodiments.

The polyimide film can be prepared from a polyamic acid solution by a chemical or thermal conversion process. The polyimide films disclosed herein are produced by thermal conversion or modified thermal conversion processes compared to chemical conversion processes, particularly when used as a flexible glass substitute in electronic devices.

Chemical conversion processes are described in US Pat. Nos. 5,166,308 and 5,298,331, which are incorporated by reference in their entirety. In this process, the conversion chemical is added to the polyamic acid solution. Conversion chemicals found useful in the present invention include (i) one or more dehydrating agents such as fatty 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 (pyridine, picoline, isoquinoline, etc.), It is not limited to these. The anhydrous dehydration material is generally used in a slightly molar excess than the amount of amic acid groups present in the polyamic acid solution. The amount of acetic anhydride used is generally about 2.0 to 3.0 moles per equivalent of polyamic acid. In general, similar amounts of tertiary amine catalyst are used.

The thermal conversion process may or may not use a conversion chemical (ie, catalyst) to convert the polyamic acid casting solution to polyimide. If conversion chemicals are used, the process can be considered a modified thermal conversion process. In both types of thermal conversion processes, only thermal energy is used to heat the film for both drying of the film solvent and carrying out the imidization reaction. A thermal conversion process is generally used with or without a conversion catalyst to prepare the polyimide films disclosed herein.

Certain method parameters are preselected taking into account that it is not only the film composition that exhibits the desired properties. rather,

The curing temperature and temperature-ramp profile also play an important role in achieving the most desirable properties for the intended use disclosed herein. The polyamic acid must be imidized above the highest temperature of any subsequent processing steps (e.g., deposition of inorganic or other layer(s) required to manufacture a functional display), but that temperature will cause severe thermal degradation of the polyimide. /It must be lower than the temperature at which discoloration occurs. It should also be noted that in general an inert atmosphere is preferred, especially when higher process temperatures are used for imidization.

For the polyamic acid/polyimide disclosed herein, temperatures of 300° C. to 320° C. are generally used if a subsequent process temperature in excess of 300° C. is required. Choosing an appropriate curing temperature can result in a fully cured polyimide with an optimal balance of thermal and mechanical properties. Because of this very high temperature, an inert atmosphere is required. In general, oxygen concentrations of less than 100 ppm should be used in ovens. At very low oxygen concentrations the highest curing temperature can be used without significant degradation/discoloration of the polymer. Catalysts that promote the imidation process are effective in achieving higher levels of imidation at curing temperatures of about 200°C to 300°C. This approach can optionally be used if the flexible device is made with an upper cure temperature that is less than the T _g of the polyimide.

The time of each potential curing step is also an important process consideration. In general, the time used for curing at the highest temperature should be kept to a minimum. For example, for curing at 320° C., the curing time may be up to 1 hour in an inert atmosphere, but at higher curing temperatures this time must be shortened to avoid thermal degradation. In general, the higher the temperature, the shorter the time should be. One of skill in the art will recognize the balance between temperature and time to optimize the properties of a polyimide for a particular end use.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the thermal conversion process, the soft baked coated substrate is then cured for two preselected time intervals at two preselected temperatures, and the preselected time intervals may be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated substrate is then cured for three preselected time intervals at three preselected temperatures, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated substrate is then cured for four preselected time intervals at four preselected temperatures, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated substrate is then cured at 5 preselected temperatures for 5 preselected time intervals, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated substrate is then cured for six preselected time intervals at six preselected temperatures, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated substrate is then cured at 7 preselected temperatures for 7 preselected time intervals, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated substrate is then cured at 8 preselected temperatures for 8 preselected time intervals, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated substrate is then cured at 9 preselected temperatures for 9 preselected time intervals, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked coated substrate is then cured at 10 preselected temperatures for 10 preselected time intervals, each of which may be the same or different.

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

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is between 2 and 60 minutes.

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is between 2 minutes and 90 minutes.

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is between 2 minutes and 120 minutes.

