KR20070017001A - Low Color Polyimide Compositions Useful in Optical Type Applications and Methods and Compositions Relating Thereto - Google Patents

Abstract

Polymer repeat units derived by contacting 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BDPA) and 2,2'-bis (trifluoromethyl) benzidine (TFMB) monomers are at least Perfluorinated polyimide (and copolyimide) compositions, in particular films, comprising 50 mole percent. The perfluorinated polyimide (and copolyimide) films of the present invention have an in-plane coefficient of thermal expansion (CTE) of -5 to +20 ppm / ° C (based on 75-micron thick films) and an average light transmittance of about 65.0 to About 99.0. Films of the present invention may provide desirable properties because they convert polyimides using chemical conversion methods instead of the thermal conversion processes typically employed. The film of the present invention is excellent as a substrate in an optical display device, and can be used in place of a rigid glass substrate. The polyimide film of the present invention may also be used to manufacture flexible display devices (eg, mobile phones, personal digital assistants, portable video game consoles, laptops, etc.).

3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BDPA), 2,2'-bis (trifluoromethyl) benzidine (TFMB) monomer, perfluorinated polyimide, light transmittance, chemical Switching method, optical display device.

Description

Low Color Polyimide Compositions Useful in Optical Type Applications and Methods and Compositions Relating Thereto}

The present invention generally relates to relatively transparent (low color) polyimide-based films having good light transmittance and low in-plane CTE (coefficient of thermal expansion). More specifically, the compositions of the present invention relate to perfluoronated polyimides useful in the field of glass type, in particular in the field of electronic displays.

U.S. Patent 5,071,997 discloses a class of polyimides useful in the field of low color films. However, these polyimides have a relatively high coefficient of thermal expansion (CTE), and a relatively low glass transition temperature (Tg), which is generally not a good choice as a substitute for high performance glass. U.S. Patent 5,071,997; 5,344,916 and 5,480,964 (and WO / 91-01340) describe polyimide classes derived from BPDA and TFMB monomers that are soluble in cresol solvents.

Summary of the Invention

The present invention is directed to perfluoropolyimide compositions that are transparent and useful in the field of low color. The composition of the present invention may be at least partially produced by contacting a first dianhydride component with a first diamine component to provide a polyimide product represented by the following formula.

In one embodiment, the polyimide product is a majority component (on a molar basis) of the filiamide film, wherein the in-plane coefficient of thermal expansion (CTE) of the polyimide film is in the range between any two of the following numbers Including: -5, -2, 0, 2, 5, 7, 10, 12, 15, 18 and 20 ppm / ℃, wherein the thickness of the film is about 5 to 200 microns, the average light transmittance The film is between and includes any of the following 65.0, 70.0, 75.0, 80.0, 85.0, 90.0, 95.0 and 99.0 when exposed to light of about 380-770 nanometers.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In one embodiment, "polymer repeats" derived from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BDPA) and 2,2'-bis (trifluoromethyl) benzidine (TFMB) monomers A new class of polyimide (and copolyimide) films are provided wherein the units are derived from at least 50 mole percent (in total polyimide). Such films have a coefficient of in-plane coefficient of thermal expansion (CTE) of -5 to +20 ppm / ° C and an average light transmittance of 65.0 to about 99.0 (when exposed to light in the wavelength range of about 380 to 770 nanometers). . The polymer repeating unit may be represented by the following formula.

The polyimide films of the present invention are typically synthesized by polycondensation reactions involving the reaction of diamines with dianhydride components. In general, polyimides can be prepared by combining the monomers with a solvent to form a polyamic acid solution (also called a polyamide solution or a polyimide precursor material). The dianhydride and diamine components typically combine a molar ratio of aromatic dianhydride component to aromatic diamine component of about 0.90 to 1.10, or about 0.98 to 1.02. The molecular weight can be controlled by controlling the molar ratio of dianhydride and diamine. As such, 'n' may be any number between 10 and 100,000, or a number within about 100 and 1000.

In one aspect of the invention, a polyamic acid solution (and / or polyamic acid molding solution) can be prepared in an organic solvent. The polyamic acid concentration is any selected from 5, 10, 12, 15, 20, 25, 27, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 weight percent It can be a range between two numbers (including two numbers).

Useful organic solvents for the synthesis of the polyimide of the present invention are preferably capable of dissolving the polyimide precursor material (eg monomer). Such solvents also have a relatively low boiling point, such as below 225 ° C., so that the polyimide can be dried at a suitable temperature (ie, more conveniently less expensive). Typically, boiling points below 210, 205, 200, 195, 190, or 180 ° C. are generally preferred. In general, the polyimide of the present invention is insoluble in cresol solvents or conventional organic solvents to be mentioned below. Low CTE (Coefficient of Thermal Expansion) films of the present invention are chemically converted from polyamic acid to polyimide before being used as a marketing part.

Solvents useful in preparing the polyimides of the present invention (ie, solvents useful for dissolving their polyamic acid precursors) can be used alone or in combination with other solvents (ie with cosolvents). Useful organic solvents include: N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), N, N'-dimethyl-formamide (DMF), dimethyl sulfoxide (DMSO), tetramethyl urea (TMU), N , N'-dimethyl-N, N'-propylene urea (DMPU), and gamma-butyrolactone. In one embodiment, preferred solvents include N-methylpyrrolidone (NMP) and dimethylacetamide (DMAc).

