Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
  • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
  • B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
  • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
  • B29K2077/10—Aromatic polyamides [polyaramides] or derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
  • B29K2995/0026—Transparent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2007/00—Flat articles, e.g. films or sheets
  • B29L2007/008—Wide strips, e.g. films, webs
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
  • B29L2031/3475—Displays, monitors, TV-sets, computer screens
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
  • B32B2457/206—Organic displays, e.g. OLED
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]
  • Y10T428/24967—Absolute thicknesses specified
  • Y10T428/24975—No layer or component greater than 5 mils thick
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
  • Y10T428/264—Up to 3 mils
  • Y10T428/265—1 mil or less

Definitions

• the invention relates to the manufacture of thermally and dimensionally stable transparent polymer films. More particularly, the invention relates to the manufacture and use of aromatic polyamides, which have a rigid backbone with a glass transition temperature higher than 300°C, yet are still soluble in conventional organic solvents without the need for the presence of inorganic salts.
• the polymer films can be prepared by solution casting, and cured at elevated temperatures. The cured films show a high optical transparency over a range of 400-750 nm, (transmittance > 80%), a low coefficient of thermal expansion (CTE ⁇ 20 ppm/°C), and good solvent resistance.
• OLED Organic Light Emitting Diode
• AMOLEDs active matrix OLEDs
• AMOLED innovations that improve these properties will further accelerate AMOLED adoption into portable devices and expand the range of devices that use them. These performance factors are largely driven by the processing temperature o the electronics.
• AMOLEDs have a thin-film transistor (TFT) array structure which is deposited on the transparent substrate. Higher TFT deposition temperatures can be used.
• glass plates are used as AMOLED substrates. They offer high processing temperatures (>500°C) and good barrier properties, but are relatively thick, heavy, rigid, and are vulnerable to breaking, which reduces product design freedom and display robustness. Thus, there is a demand by portable device manufacturers for a lighter, thinner, and more robust replacement. Flexible substrate materials would also open new possibilities for product design, and enable lower cost roll-to-roll fabrication.
• Fiber reinforced polymer composite films such as reported by H. Ito (Jap. J. Appl. Phys., 45, No.5B, pp4325, 2006), combine the dimensional stability of fiber glass in a polymer film, offering an alternative way to achieve a low CTE.
• the refractive indices of the matrix polymer and the fiber must be precisely matched, which greatly limits the choice of the matrix polymer within an organic silicon resin.
• nanoparticles as filler, the effect of lowering CTE is not significant (JM Liu, et al, J. SID, Vol. 19, No. 1 , 201 1)
• JP 2009-7921 OA describes a thin film prepared from a fluorine containing aromatic polyamide that displays a very low CTE ( ⁇ 0 ppm/°C), good transparency (T% >80 between 450 -700 nm), and excellent mechanical properties.
• the maximum thickness of films made from this polymer is 20 ⁇ , because a dry-wet method where the salt is removed must be used for the film preparation.
• the film also displays poor resistance to strong organic solvents.
• the present invention is directed toward transparent films prepared from aromatic copolyamides with T g s greater than 300°C that have CTEs less than 20 ppm/°C.
• the films are cast using solutions of the polyamides in ⁇ , ⁇ -dimethylacetamide (DMAc), N-methyl-2- pyrrolidinone (NMP), or other polar solvents.
• DMAc ⁇ , ⁇ -dimethylacetamide
• NMP N-methyl-2- pyrrolidinone
• the present invention can be produced in the absence of an inorganic salt.
• DMAc ⁇ , ⁇ -dimethylacetamide
• NMP N-methyl-2- pyrrolidinone
• the present invention can be produced in the absence of an inorganic salt.
• a process for manufacturing a thermally and dimensionally stable transparent aromatic copolyamide film comprising the steps of: (A) forming a mixture of two or more aromatic diamines wherein at least one of the diamines contains one or more free carboxylic acid groups, such that the amount of the carboxylic acid containing diamine is greater than approximately 1 mole percent and less than approximately 10 mole percent of the total diamine mixture; (B) dissolving the aromatic diamine mixture in a polar solvent; (C) reacting the diamine mixture with at least one aromatic diacid dichloride, wherein hydrochloric acid and a polyamide solution is generated; (D) eliminating the hydrochloric acid with a reagent; (E) casting the polyamide solution into a film; and (F) curing the film at a temperature, wherein the temperature is at least 90% of the glass transition temperature of the film.
• the curing process involves heating the polymer films containing a free acid group near the T g for several minutes under an inert atmosphere or under reduced pressure. After the curing process, the film resists dissolution and/or swelling in commonly used organic solvents, including NMP, DMAc, dimethylsulfoxide (DMSO), etc.
• organic solvents including NMP, DMAc, dimethylsulfoxide (DMSO), etc.