In some embodiments of the thermal conversion process, a method of making a polyimide film comprises coating a polyamic acid solution on a substrate; Soft baking the coated substrate; By sequentially including the step of treating the soft baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, the polyimide film exhibits satisfactory properties for use in electronic devices such as those disclosed herein. .

In some embodiments of the thermal conversion process, a method of making a polyimide film comprises coating a polyamic acid solution on a substrate; Soft baking the coated substrate; By sequentially treating the soft baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, the polyimide film exhibits satisfactory properties for use in electronic devices such as those disclosed herein. .

In some embodiments of the thermal conversion process, the method of making a polyimide film essentially comprises: coating a polyamic acid solution onto a substrate; Soft baking the coated substrate; By sequentially treating the soft baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, the polyimide film exhibits satisfactory properties for use in electronic devices such as those disclosed herein. .

In general, the polyamic acid solution/polyimide disclosed herein is coated/cured onto a supporting glass substrate to facilitate processing through the rest of the display manufacturing process. At some point in the process as determined by the display manufacturer, the polyimide coating is removed from the supporting glass substrate by a mechanical separation or laser separation process. This process separates the polyimide from the glass as a film on which the display layer is deposited, thereby enabling a flexible form. Usually, this polyimide film with a deposited layer is then bonded to a thicker but still flexible plastic film to provide support for the subsequent manufacture of the display.

A modified thermal conversion process is also provided in which the conversion catalyst generally causes the imidation reaction at a temperature lower than the temperature at which the imidation reaction can occur without such conversion catalyst.

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

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

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

In some embodiments of the modified thermal conversion process, the conversion catalyst is present at no more than 5% by weight of the polyamic acid solution.

In some embodiments of the modified thermal conversion process, the conversion catalyst is present at up to 3% by weight of the polyamic acid solution.

In some embodiments of the modified thermal conversion process, the conversion catalyst is present at no more than 1% by weight of the polyamic acid solution.

In some embodiments of the modified thermal conversion process, the conversion catalyst is present as 1% by weight of the polyamic acid solution.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the modified thermal conversion process, the coated substrate 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 substrate is then cured for two preselected time intervals at two preselected temperatures, and the preselected time intervals may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated substrate is then cured at three preselected temperatures for three preselected time intervals, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated substrate is then cured for four preselected time intervals at four preselected temperatures, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated substrate is then cured at 5 preselected temperatures for 5 preselected time intervals, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated substrate is then cured for six preselected time intervals at six preselected temperatures, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated substrate is then cured at 7 preselected temperatures for 7 preselected time intervals, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated substrate is then cured at 8 preselected temperatures for 8 preselected time intervals, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated substrate is then cured at 9 preselected temperatures for 9 preselected time intervals, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked coated substrate is then cured at 10 preselected temperatures for 10 preselected time intervals, each of which may be the same or different.

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

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is between 2 and 60 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is between 2 minutes and 90 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is between 2 minutes and 120 minutes.

In some embodiments of the modified thermal conversion process, a method of making a polyimide film comprises coating a substrate with a polyamic acid solution comprising a conversion chemical; Soft baking the coated substrate; By sequentially including the step of treating the soft baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, the polyimide film exhibits satisfactory properties for use in electronic devices such as those disclosed herein. .

In some embodiments of the modified thermal conversion process, a method of making a polyimide film comprises coating a substrate with a polyamic acid solution comprising a conversion chemical; Soft baking the coated substrate; By sequentially treating the soft baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, the polyimide film exhibits satisfactory properties for use in electronic devices such as those disclosed herein. .

In some embodiments of the modified thermal conversion process, a method of making a polyimide film essentially comprises the steps of: coating a substrate with a polyamic acid solution comprising the conversion chemical; Soft baking the coated substrate; By sequentially treating the soft baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, the polyimide film exhibits satisfactory properties for use in electronic devices such as those disclosed herein. .