Cosolvents may also be used in about 5 to 50 weight percent of the total solvent. Useful cosolvents include xylene, toluene, benzene, diethylene glycol diethyl ether, 1,2-dimethoxyethane (monoglyme), diethylene glycol dimethyl ether (diglyme), 1,2-bis- (2-methoxy Ethoxy) ethane (triglyme), bis [2- (2-methoxyethoxy) ethyl)] ether (tetraglyme), bis- (2-methoxyethyl) ether, tetrahydrofuran, butyl cellosolve Butyl cellosolve acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

Dianehydride components contemplated as useful herein include at least 50 mole percent of 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA) of the total dianhydride component. The BPDA monomers can be used alone (ie, at a molar ratio of 100% of the total dianhydride component) or can be used with one or more of the other dianhydrides selected from the group disclosed herein. These additional dianhydrides, when used alone or in combination, cannot exceed 50 mole percent of the total dianhydride component. Additional dianhydrides include 4,4'-oxydiphthalic anhydride (ODPA); 4,4 '-(4,4'-isopropylidenediphenoxy) bis (phthalic anhydride) (BPADA); 2,3,3 ', 4'-biphenyl tetracarboxylic dianhydride; 2,2 ', 3,3'-biphenyl tetracarboxylic dianhydride; 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA); Diphenylsulfontetracarboxylic dianhydride (DSDA); 4,4'-bisphenol A dianhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride; (-)-[1S *, 5R *, 6S *]-3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3- (tetrahydrofuran-2,5-dione) [Ie, (-)-DAN, manufactured by JSR Corp., and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and cycloaliphatic dianhydride Can be selected from the group consisting of

Other useful dianhydrides include 9,9-disubstituted xanthenes. Non-limiting examples of these dianhydrides include 9,9-bis- (trifluoromethyl) xanthenetetracarboxylic dianhydride (6FCDA); 9-phenyl-9- (trifluoromethyl) xanthenetetracarboxylic dianhydride (3FCDA); 9,9-diphenyl-2,3,6,7-xanthatetetracarboxylic dianhydride (PPXDA); 9,9-diphenyl-2,3,6,7-tetramethylxanthene (TMPPX); 9,9-diphenyl-2,3,6,7-xanthenetetracarboxylic bis (p-anisidylimide); 9,9-diphenyl-2,3,6,7-xanthatetetracarboxylic bis (butylimide); 9,9-diphenyl-2,3,6,7-xanthenetetracarboxylic bis (p-tolylimide); 9-phenyl-9-methyl-2,3,6,7-xanthatetetracarboxylic dianhydride (MPXDA); 9-phenyl-9-methyl-2,3,6,7-xanthatetetracarboxylic bis (propylimide); 9-phenyl-9-methyl-2,3,6,7-xanthenetetracarboxylic bis (p-tolylimide); 9,9-dimethyl-2,3,6,7-xanthatetetracarboxylic dianhydride (MMXDA); 9,9-dimethyl-2,3,6,7-xanthenetetracarboxylic bis (propylimide); 9,9-dimethyl-2,3,6,7-xanthenetetracarboxylic bis (tolylimide); 9-ethyl-9-methyl-2,3,6,7-xanthatetetracarboxylic dianhydride (EMXDA); ); 9,9-diethyl-2,3,6,7-xanthatetetracarboxylic dianhydride (EEXDA); Et al. (See, eg, those described in Polyimides Based on 9,9-Disubstituted Xanthene Dianhydrides, Trofimenko and Auman, Macromolecules, 1994, vol. 27, p. 1136-1146). Include. Many (but not all) of the aforementioned dianhydrides are in 'tetraacid form' (or as mono, di, tri, or tetra esters of tetraacids), or their diester acid halides ( Chloride). However, in some embodiments of the present invention, dianhydride forms are preferred because they are generally more reactive than acids or esters.

Diamine components that are considered useful in the present invention include at least 50 mole percent of 2,2'-bis (trifluoromethyl) benzidine (TFMB). In addition, TFMB diamine monomers may be used alone (ie, at 100 mole percent of the molar ratio of the total diamine component) or in combination with one or more diamines in the groups listed herein. These additional diamines, when used alone or in combination, should not exceed 50 mole percent of the total diamine component. These diamines include trans-1,4-diaminocyclohexane (CHDA); Diaminocyclooctane; Tetramethylenediamine; Hexamethylenediamine; Octamethylenediamine; Dodecamethylene-diamine; Aminomethylcyclooctylmethanamine; Aminomethylcyclododecylmethanamine; Aminomethylcyclohexylmethanamine; 3,5-diaminobenzotrifluoride; 2- (trifluoromethyl) -1,4-phenylenediamine; 5- (trifluoromethyl) -1,3-phenylenediamine; 1,3-diamino-2,4,5,6-tetrafluorobenzene; 2,2-bis [4- (4-aminophenoxy) phenyl] -hexafluoropropane (BDAF); 2,2-bis (3-aminophenyl) 1,1,1,3,3,3-hexafluoropropane; 2,2'-bis- (4-aminophenyl) -hexafluoropropane (6F diamine); 3,4'-oxydianiline (3,4'-ODA), m-phenylene diamine (MPD), 4,4-bis (trifluoromethoxy) benzidine, 3,3'-diamino-5,5 '-Trifluoromethyl biphenyl, 3,3'-diamino-6,6'-trifluoromethyl biphenyl, 3,3'-bis (trifluoromethyl) benzidine; 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (4-BDAF), 4,4'-diaminodiphenyl sulfide (4,4'-DDS); 3,3'-diaminodiphenyl sulfone (3,3'-DDS); 4,4'-diaminodiphenyl sulfone; And 4,4'-trifluoromethyl-2,2'-diaminobiphenyl.

In an embodiment of the invention, the polyimide film generally has 50 mole% BPDA-TFMB (ie, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA) / in the backbone of the polyimide. / 2,2'-bis (trifluoromethyl) benzidine), and the polyimide film is characterized by a complete thermal conversion process (i.e., a completely thermal conversion method) only by heat to cure the polyimide from the polyamic acid precursor state. It is preferable to manufacture using a method other than). In one embodiment, the polyimide film is produced primarily by chemical conversion methods that are not all, but easy to moderate CTE, thereby preventing unreasonably high CTE as in thermal conversion.

In one embodiment, the film of the present invention is converted to polyimide by a polyimide chemical conversion method, wherein greater than 50 mole% BPDA-TFMB (3,3 ', 4,4'-biphenyl) in the polyimide backbone. Tetracarboxylic dianhydride (BPDA) // 2,2'-bis (trifluoromethyl) benzidine) reaction product. The film obtained will generally have a low CTE (ie less than about 20 ppm / ° C.) and good light transmittance (ie greater than about 65% based on 3-mil (75-micron) film).

As an embodiment of the invention, the dianhydride (or diamine) used to form the polyimide herein may optionally include reactive end group (s). Some of these reactive end groups may be nadic, acetylene, n-propargyl, cyclohexene, maleic, n-styrenyl, phenylethynyl. These reactive end groups can be used to form lower molecular weight polymers to help reduce the final CTE of the polyimide or to help crosslink the polymers to cap the ends of the polymers. Further crosslinking of the polymer can increase the Tg and mechanical modulus of the final polyimide. In some instances, when low molecular weight polymers (ie oligomers) are formed, the polymers can be crosslinked to a relatively high degree to form polyimides having exceptional resistance to attack of solvents.

Useful methods for forming polyimide films using chemical conversion methods (ie, methods according to the present invention) are described in US Pat. Nos. 5,166,308 and 5,298,331, which have the effect of being incorporated herein by reference and all of which are taught herein. It can be found in the arc.

The polyimide of the present invention can be prepared using a variety of different methods of how the components (ie, monomer and solvent) are introduced into each other. Various methods of preparing polyamic acid solutions include the following:

(a) A method in which the diamine component and the dianhydride component are preliminarily mixed with each other and then the mixture is added in portions to the solvent with stirring.

(b) A method of adding a solvent (unlike the method of (a) above) to a stirring mixture of diamine and dianhydride components.

(c) a method in which the diamine is exclusively dissolved in a solvent, and then the dianhydride component is added at a rate capable of controlling the reaction rate.

(d) A method in which the dianhydride component is exclusively dissolved in a solvent, and then the amine component is added in a ratio capable of controlling the reaction rate.

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

(f) reacting with each other in the reactor in such a way as to preliminarily form a polyamic acid with excess amine component and another polyamic acid with excess dianhydride component and then produce a particularly random or block copolymer. How to let.

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

(h) A method in which the components can be added in part or in part to all or part of the solvent in any order, and also any part or part of any of the components as part or all of the solvent as a solution.

(i) first reacting one of the dianhydride components with one of the diamine components to obtain a first polyamic acid, and then reacting the other dianhydride component with another amine component to obtain a second polyamic acid, A method of combining the polyamic acid by employing any of a variety of methods prior to film formation.

Generally speaking, the polyamic acid molding solution can be derived from any of the polyamic acid solution preparation methods disclosed above.

The polyamic acid molding solution of the present invention can be combined with a certain amount of the conversion compound. Non-limiting examples of conversion compounds deemed useful in the present invention include (i) at least one dehydrating agent such as aliphatic acid anhydrides (acetic anhydrides, etc.) and aromatic acid anhydrides; And (ii) one or more catalysts such as aliphatic quaternary amines (triethylamine, etc.), aromatic quaternary amines (dimethylaniline, etc.) and heterocyclic quaternary amines (pyridine, picoline, isoquinoline, etc.). . Anhydride dehydration materials are typically used in moles in excess of the amount of amide acid groups present in the polyamic acid solution. The amount of acetic anhydride used is typically about 2.0-3.0 mmol, per equivalent of polyamic acid. Generally, a significant amount of quaternary amine catalyst is used. Surprisingly, when chemical conversion methods are used herein (ie, instead of more conventional thermal methods), (i) in-plane CTE, (ii) glass transition temperatures are more preferred than films converted using thermal methods having the same composition. And (iii) a film having a light transmittance coefficient. The examples, comparative examples and data tables disclosed herein explain this phenomenon in detail.

As used herein, the term “thermal conversion method” refers to a solvent film that does not use a conversion compound (ie, a chemical catalyst) for converting a polyamic acid molding solution into a polyimide (ie, only uses thermal energy to heat the film thereby). To dry and carry out the imidization reaction.

The polyamic acid solution (and / or molding solution) of the present invention may optionally further comprise any one or more of a number of additives. Such additives include processing aids (eg oligomers), antioxidants, light stabilizers, light extinction coefficient modifiers, flame retardant additives, antistatic agents, heat stabilizers, ultraviolet absorbers, inorganic fillers or various reinforcing agents.

According to the present invention, additional monomers may be used to form polyimide films, and these may be specifically selected to impart important physical properties to the film. Commonly desired advantageous properties include, but are not limited to, high or low modulus, good mechanical elongation, low in-plane thermal flatness coefficient (CTE), low wet expansion coefficient (CHE), and special glass transition temperature (Tg).

In general, the solvated mixture (ie, polyamic acid molding solution comprising the above-mentioned conversion compound) is molded or applied onto a support (such as an endless belt or a rotating drum) to obtain a film. Next, the solvent-containing film (gel film) can be cured (ie chemically cured) at a suitable temperature to be converted to a self-supporting polyimide film to produce a dry film. The film can then be separated from the support prior to complete drying and molecularly oriented with further curing via a tenting oven. For the purposes of the present invention, a cured polyimide film means a polyimide in which at least 90, 92, 94, 96, 98, 99 or 99.9 percent of the amic-acid residues are converted to amide residues. As used herein, a dry film defines a film in which the amount of volatiles (eg, solvent) remaining in the polyimide film composite is less than 2, 1.5, 1.0, 0.5, 0.1, 0.05, and 0.01 weight percent.

In one embodiment of the invention, the thickness is 5, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 A polyimide film is made that is between any two values selected from among 75, 80, 85, 90, 95, 100, 125, 150, 175 and 200 microns (including both values).

In one embodiment of the present invention, a polyimide film having a glass transition temperature (Tg) in a specific range is made. The glass transition temperature value of the polyimide film of the present invention is measured using a TA Instruments 2980 dynamic mechanical analyzer. Tg measurement used a collection frequency of about 1.0 Hz (wavelength of about 10.0 μm) and a preload weight of about 0.01 N. A rate of temperature rise of about 5 ° C. min ⁻¹ was used. Tg was measured as the peak of tan δ response. Found that the glass transition temperature of the film of the present invention is between any two values (including two values) selected among 250, 275, 300, 325, 350, 375, 400, 425, 450, 475 and 500 ° C It was.

In one embodiment of the present invention, a polyimide film having a specific range of in-plane coefficient of thermal expansion (CTE) can be made. In-plane CTE of the polyimide film of the present invention was measured using a TA Instruments TMA 2940 thermal mechanical analyzer. The swelling degree of the film was measured at about 50 ° C. to about 250 ° C. on the second pass. The degree of expansion was then divided by the temperature difference (and sample length) to give a CTE in ppm ° C- ¹ units. The first pass is used to remove shrinkage from the sample over the same temperature range and to dry the sample (from absorbed water). This provides a CTE value (which eliminates water absorption and the effect that water can have on the CTE of the film), which is the inherent property of the film on the next pass. This method employs 0.05 N loading force and operates at an elevated temperature of about 10 ° C. min ⁻¹ within the above-mentioned temperature range. The in-plane CTE values of the polyimide films useful in the present invention are between any two values selected from -5, 0, 2, 4, 6, 8, 10, 12, 14, 16, 18 and 20 ppm / ° C. Inclusive).