5. Electronic device

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, and the like. The specific material property requirements for each application are unique and can be addressed by the composition(s) and process condition(s) appropriate for the polyimide film disclosed herein.

In some embodiments, the flexible glass substitute in the electronic device is a polyimide film having repeating units of Formula V as detailed above.

An organic electronic device that may have advantages by having one or more layers containing at least one compound as described herein is (1) a device that converts electrical energy into radiation (e.g., a light emitting diode, a light emitting diode display, a lighting device) , Lighting fixtures, or diode lasers); (2) devices that detect signals through electronic processes (eg, photodetectors, photoconductive cells, photoresistors, optical switches, phototransistors, optical tubes, IR detectors, biosensors); (3) devices that convert radiation into electrical energy (eg, photovoltaic devices or solar cells); (4) a device that converts light of one wavelength into light of a longer wavelength (eg, a downconverting phosphorescent device); And (5) devices (eg, transistors or diodes) including one or more electronic components including one or more organic semiconductor layers. Other uses of the composition according to the present invention include coating materials for memory storage devices, antistatic membranes, biosensors, electrochromic devices, solid electrolyte capacitors, energy storage devices such as rechargeable batteries, and electromagnetic shielding articles.

An example of a polyimide film that can serve as a flexible glass substitute as described herein is shown in FIG. 1. The flexible film 100 may have properties as described in the embodiments of the present invention. In some embodiments, a polyimide film capable of acting as a flexible glass substitute is included in the electronic device. 2 illustrates a case where the electronic device 200 is an organic electronic device. The device 200 has a substrate 100, an anode layer 110 and a second electrical contact layer, a cathode layer 130, and a photoactive layer 120 therebetween. 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) including a hole transport material. Adjacent to the cathode, there may be an electron transport layer (not shown) including an electron transport material. Optionally, the device includes one or more additional hole injection layers or hole transport layers (not shown) next to the anode 110, and/or one or more additional electron injection layers or electron transport layers (not shown) next to the cathode 130. Can be used. The layers between 110 and 130 individually and collectively are referred to as the organic active layer. Additional layers that may or may not be present include color filters, touch panels, and/or cover sheets. In addition to the substrate 100, one or more of these layers may also be made of the polyimide film disclosed herein.

Different layers are further discussed herein with reference to FIG. 2. However, the discussion also applies to other configurations.

In some embodiments, the different layers have the following thickness range: substrate 100, 5-100 microns; Anode 110, 500-5000 Å (1000-2000 Å in some embodiments); Hole injection layer (not shown), 50-2000 Å (200-1000 Å in some embodiments); Hole transport layer (not shown), 50-3000 Å (200-2000 Å in some embodiments); Photoactive layer 120, 10-2000 Å (100-1000 Å in some embodiments); Electron transport layer (not shown), 50-2000 Å (100-1000 Å in some embodiments); Cathode 130, 200-10000 Å (300-5000 Å in some embodiments). The preferred ratio of layer thickness will depend on the exact nature of the material used.

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

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

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

The optional hole injection layer may include a hole injection material. The term "hole injection layer" or "hole injection material" refers to an electrically conductive or semiconducting material, and one or more functions (planarization of the lower layer, charge transport and/or charge injection properties, oxygen or metal ions, etc.) Removal of impurities of the organic electronic device, and other aspects for promoting or improving the performance of the organic electronic device, but is not limited thereto. The hole injection material may be a polymer, oligomer, or small molecule, and may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture, or other composition.