As one embodiment, the polyimide film of the present invention may be suitable as an alternative to glass in electronic display devices under the conditions that the polyimide has suitable light transmitting properties. The poly of the present invention over a range of from about 380 nanometers to about 770 nanometers (including two values) (at intervals of about 2 nanometers using a Hewlett Packard 8452A Spectrophotometer) The light transmittance of the mid film was measured. The average light transmittance used in the polyimide of the present invention is between any two values selected from 65.0, 70.0, 75.0, 80.0, 85.0, 90.0, 95.0 and 99.0 when the film is exposed to light with a wavelength of 380-770 nanometers. It was found to be light transmissive.

In one embodiment of the present invention, the polyimide film disclosed herein may be used as one component in liquid crystal displays (LCDs). In general, liquid crystal display (LCD) devices require very low power consumption. These devices may also require a lightweight (flat) structure with respect to the screen surface. These properties allow LCDs to be used in display devices such as wristwatches, portable calculators and personal computers, PDAs, airplane dashboard displays, and many other fields.

In its simplest form, a liquid crystal display device typically consists of a liquid crystal layer having two opposing faces, an electrode set on one of the faces of the liquid crystal layer and an alignment layer between each set of electrodes and liquid crystal layers. Electrodes comprising an alignment layer are typically supported by a substrate made of glass or plastic. The alignment of the liquid crystal molecules occurs at a certain angle with respect to the surface of the two substrates inside (eg, glass plate, glass sheet, quartz plate or other alignment layer supporting the electrode) (surface tilt angle or simply referred to as 'tilt angle'). being). The alignment layer (ie, these substrates) may have a coating (sets of transparent electrodes or electrical conductors) typically made of indium-tin oxide (ITO). These electrode sets can be patterned to match the information displayed by the LCD (eg by etching). Displays using the TN or STN effect typically use electrodes on opposite sides of the liquid crystal layer to obtain primarily vertical electric fields that may be required to switch the liquid crystals while changing the display mode. This TN effect can be widely used in so-called "active matrix TN displays", ie displays which feature electronically active switching elements (eg TFTs or diodes) within each pixel. TN-displays are already widely used, for example, in monitors for desktop computers.

Another display mode in the LCD may be in-plane switching (IPS) mode. Here, the electrodes of one pixel are on the same side of the liquid crystal layer, and switching is obtained by essentially a horizontal electric field (ie an electric field which can be essentially parallel to the liquid crystal layer). IPS displays are often mentioned in terms of a matrix of active elements (typically TFTs).

In one embodiment of the present invention, the disclosed polyimide can be used as an alignment layer of a display device. By applying the polymer onto a substrate (eg glass or silicon) via a solution-forming step (eg spin coating, roller coating, dipping, spraying, printing and / or doctor blading), the organic base (eg For example, the process of establishing a polyimide) alignment layer can be easily performed. After removal of the solvent and / or curing of the polymer, the polymer substrate can be established in one direction of optical direction by rubbing or rubbing the polymer substrate in one direction with a cloth. In some aspects, it may have a barrier passivation layer on the opposite side of the substrate. After the substrate is empty, it can be rotated from 0 to 360 degrees relative to the other polymer substrate. In other cases, organic adhesives may be used to attach these layers to other layers. Often, spacers are used to maintain a constant thickness gap between the substrates. In other cases, these substrates may be filled with various mixtures of liquid crystal materials. In addition, the deflection film and / or compensation film may be attached to the outer surface of the substrate by a lamination method. Finally, electrical connections can be made to both substrates in a manner consistent with electrical and display designs. Currently, rubbed polymer films (ie alignment direction and tilt angle control films) are predominantly used in known process techniques used in the production of all classes of liquid crystal displays. For this reason, a polyimide base film can be used as a flexible, low cost, reliable alignment film.

In another embodiment of the present invention, the polyimide film disclosed herein may be used as one component in organic electronic devices having organic light emitting diodes (OLEDs). Organic electronic devices play an important role in the industry. For example, organic light emitting diodes (OLEDs) are promising because of their high power conversion efficiency and relatively low processing cost. Such displays are particularly promising for battery charging, portable electronic devices, including cell phones, personal digital assistants (PDAs), portable computers, and DVD players. These fields require displays with high information content, full color, high speed, and video response time with low power consumption.

As used herein, the term "organic electronic device" or sometimes "electronic device" means a device comprising one or more semiconductor layers or materials. Non-limiting examples of organic electronic devices include (1) devices that convert electrical energy into radiation (for example, light emitting diodes, light emitting diode displays, diode lasers, or light emitting panels), and (2) signals using electrotechnical processes. (Eg) photodetectors, photoconductive cells, photoresistors, optical switches, phototransistors, optical tubes, infrared (IR) detectors, or biosensors), (3) devices that convert radiation into electrical energy (Eg, photovoltaic device or solar cell), (4) a component device (eg transistor or diode) comprising one or more electronic components comprising one or more organic semiconductor layers or item (1) And any combination of the devices of (4).

OLEDs typically include an organic field-emitting (EL) material layer between the anode and the cathode. Like other organic electronic devices, OLEDs may include active materials such as buffer layers and charge transport layers. The EL material may be a small molecular material, such as fluorescent dyes and organometallic complexes, or may be a larger molecular material, such as conjugated polymers and oligomers. Each EL or active material layer contributes to the overall performance of the display.

The layers constituting the OLED device are generally formed on a substrate. The term "substrate" means a base material that can be rigid or flexible and can include one or more layers made of one or more materials. Non-limiting examples of these materials include glass, polymer, metal or ceramic materials or combinations thereof. The substrate may or may not include electronic components, circuits, or conductive members.

Polymer films used for such applications typically require high thermal stability while maintaining colorlessness. Occasionally, the display device may be designed to support full color in the transmitted or reflected spectrum. Therefore, the low color properties of these polymer films are essential. In addition, new flexible display applications require flexible thin film transistor (TFT) backplanes. Therefore, conventional glass substrates (used on the TFT backside) must be replaced with flexible, transparent organic films. A common problem when using polymer films in these applications is that amorphous silicon thin film transistors (on glass in the display field) are typically processed at 300 ° C to 350 ° C. Such processing temperatures are generally too high for many plastics, including poly (ethylene terephthalate) and poly (ethylene naphthalate) (typically plastics having Tg of 70 ° C.-100 ° C. and about 120 ° C., respectively). In addition, to suppress leakage (loss of current which may make it impossible to store data on the pixel capacitor over display time) and to increase the flow of the TFT, higher processing temperatures (about 250 ° C to 275 ° C) Range) may be required. Low flow rates can typically limit the brightness of an OLED. As such, the colorless polyimide film may be an ideal substrate (ie, a material with Tg ≧ 280 ° C.). The same can be applied to the manufacture of LCD displays in that the temperature for processing the active TFT type can range from about 250 ° C to 275 ° C.

In many optoelectronic devices, transparent conductors are an essential component. Non-limiting examples of these devices include displays, touch screens, and photovoltaic devices (eg, solar cells). In these devices, indium tin oxide (ITO) can be used as a conductor. Film composites comprising conductive polymers, optionally carbon nanotubes, as an electrically conductive medium can be used as substitutes for metal oxides. As such, these types of film composites may be suitable for use in flexible displays. Zinc oxide and doped zinc oxide films can be used as replacements for ITO films because zinc oxide is generally nontoxic and inexpensive. Finally, the film of the present invention can be used as a transparent protective filter of a camera.

EXAMPLE

The advantages of the present invention are illustrated in the following non-limiting examples. The processing and testing procedures used in the preparation and testing of the polyimide film are described below. In each of the Examples and Comparative Examples, about 75 microns (~ 3.0 mils) thick. If a sample of thickness 25-micron is prepared, according to the present invention, the light transmittance may exceed 90.0. The polyamic acid precursor material (precursor for making the polyimide film) is equilibrated to obtain the final viscosity.

The other film properties of the films of the invention and the properties of the corresponding precursor materials were measured as follows. The solution viscosity of the polyamic acid of the present invention was measured with a Brookfield HADV-II + Viscometer equipped with a # 5 spindle operating at a speed of about 20 rpm. Young's modulus, tensile strength, and film elongation were measured using an Instron Model 1122 Series IX Automated Materials Testing System version 8.10.00. The crosshead speed was set to about 1.0 inch / min using a 100.0 lbf load cell. The dimensions of the polyimide film were about 3.0 mil (about 150 microns) thick 0.5 "(about 12.7 mm) thick for each test strip. The apparatus used a 1.0" jaw opening. Test conditions were performed at about 73 ° C. and about 50% relative humidity.

Example 1

38.43 g (0.12 moles) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 334 milliliters of N, N into a dried 500 milliliter three-neck round bottom flask equipped with nitrogen inlet, mechanical stirrer and thermometer Dimethylacetamide (DMAc) was added.

The mixture was heated and stirred at 45 ° C. for several minutes to completely dissolve the diamine to give a pale yellow solution. Next, 26.47 g (0.09 moles) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 13.326 (0.03 moles) of 4,4'-(hexafluoroisopropyl) Liden) diphthalic anhydride (6FDA) was added to the diamine solution (in the reaction vessel). Stirring was continued until all solids were dissolved to form a polyamic acid solution. The solution was poured and stored at 0 ° C. for use in film molding.

The polyimide film derived from the polyamic acid (BPDA / 6FDA // TFMB) was chemically imidized by the use of a catalyst solution. The chemically imidized film was made by molding the polymer into a DuPont MYLAR® film. The polymer (and support sheet) was immersed in a catalyst solution comprising acetic anhydride to β-picolin in a 1: 1 ratio. Within minutes (when partially imidized), gel films formed. This gel film was peeled from the support sheet and transferred to a restraining frame (pin frame).

The film was then heated using a forced air oven to further imidize the polymer and remove the solvent. The film was exposed to 100 ° C., 150 ° C., 200 ° C. and 300 ° C. for about 1/2 hour. The film was removed from the pin frame and analyzed. The data is shown in Table 1.

Example 2

Polyamic acid was prepared according to Example 1. However, instead of using 6FDA anhydride as part, the polymer only contains two monomers, 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 3,3 ', 4,4'-biphenyltetra Derived from carboxylic dianhydride (BPDA).

In a dried 500 milliliter round bottom flask equipped with nitrogen inlet, mechanical stirrer, and thermometer, 16.181 g (0.055 moles) of BPDA and 17.163 g (0.055 moles) of TFMB were added. Both monomers were dissolved in 131.68 milliliters of DMAc. A chemical reaction occurred to form a polyamic acid solution. The solution was poured, stored at 0 ° C. and used for film molding.

The polyimide film derived from the polyamic acid (BPDA // TFMB) prepared above was chemically imidized by using a catalyst solution. The above chemically imidized film was prepared by molding the polymer in a DuPont Myra film. The polymer (and support sheet) was immersed in a catalyst solution comprising acetic anhydride to β-picolin in a 1: 1 ratio. Within minutes (partially imidized), a gel film formed. This gel film was peeled off from the support sheet and transferred to the re-extension frame (pin frame).

The film was then heated using a forced air oven to further imidize the polymer and remove the solvent. The film was exposed to 100 ° C., 150 ° C., 200 ° C. and 300 ° C. for about 1/2 hour. The film was removed from the pin frame and analyzed. The data is shown in Table 1.

Example 3

Polyamic acid was prepared according to Example 1. However, instead of using 6FDA anhydride as part, the polymer may contain three monomers: 2,2'-bis (trifluoromethyl) benzidine (TFMB), 3,5-diaminobenzotrifluoride (DABTF) And 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA).

In a dried 500 milliliter round bottom flask equipped with nitrogen inlet, mechanical stirrer, and thermometer, 24.658 g (0.077 mole) of TFMB and 5.911 g (0.033 mole) of 3,5-diaminobenzotrifluoride (DABTF) were charged. . Both monomers were dissolved in 252.6 milliliters of DMAc. Next, 32.362 g (0.11 mole) of BPDA was added and dissolved. A chemical reaction occurred to form a polyamic acid solution. The solution was poured, stored at 0 ° C. and used for film molding.