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

Another layer may include a hole transport material. Examples of hole transport materials for the hole transport layer are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang]. Both hole transporting small molecules and polymers can be used. Commonly used hole transport molecules are 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, but are not limited thereto. 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 a hole transport polymer by doping a polymer such as polystyrene and polycarbonate with hole transport molecules such as those mentioned above. In some cases, triarylamine polymers, especially triarylamine-fluorene copolymers are used. In some cases, the polymer and copolymer are crosslinkable. Examples of crosslinkable hole transport polymers can be found in, for example, US published patent application 2005-0184287 and PCT published application WO 2005/052027. In some embodiments, the hole transport layer is doped with a p-dopant 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 is a light-emitting layer that is activated by an applied voltage (as in a light-emitting diode or a light-emitting electrochemical cell), and absorbs light (as in a down-converting phosphorescent device) to provide longer wavelength light. It may be a layer of material that emits a light source, 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 includes a compound comprising a light emitting compound having a photoactive material. In some embodiments, the photoactive layer further comprises a host material. Examples of host materials include chrysene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, carbazole, indolocarbazole, furan, benzofuran, dibenzofuran. , Benzodifuran, and metal quinolinate complexes, but are not limited thereto. In some embodiments, the host material is deuterated.

In some embodiments, the photoactive layer includes (a) a dopant capable of electroluminescence having a maximum emission value from 380 nm to 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) a dopant capable of electroluminescence having a maximum emission value from 380 nm to 750 nm, (b) a first host compound, and (c) a second host compound, and There are no additional substances that substantially alter the principle of operation or distinguishing characteristics.

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

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

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

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

In some embodiments, the photoactive layer comprises (a) a green emissive 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 not only facilitates electron transport, but can also function to serve as a confinement layer preventing quench of excitons at the layer interface. Preferably, this layer promotes electron mobility and reduces exciton quench.

In some embodiments, these layers include other electron transport materials. Examples of electron transport materials that can be used in the selective electron transport layer are tris(8-hydroxyquinolato)aluminum (AlQ), bis(2-methyl-8-quinolinolato)(p-phenylphenolato)aluminum. Metal chelate oxy, including metal quinolate derivatives such as (BAlq), tetrakis-(8-hydroxyquinolato)hafnium (HfQ), and tetrakis-(8-hydroxyquinolato)zirconium (ZrQ) Noid compounds; 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD), 3-(4-biphenylyl)-4-phenyl-5- Azole compounds such as (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); Triazine; Fullerene; And mixtures thereof. In some embodiments, the electron transport material is selected from the group consisting of metal quinolate and phenanthroline derivatives. In some embodiments, the electron transport layer further comprises an n-dopant. N-dopant materials are well known. N-dopants are 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 (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido-[1,2-a] -Pyrimidine) and cobaltocene, tetrathianapthacene, bis(ethylenedithio)tetrathiafulvalene, heterocyclic radical or diradical, and heterocyclic radical or diradical dimer, oligomer, polymer, dispyro Compounds and polycycles, but are not limited thereto.

An optional electron injection layer may 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 . Does not. These layers can react with the lower electron transport layer, the upper cathode, or both. When the electron injection layer is present, the amount of the deposited material is generally in the range of 1 to 100 Å, and in some embodiments, 1 to 10 Å.

The cathode 130 is a particularly efficient electrode for injecting electron or negative charge carriers. The cathode can be any metal or non-metal with a lower work function than the anode. The material for the cathode may be selected from Group 1 alkali metals (eg Li, Cs), Group 2 metals (alkaline earth metals), rare earth elements and Group 12 metals including lanthanide elements, and actinium group 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 different layers. For example, between the anode 110 and the hole injection layer (not shown), there may be a layer (not shown) that controls the injection amount of positive charge and/or provides band gap matching of the layer, or functions as a protective layer. have. Layers known in the art such as copper phthalocyanine, silicon oxynitride, fluorocarbon, silane, or ultra-thin layers of metals such as Pt may be used. Alternatively, some or all of the anode layer 110, the active layer 120, or the cathode layer 130 may be surface-treated to increase charge carrier transport efficiency. The choice of material for each component layer is preferably determined by balancing the positive and negative charges in the emitter layer to provide a device with high electroluminescent efficiency.

It is understood that each functional layer may be composed of two or more layers.

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

In the case of a liquid deposition method, a suitable solvent for a specific compound or a related kind of compound can be readily determined by a person skilled in the art. For some applications, it is preferred that the compound is 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 relative to C ₁ to C ₁₂ alkanes, or aromatics such as toluene, xylene, and trifluorotoluene. Can be non-polar. Other liquids suitable for use in preparing liquid compositions comprising the novel compounds as solutions or dispersions described herein are chlorinated hydrocarbons (e.g. methylene chloride, chloroform, chlorobenzene), aromatic hydrocarbons (e.g., trifluorotoluene, etc.). Substituted and unsubstituted toluene and xylene), polar solvents (e.g. tetrahydrofuran (THP), N-methyl pyrrolidone), esters (e.g. ethyl acetate), alcohols (isopropanol), ketones (cyclopentanone), And mixtures thereof, but are not limited thereto. Suitable solvents for electroluminescent materials are described, for example, in PCT published application 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 vapor deposition of an anode, an electron transport layer, an electron injection layer, and a cathode.

It is understood that the efficiency of the device can be improved by optimizing the different layers of the device. For example, more efficient cathodes such as Ca, Ba or LiF can be used. New hole transport materials and molded substrates that reduce the operating voltage or increase quantum efficiency are also applicable. Additional layers may 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: a substrate, an anode, a hole injection layer, a hole transport layer, a photoactive layer, an electron transport layer, an electron injection layer, a cathode.

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

Example

The concepts described herein are further illustrated in the following examples, but this does not limit the scope of the invention described in the claims.

Synthesis Example 1

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

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

In a 1 L three-necked flask equipped with a magnetic stir bar, 2,5-difluoroaniline (152.3 g) was dissolved in 500 ml of dichloromethane and then acetic anhydride (134.5 g) was added, and the internal temperature during the addition Was kept below 14° C. and the mixture was cooled with an ice/water bath. The product was filtered, washed with hexane and dried in vacuo. The filtrate was evaporated to a volume of about 200 ml, diluted with hexane, and an additional amount of product was collected by filtration. A total of 479.4 g of 2,5-difluoroaniline was used to react three times in a row. Combined yield of N-(2,5-difluorophenyl)-acetamide 1 : 572.4 g (90.4%). ¹ H-NMR (acetone-d ₆ , 500 MHz): 2.19 (s, 3H), 6.81-6.86 (m, 1H), 7.16-7.20 (m, 1H), 8.15-8.19 (m, 1H), 9.10 ( br.s, 1H).

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

To a stirred suspension of N-(2,5-difluorophenyl)-acetamide 1 (235 g) in acetic acid (30 ml) and concentrated sulfuric acid (350 ml) in a three neck 1 L flask, nitric acid (120 ml) and concentrated A mixture of sulfuric acid (120 ml) was added dropwise while maintaining the internal temperature at 12 to 13°C. After the addition was complete (about 2 hours), the reaction mixture was stirred with a water bath for 3 hours. The reaction mixture was poured onto ice, and the precipitate was collected by filtration and washed with water. A total of 572.3 g of N-(2,5-difluorophenyl)-acetamide was used to react three times in a row. The combined yield of 716.5 g of crude N-(2,5-difluoro-4-nitrophenyl)-acetamide 2 was used in the next step without further purification. ¹ H-NMR (acetone-d ₆ , 500 MHz): 2.27 (s, 3H), 8.01-8.04 (m, 1H), 8.51-8.55 (m, 1H), 9.74 (br. s, 1H).

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

About 358 g of crude (2,5-difluoro-4-nitrophenyl)-acetamide 2 was added little by little while stirring using a mechanical stirrer to a 3-neck 1 L flask containing 450 ml of concentrated sulfuric acid. The mixture was heated to 95-100[deg.] C. over about 45 minutes and held in the range of 95-100[deg.] C. for 10 minutes. The mixture was cooled with an ice bath, poured onto ice, filtered, and the precipitate was washed with water (twice). A total of 716.5 g of N-(2,5-difluorophenyl)-acetamide 2 was used to react twice in succession. Combined yield of crude 2,5-difluoro-4-nitro-benzeneamine 3: 477 g (83%). ¹ H-NMR (acetone-d ₆ , 500 MHz): 6.88 (br. s, 2H), 6.72-6.76 (m, 1H), 7.82-7.86 (m, 1H).