The polyimide film derived from the polyamic acid (BPDA // TFMB / DABTF) prepared above was chemically imidized by using a catalyst solution. The above chemically imidized film was prepared by molding the polymer in a DuPont Myra film. The polymer (and support sheet) was immersed in a catalyst solution comprising acetic anhydride to β-picolin in a 1: 1 ratio. Within minutes (when partially imidized), gel films formed. This gel film was peeled off from the support sheet and transferred to the re-extension frame (pin frame).

The film was then heated using a forced air oven to further imidize the polymer and remove the solvent. The film was exposed to 100 ° C., 150 ° C., 200 ° C. and 300 ° C. for about 1/2 hour. The film was removed from the pin frame and analyzed. The data is shown in Table 1.

Example 4

Polyamic acid was prepared according to Example 1. However, the polymers include three monomers, three monomers, 2,2'-bis (trifluoromethyl) benzidine (TFMB), trans-1,4-diaminocyclohexane (CHDA), and 3,3 ', 4, Derived from 4'-biphenyltetracarboxylic dianhydride (BPDA).

In a dried 500 milliliter round bottom flask equipped with nitrogen inlet, mechanical stirrer, and thermometer, 12.52 g (0.04 mole) of TFMB and 0.79 g (0.007 mole) of trans-1,4-diaminocyclohexane (CHDA) were added. . Both monomers were dissolved in 114 milliliters of DMAc. Next, 13.5 g (0.046 mole) BPDA was added and dissolved. A chemical reaction occurred to form a polyamic acid solution. The solution was poured, stored at 0 ° C. and used for film molding.

The polyimide film derived from the polyamic acid (BPDA // TFMB / CHDA) prepared above was chemically imidized by using a catalyst solution. The above chemically imidized film was prepared by molding the polymer in a DuPont Myra film. The polymer (and support sheet) was immersed in a catalyst solution comprising acetic anhydride to β-picolin in a 1: 1 ratio. Within minutes (when partially imidized), gel films formed. This gel film was peeled off from the support sheet and transferred to the re-extension frame (pin frame).

The film was then heated using a forced air oven to further imidize the polymer and remove the solvent. The film was exposed to 100 ° C., 150 ° C., 200 ° C. and 300 ° C. for about 1/2 hour. The film was removed from the pin frame and analyzed. The data is shown in Table 1.

Comparative Example 1

A polyamic acid of 2,000-poise viscosity was prepared according to Example 1. The polymer was molded using a thermal method (ie, without using a catalyst compound) to convert to a polyimide film.

A polyimide film was prepared by molding a polyamic acid solution on a 316 stainless steel plate. The polyamic acid solution was spread using an aluminum blade with a gap. The gap was set so that the final thickness was about ˜3.0 mil.

A stainless steel plate was then placed along with the wet film on the hot plate and heated until the film was not sticky or to about 80 ° C. The dried film was then transferred to a re-extension frame (pin frame). While placed on the fin frame, the film was thermally converted to polyimide using forced hot air for about 1/2 hour at 100 ° C., 150 ° C., 200 ° C. and 300 ° C., respectively. The film was removed from the pin frame and analyzed. The results are shown in Table 1.

Comparative Example 2

A polyamic acid of 3,100-poise viscosity was prepared according to Example 2 (BPDA // TFMB). The polymer was molded using a thermal method (ie, without using a catalyst compound) to convert to a polyimide film.

A polyimide film was prepared by molding a polyamic acid solution on a 316 stainless steel plate. The polyamic acid solution was spread using an aluminum blade with a gap. The gap was set so that the final thickness was about ˜3.0 mil.

A stainless steel plate was then placed along with the wet film on the hot plate and heated until the film was not sticky or to about 80 ° C. The dried film was then transferred to a re-extension frame (pin frame). While placed on the fin frame, the film was thermally converted to polyimide using forced hot air at 100 ° C., 150 ° C., 200 ° C. and 300 ° C. for about 1/2 hour. The film was removed from the pin frame and analyzed. The results are shown in Table 1.

Comparative Example 3

Polyamic acid of 2,300-poise viscosity was prepared according to Example 2 (BPDA // TFMB / DABTF). The polymer was molded using a thermal method (ie, without using a catalyst compound) to convert to a polyimide film.

A polyimide film was prepared by molding a polyamic acid solution on a 316 stainless steel plate. The polyamic acid solution was spread using an aluminum blade with a gap. The gap was set so that the final thickness was about ˜3.0 mil.

A stainless steel plate was then placed along with the wet film on the hot plate and heated until the film was not sticky or to about 80 ° C. The dried film was then transferred to a re-extension frame (pin frame). While placed on the fin frame, the film was thermally converted to polyimide using forced hot air at 100 ° C., 150 ° C., 200 ° C. and 300 ° C. for about 1/2 hour. The film was removed from the pin frame and analyzed. The results are shown in Table 1.

Comparative Example 4

Polyamic acid was prepared according to Example 1. However, instead of using BPDA anhydride as part, only 6FDA was used. The diamine employed was 2,2'-bis (trifluoromethyl) benzidine (TFMB).

In a dried 500 milliliter round bottom flask equipped with nitrogen inlet, mechanical stirrer, and thermometer, 16.012 g (0.05 moles) of TFMB (to melt it) and 22.21 g (0.05 mole) of 6FDA were added. The amount of DMAc used was 148.93 milliliters. A chemical reaction occurred to form a polyamic acid solution. The solution was poured, stored at 0 ° C. and used for film molding. No chemical conversion compound was added.

A polyimide film was prepared by molding a polyamic acid solution on a 316 stainless steel plate. The polyamic acid solution was spread using an aluminum blade with a gap. The gap was set so that the final thickness was about ˜3.0 mil.

A stainless steel plate was then placed along with the wet film on the hot plate and heated until the film was not sticky or to about 80 ° C. The dried film was then transferred to a re-extension frame (pin frame). While placed on the fin frame, the film was thermally converted to polyimide using forced hot air at 100 ° C., 150 ° C., 200 ° C. and 300 ° C. for about 1/2 hour. The film was removed from the pin frame and analyzed. The results are shown in Table 1.