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

Starting material 2,5-difluoro-4-nitro-benzeneamine 3 (100 g) once in a solution of tin chloride dihydrate (520 g) in methanol (400 ml) containing concentrated hydrochloric acid (35 ml) Was added to. Thereafter, the reaction mixture was heated to about 34-40° C. with a heating mantle. An exothermic reaction was made to reach a constant reflux with occasional application of an ice/water bath. After about 20 minutes of exothermic reaction, the mixture was heated at 59° C. for 30 minutes and left at room temperature overnight. The reaction mixture was filtered and washed with methanol to obtain a hydrochloride salt of the desired diamine. The reaction was repeated 4 times in a row using a total of 418 g of 2,5-difluoro-4-nitro-benzeneamine 3 . The combined hydrochloride salt was suspended in 700 ml of water and neutralized with 50% aqueous sodium hydroxide solution. The mixture was diluted with 1.5 L of water and sodium hydroxide until the initially formed precipitate dissolved. The mixture was extracted with ethyl acetate (4 times). The combined ethyl acetate extract was passed through a filter filled with silica gel eluting with ethyl acetate. Ethyl acetate was distilled off to a minimum volume using a rotary evaporator and treated with hexane. The precipitated product was collected by filtration and dried in vacuo to give 167 g of product. The initial filtrate of the reduction step was hydrolyzed with 50% aqueous sodium hydroxide solution, extracted with ethyl acetate (twice), ethyl acetate was distilled to a minimum volume, treated with hexane, and the precipitate was collected by filtration and dried. To give an additional amount of crude product (94.5 g). Total yield of crude product: 254.5 g (74%). The crude product was sublimed little by little in a vacuum at 150° C. to obtain 245.5 g of 2,5-difluoro-1,4-benzenediamine, compound IV-A. Sublimation can be repeated until a product of the desired purity is obtained. ¹ H-NMR (acetone-d ₆ , 500 MHz): 4.41 (br. s, 4H), 6.47 (t, 2H, J = 10 Hz).

Synthesis Example 2

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

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

To a stirred solution of tin chloride dihydrate (200 g) and concentrated hydrochloric acid (30 ml) in methanol (500 ml) was added 2,4-difluoro-5-nitro-benzeneamine (25 g) at once, The reaction mixture was cooled with an ice bath. The mixture was then heated at 70° C. for 30 minutes. The reaction mixture was cooled, quenched with 50% aqueous sodium hydroxide solution, filtered, and the solid was washed with methanol. After evaporation of methanol, the residue was extracted with acetone, and filtered through a filter filled with silica gel eluting with acetone. After evaporation of acetone, the residue was dissolved in a dichloromethane-acetone mixture and passed again through a plug of silica gel eluting with acetone. Acetone was distilled off, and the residue was sublimated in a vacuum glove box at 180° C. to obtain 9.5 g of a product. The product was sublimed again twice more to give 8.1 g of purified 4,6-difluoro-1,3-benzenediamine, compound IV-E. ¹ H-NMR (acetone-d ₆ , 500 MHz): 4.63 (br. s, 4H), 6.15 (t, 1H, J = 9 Hz), 6.77 (t, 1H, J = 11 Hz).

Synthesis Example 3

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

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

In a nitrogen atmosphere, a 1 L three necked round bottom flask was charged with 500 ml of 1 M LDA in tetrahydrofuran/hexane and cooled to about -68° C. using a dry ice/acetone bath. Thereafter, a solution of 2,3-difluorobenzoic acid in 75 ml of anhydrous tetrahydrofuran was added dropwise through a syringe while maintaining the internal temperature below -60°C and stirring with a mechanical stirrer. The resulting suspension was stirred at -78°C for 1.5 hours, poured little by little on dry ice, and allowed to reach room temperature over 2 hours. The solvent was distilled off, and the residue was suspended in water, followed by acidification with concentrated hydrochloric acid. The precipitated product was collected by filtration, washed with water and dried in vacuo to give 32 g of crude product, which was dissolved in acetone (ca. 500 ml). Acetone was distilled off using a rotary evaporator, and the precipitated product was collected by filtration and dried in vacuo to give about 16 g of product. Acetone was evaporated to a minimum and the residue was diluted with toluene to form an additional amount of precipitate (2.2 g). ¹ H-NMR (acetone-d ₆ , 500 MHz): 7.83-7.84 (m, 2H), 12.08 (br.s, 2H).