Comparative Example 5

By the same methods and conditions described in Comparative Example 4 of the present invention, 22.065 g (0.075 mole) BPDA was added to 18.622 g (0.075 mole) of 3,3'-diaminodiphenyl sulfone already dissolved in 148.93 milliliters DMAc. A chemical reaction occurred to form a polyamic acid solution. The solution was poured, stored at 0 ° C. and used for film molding. No chemical conversion compound was added.

A polyimide film was prepared by molding a polyamic acid solution on a 316 stainless steel plate. The polyamic acid solution was spread using an aluminum blade with a gap. The gap was set so that the final thickness was about ˜3.0 mil.

A stainless steel plate was then placed along with the wet film on the hot plate and heated until the film was not sticky or to about 80 ° C. The dried film was then transferred to a re-extension frame (pin frame). While placed on the fin frame, the film was thermally converted to polyimide using forced hot air for about 1/2 hour at 100 ° C., 150 ° C., 200 ° C. and 300 ° C., respectively. The film was removed from the pin frame and analyzed. The results are shown in Table 1.

Comparative Example 6

By the same methods and conditions described in Comparative Example 4 of the present invention, 22.065 g (0.075 mole) BPDA was added to 18.622 g (0.075 mole) of 3,3'-diaminodiphenyl sulfone already dissolved in 148.93 milliliters DMAc. A chemical reaction occurred to form a polyamic acid solution. The solution was poured, stored at 0 ° C. and used for film molding. No chemical conversion compound was added.

A polyimide film was prepared by molding a polyamic acid solution on a 316 stainless steel plate. The polyamic acid solution was spread using an aluminum blade with a gap. The gap was set so that the final thickness was about ˜3.0 mil.

A stainless steel plate was then placed along with the wet film on the hot plate and heated until the film was not sticky or to about 80 ° C. The dried film was then transferred to a re-extension frame (pin frame). While placed on the fin frame, the film was thermally converted to polyimide using forced hot air at 100 ° C., 150 ° C., 200 ° C. and 300 ° C. for about 1/2 hour. The film was removed from the pin frame and analyzed. The results are shown in Table 1.

Comparative Example 7

According to Example 1 (ie, imidating the film using chemical conversion method), a polyimide film was prepared. Instead, however, the polymer contains four monomers, 2,2'-bis (trifluoromethyl) benzidine (TFMB), 3,4-oxydianiline (3,4-ODA), pyromellitic dianhydride (PMDA). ) And 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA).

In a dried 500 milliliter round bottom flask equipped with nitrogen inlet, mechanical stirrer, and thermometer, 12.8 g (0.04 mole) of TFMB and 8.0 g (0.04 mole) of 3,4-oxydianiline (3,4-ODA) Put in. Both monomers were dissolved in 169 milliliters of DMAc. Next, 14.0 g (0.046 mole) of PMDA and 4.7 g (0.16 mole) of BPDA were added and dissolved.

A chemical reaction occurred to form a polyamic acid solution. A small amount of 6.0% by weight of pyromellitic dianhydride solution in DMAc was added to the polyamic acid solution until the viscosity of the solution reached about 2,400 poise. The solution was poured and stored at 0 ° C. until used for film molding.

The polyimide film derived from the polyamic acid (PMDA / BPDA / TFMB / 3,4-ODA) prepared above was chemically imidized by using a catalyst solution. The above chemically imidized film was prepared by molding the polymer in a DuPont Myra film. The polymer (and support sheet) was immersed in a catalyst solution comprising acetic anhydride to β-picolin in a 1: 1 ratio. Within minutes (when partially imidized), gel films formed. This gel film was peeled off from the support sheet and transferred to the re-extension frame (pin frame).

The film was then heated using a forced air oven to further imidize the polymer and remove the solvent. The film was exposed to 100 ° C., 150 ° C., 200 ° C. and 300 ° C. for about 1/2 hour. The film was removed from the pin frame and analyzed. The data is shown in Table 1.

Comparative Example 8

According to Example 1 (ie, imidating the film using chemical conversion method), a polyimide film was prepared. Instead, however, the polymer contains four monomers, 4,4-oxydianiline (4,4-ODA), p-phenylene diamine (PPD), pyromellitic dianhydride (PMDA) and 3,3 ', 4 Derived from, 4'-biphenyltetracarboxylic dianhydride (BPDA).

In a dried 500 milliliter round bottom flask with nitrogen inlet, mechanical stirrer, and thermometer, 38.4 g (0.192 mole) of 4,4-oxydianiline (4,4-ODA) and 31.1 g (0.288 mole) of p- Phenylene diamine (PPD) was added. Both monomers were dissolved in 168 milliliters of DMAc. Next, 60.0 g (0.275 mole) PMDA and 56.5 g (0.192 mole) BPDA were added and dissolved.

A chemical reaction occurred to form a polyamic acid solution. A small amount of 6.0% by weight of pyromellitic dianhydride solution in DMAc was added to the polyamic acid solution until the viscosity of the solution reached about 2,200 poise. The solution was poured and stored at 0 ° C. until used for film molding.

The polyimide film derived from the polyamic acid (PMDA / BPDA // 4,4-ODA / PPD) prepared above was chemically imidized by using a catalyst solution. The above chemically imidized film was prepared by molding the polymer in a DuPont Myra film. The polymer (and support sheet) was immersed in a catalyst solution comprising acetic anhydride to β-picolin in a 1: 1 ratio. Within minutes (when partially imidized), gel films formed. This gel film was peeled off from the support sheet and transferred to the re-extension frame (pin frame).

The film was then heated using a forced air oven to further imidize the polymer and remove the solvent. The film was exposed to 100 ° C., 150 ° C., 200 ° C. and 300 ° C. for about 1/2 hour. The film was removed from the pin frame and analyzed. The data is shown in Table 1.

Comparative Example 9

By the same methods and conditions described in Comparative Example 4 of the present invention (thermal conversion), 22.8 (0.90 mole) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) was dissolved in 267 milliliters of DMAc. 30.0 g (0.675 mole) 6FDA and 6.6 g (0.0225 mole) BPDA were added and a chemical reaction occurred to form a polyamic acid solution. The solution was poured, stored at 0 ° C. and used for film molding.