(b) 3,4-difluoro-1,4-benzenediamine (Compound IV-C) .

The above crude 2,3-difluoro-1,4-benzenedicarboxylic acid (8 g), tert-butanol (100 ml), toluene (400 ml), diphenylphosphoryl azide (27.23 g), and triphenyl A mixture of ethylamine (100 g) was stirred at room temperature for 1 hour, then slowly heated from 50° C. to 100° C. over about 1.7 hours, and further heated at 100° C. for 3 hours. The reaction was repeated again using 17 g of crude 2,3-difluoro-1,4-benzenedicarboxylic acid, 57.87 g of diphenylphosphoryl azide. The combined reaction mixture was washed with water (twice), the toluene layer was separated, passed through a short silica gel plug, and celite was washed with toluene. Toluene was distilled off to a volume of about 200 ml using a rotary evaporator, and the intermediate BOC-protected compound was filtered by a filter ( ¹ H-NMR: dmso-d ₆ , 500 MHz: 500 MHz: 1.44 (s, 18 H ), 7.22-7.23 (m, 2H), 9.06 (s, 2H)), 300 ml of toluene and 30 ml of concentrated hydrochloric acid were heated at 90° C. for 3 days. The toluene layer was separated, and the aqueous layer was diluted with 200 ml of water. The aqueous layer was extracted with ethyl acetate, and the extract was passed through a short silica gel plug. Ethyl acetate was distilled off using a rotary evaporator to obtain a crude product (8.14 g), which was sublimated in vacuo and then crystallized from an ethyl acetate-cyclohexane mixture to 6 g of purified 3,4-difluoro-1, 4-benzenediamine, compound IV-C was obtained. ¹ H-NMR (dmso-d ₆ , 500 MHz): 4.46 (s, 4H), 6.27-6.39 (m, 2H). ¹⁹ F-NMR (dmso-d ₆ , 500 MHz): 159.9.

Polymer Example 1

This example illustrates the use of compound IV-A as diamine to form polyamic acid.

2,5-difluoro-1,4-benzenediamine (6 g), 3,3',4,4'-biphenyltetracarbocyclic dianhydride (12.19 g, 0.995 eq), N-methylpyrroly Don (103.4 g) was stirred for 2 weeks under a nitrogen atmosphere to obtain a polymer solution having a viscosity of 3358 cps. GPC: Mn = 61889, Mw = 143777, Mp = 139220, Mz = 232140, PDI = 2.33.

Polymer Example 2

This example illustrates the use of Compound IV-E as one of two diamines to form a polyamic acid.

Using DMAc as a solvent, the monomer was reacted as described above to form a polymer solution. The ratio of Bis-P to compound IV-E was 90:10. GPC: Mn = 61759; Mw = 215,962.

Polymer Example 3

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

The polyamic acid solution obtained in Polymer Example 2 was filtered through a microfilter, spin-coated on a clean silicon wafer, soft baked at 90°C on a hot plate, and placed in a furnace. The furnace was purged with nitrogen and heated stepwise to a maximum curing temperature of 260°C. The wafer was removed from the furnace, immersed in water, and manually peeled to obtain a polyimide film sample. The film properties are as follows.

thickness: 9.78 μm

T _g : 260℃

CTE (first scan) 53.1 ppm/℃

CTE (second scan) 59.1 ppm/℃

Optical phase delay 15

b* 2.48

YI 4.25

CTE was measured in the range of 50-250°C.

As can be seen from the above examples, the fluorinated diamine compounds having Formulas II and III are sufficiently reactive in atmospheric conditions to produce a polymer having a molecular weight greater than 100,000. They can be used to form polyimide films with desired properties.

For reference, not all of the above-described actions are required in the overall description or embodiments, some of the specific actions may not be required, and one or more additional actions may be performed in addition to those described. Also, the order of the listed actions is not necessarily the order in which the actions are performed.

In the foregoing specification, the concept has been described with reference to specific embodiments. However, those skilled in the art understand that various modifications and changes may be made without departing from the scope of the invention as set forth in the following claims. Accordingly, the specification and drawings are to be regarded as illustrative rather than in a limiting sense, and all such modifications are intended to be included within the scope of the invention.

Advantages, other advantages, and problem solutions have been described above with respect to specific implementations. However, advantages, advantages, problem solutions, and any feature(s) that may result in or make any advantage, advantage, or solution more clarified, are important, essential or essential features of any or all claims. It should not be interpreted as.

For the sake of clarity, it should be understood that certain features described herein in the context of separate embodiments may be provided in combination in a single embodiment. Conversely, for the sake of brevity, the various features described in the context of a single embodiment may be provided individually or in any subcombination. Use of the numerical ranges of the various ranges specified herein is indicated as an approximation, as if the word "about" precedes both the minimum and maximum values within the specified range. In this way, slight vertical deviations of the specified range can be used to achieve substantially the same results as values within the range. Further, the disclosure of these ranges is intended as a continuous range that includes all values between the minimum and maximum average values, including fractional values that may appear when some components of one value are mixed with components of another value. Further, where wider and narrower ranges are disclosed, fitting the minimum value of one range to the maximum value of another range and vice versa is within the spirit of the invention.

Claims (6)

A liquid composition having a solid content of 10 wt% or more and a viscosity of 3000 cps or more,
(a) polyamic acid having a repeating unit structure of formula I
[Formula I]

(In the formula,
R ^a is the same or different at each occurrence and represents one or more tetracarboxylic acid moieties;
R ^b is the same or different at each occurrence and represents one or more aromatic diamine moieties;
30-100 mol% of R ^b has Formula II or Formula III,

In the formula,
R ¹ and R ² are the same or different and are selected from the group consisting of F, R _f , and OR _f ;
R _f is C _1-3 perfluoroalkyl;
* Indicates the point of attachment;
R ¹ and R ² are both adjacent to the point of attachment) and;
(b) high boiling point aprotic solvent
Composition comprising a. The composition of claim 1, wherein R ^b represents a moiety from a diamine selected from the group consisting of compounds IV-A to IV-F.

The composition of claim 1, wherein R ^a represents at least two tetracarboxylic acid component residues, and the tetracarboxylic acid component is selected from the group consisting of BPDA, 6FDA, PMDA, and CBDA. As a polyimide film, the polyimide has a weight average molecular weight of 100,000 or more, and includes a repeating unit structure of formula (V),
[Formula V]

(In the formula,
R ^a is the same or different at each occurrence and represents one or more tetracarboxylic acid moieties;
R ^b is the same or different at each occurrence and represents one or more aromatic diamine moieties;
30-100 mol% of R ^b has Formula II or Formula III,

In the formula,
R ¹ and R ² are the same or different and are selected from the group consisting of F, R _f , and OR _f ;
R _f is C _1-3 perfluoroalkyl;
* Indicates the point of attachment;
Both R ¹ and R ² are adjacent to the point of attachment);
Also,
Coating a substrate with a polyamic acid solution comprising at least one tetracarboxylic acid component and at least one diamine component in a high boiling point aprotic solvent;
Soft baking the coated substrate;
A polyimide film prepared according to a method comprising the step of treating the soft baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals in sequence without repetition. The polyimide film of claim 4, wherein the preselected maximum temperature is 375°C. The polyimide film of claim 5, wherein the method is performed in an inert atmosphere.

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