A polyimide film was prepared by molding a polyamic acid solution on a 316 stainless steel plate. The polyamic acid solution was spread using an aluminum blade with a gap. The gap was set so that the final thickness was about ˜3.0 mil.

The stainless steel plate was then placed together with the wet film on a hot plate and heated until the film was not sticky or to about 80 ° C. The dried film was then transferred to a re-extension frame (pin frame). While placed on the fin frame, the film was thermally converted to polyimide using forced hot air at 100 ° C., 150 ° C., 200 ° C. and 300 ° C. for about 1/2 hour. The film was removed from the pin frame and analyzed. The results are shown in Table 1.

Using chemical conversion methods such as herein (i.e., instead of more conventional thermal methods), (i) in-plane CTE, (ii) glass transition temperatures are more desirable than films converted using thermal methods having the same composition. , And (iii) a film having a light transmittance coefficient is formed. Polymeric films are typically suitable for use in flexible displays and the like because they exhibit high thermal stability while maintaining colorlessness.

Claims (13)

A film comprising a polyimide comprising a perfluoro-imide moiety represented by the following formula obtained by contacting a first dianhydride component and a first diamine component, The in-plane coefficient of thermal expansion (CTE) of the polyimide film is any two values selected from -5, 0, 2, 4, 6, 8, 10, 12, 14, 16, 18 and 20 ppm / ° C. Coefficient of thermal expansion between (including those two values), The thickness of the film is the thickness between any two values selected from 5, 10, 15, 20, 25, 50, 75, 100, 125, 150, 175 and 200 microns (including those two values),  The average light transmittance of the film is between any two values selected from 65.0, 70.0, 75.0, 80.0, 85.0, 90.0, 95.0 and 99.0 when the film is exposed to light at a wavelength of 380 to 770 nanometers (the two values being Film).

Where n is the number of repeating perfluoro-imide residues, n is an integer from 10 to 100,000, The perfluoro-imide moiety is any two selected values of 100, 95, 90, 85, 80, 75, 70, 65, 60, 55 and 50 mole percent based on the total moles of imide residues in the polyimide film. It is present in mole percent between (including those two values). The method according to claim 1, wherein the glass transition temperature (Tg) of the polyimide is a temperature between any two values selected from 250, 275, 300, 325, 350, 375, 400, 425, 450, 475 and 500 ° C. Including numerical values). The total diamine component of claim 1, wherein the polyimide is derived from a second diamine component, wherein the first diamine component and the second diamine component comprise a total diamine component, wherein the second diamine component is reacted with the polyimide. Polyimide and mole percent value between any two values selected from among 1, 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, and 50 mole percent of Reacted, The second diamine component is trans-1,4-diaminocyclohexane; Diaminocyclooctane; Tetramethylenediamine; Hexamethylenediamine; Octamethylenediamine; Dodecamethylene-diamine; Aminomethylcyclooctylmethanamine; Aminomethylcyclododecylmethanamine; Aminomethylcyclohexylmethanamine; 3,5-diaminobenzotrifluoride; 2- (trifluoromethyl) -1,4-phenylenediamine; 5- (trifluoromethyl) -1,3-phenylenediamine; 1,3-diamino-2,4,5,6-tetrafluorobenzene; 2,2-bis [4- (4-aminophenoxy) phenyl] -hexafluoropropane; 2,2-bis (3-aminophenyl) 1,1,1,3,3,3-hexafluoropropane; 2,2'-bis- (4-aminophenyl) -hexafluoropropane (6F diamine); 3,3'-bis (trifluoromethyl) benzidine; 4,4'-diaminodiphenyl sulfide (4,4'-DDS); 3,3'-diaminodiphenyl sulfone (3,3'-DDS); 4,4'-diaminodiphenyl sulfone; And 4,4'-trifluoromethyl-2,2'-diaminobiphenyl. The method of claim 1, wherein the polyimide is also derived from a second dianhydride component, wherein the first dianhydride component and the second dianhydride component comprise a total dianhydride component and a second dianhydride component. The molar percentage between any two values selected from among 1, 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, and 50 mole percent of this total dianhydride component, including both values. Into the polyimide, The second dianhydride component is 4,4′-oxydiphthalic anhydride (ODPA); 4,4 '-(4,4'-isopropylidenediphenoxy) bis (phthalic anhydride) (BPADA); 2,3,3 ', 4'-biphenyl tetracarboxylic dianhydride; 2,2 ', 3,3'-biphenyl tetracarboxylic dianhydride; 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA); Diphenylsulfontetracarboxylic dianhydride (DSDA); 4,4'-bisphenol A dianhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride; (-)-[1S ^* , 5R ^* , 6S ^* ]-3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3- (tetrahydrofuran-2,5-dione) ; Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; And 9,9-disubstituted xanthene dianhydride. The polymer film of claim 1, further comprising a filler selected from the group consisting of dicalcium phosphate, silicon dioxide, alumina, and titanium dioxide. A laminate comprising the film of claim 1 and an indium tin oxide layer, wherein the film of claim 1 and the indium tin oxide layer are adjacent. 7. The laminate of claim 6, wherein the laminate is formed using an indium tin oxide deposition process. A laminate comprising the film of claim 1 and a passivation barrier layer, wherein the film of claim 1 and the passivation barrier layer are adjacent and the passivation barrier layer is present on one or both sides of the film. The laminate of claim 8, wherein the passivation barrier layer is an oxygen passivation layer, a vapor passivation barrier layer, or both. The laminate of claim 8, wherein the passivation barrier layer comprises a material having the formula SiO _x or SiN _x (where X is one of 2, 3 or 4). The laminate of claim 8, wherein the passivation barrier layer optionally comprises Al ₂ O ₃ together with SiO _x or SiN _x (where X is one of 2, 3 or 4). The laminate of claim 8, wherein the passivation barrier layer is applied to the film using an atomic deposition process. A laminate comprising the film of claim 1 and a conductor layer, wherein the conductor layer comprises a polymer in which electrically conductive particles are dispersed, wherein the electrically conductive particles are carbon nanotubes, carbon powder, indium tin oxide and zinc. A laminate selected from the group comprising substrate oxides.