• DMSO dimethylsulfoxide
• a transparent aromatic copolyamide film is produced having at least two repeat units of a general formula (I) and (11):
• n 1 to 4 including, without limitation. 1 , 2, 3, and 4
• Ax ⁇ is selected from the group of aromatic units which form aromatic diacid chlorides:
• R5 are selected from the group comprising hydrogen, halogen (fluoride, chloride, bromide, and iodide), alkyl, substituted alkyl such as halogenated alkyls, nitro, cyano, thioalkyl, alkoxy, substituted alkoxy such as halogenated alkoxy, aryl. or substituted aryl such as halogenated aryls. alkyl ester and substituted alkyl esters, and combinations thereof.
• halogen fluoride, chloride, bromide, and iodide
• each R i can be different, each R 2 can be different, each R 3 can be different, each R4 can be different, and each R5 can be different.
• Gj is selected from a group comprising a covalent bond; a CH 2 group; a C(CH 3 ) 2 group; a C(CF 3 ) 2 group; a C(CX 3 ) 2 group, wherein X is a halogen; a CO group; an O atom: a S atom; a S0 2 group; a Si (CH 3 ) 2 group; 9, 9-fluorene group; substituted 9, 9-fluorene; and an ( )/.() group, wherein Z is a aryl group or substituted aryl group, such as phenyl group, biphenyl group,
• R$ are selected from the group comprising hydrogen, halogen (fluoride, chloride, bromide, and iodide), alkyl, substituted alkyl such as halogenated alkyls, nitro, cyano, thioalkyl, alkoxy, substituted alkoxy such as halogenated alkoxy, aryl, substituted aryl such as halogenated aryls, alkyl ester, and substituted alkyl esters, and combinations thereof. It is to be understood that each R 6 can be different, each R can be different, and each Rg can be different.
• G 2 is selected from a group comprising a covalent bond; a CH 2 group; a C(CH 3 ) 2 group; a C(CF 3 ) 2 group; a C(CX 3 ) 2 group, wherein X is a halogen; a CO group; an O atom; a S atom; a S0 2 group; a Si (CH 3 ) 2 group; 9, 9-fluorene group; substituted 9, 9-fluorene; and an OZO group, wherein Z is a aryl group or substituted aryl group, such as phenyl group, biphenyl group, perfluorobiphenyl group, 9, 9-bisphenylfluorene group, and substituted 9, 9- bisphenylfluorene.
• Ar 3 is selected from the group of aromatic units which form diamines containing free carboxylic acid group:
• R 9 can be different, each Rio can be different, and each Ri i can be different.
• G 3 is selected from a group comprising a covalent bond; a CH 2 group: a C(CH 3 ) 2 group; a C(CF 3 ) 2 group; a C(CX ) 2 group, wherein X is a halogen; a CO group: an O atom; a S atom; a S0 2 group; a Si (CH 3 ) 2 group; 9, 9-fluorene group; substituted 9, 9-fluorene; and an OZO group, wherein Z is a aryl group or substituted aryl group, such as phenyl group, biphenyl group, perfluorobiphenyl group, 9, 9-bisphenylfluorene group, and substituted 9, 9-bisphenylfluorene. It should be understood that the copolymer may contain multiple repeat units with structures (I) and (II) where Ari, Ar 2 , and Ar 3 may be the same or different.
• a method of preparing a transparent film having a CTE less than 20 ppm/°C that is stable for at least one hour at 300°C comprising the steps of:
• n 1 to 4 (including, without limitation, 1 , 2, 3, and 4), wherein Ar is selected from the group of aromatic units which form diamines containing free carboxylic acid group: wherein m 1 or 2. wherein t - 1 to 3.
• R9, Rio, Ri 1 are selected from the group comprising hydrogen, halogen (fluoride, chloride, bromide, and iodide), alkyl, substituted alkyl such as halogenated alkyls, nitro, cyano, thioalkyl, alkoxy, substituted alkoxy such as a halogenated alkoxy, aryl, substituted aryl such as halogenated aryls, alkyl ester, and substituted alkyl esters, and combinations thereof. It is to be understood that each R can be different, each Rio can be different, and each R] 1 can be different.
• G3 is selected from a group comprising a covalent bond; a CH 2 group; a C(CH 3 ) 2 group; a C(CF 3 ) 2 group; a C(CX 3 ) 2 group, wherein X is a halogen; a CO group; an O atom; a S atom; a S0 2 group; a Si (CH 3 ) 2 group; 9, 9-fluorene group; substituted 9, 9-fluorene; and an OZO group, wherein Z is a aryl group or substituted aryl group, such as phenyl group, biphenyl group, perfluorobiphenyl group, 9, 9-bisphenylfluorene group, and substituted 9, 9-bisphenylfluorene; with aromatic diacid chlorides to afford a copolyamide containing pendant carboxyl groups;
• polyamides containing small amounts of DAB (less than 1 mol%) useful for reverse osmosis membranes are described.
• polyamides containing more than 10 mol% DADP useful for high performance fibers are described.
• the carboxylic acid content would have been too low to affect cross linking, and in the case of the DADP polymers, the degree of cross linking would have been so high that the films would have been extremely brittle and unsuitable for flexible substrates.
• the crosslinked films can be used as flexible substrates that will enable the high temperature fabrication of thin film transistors needed for a wide range of microelectronic applications, particularly for ruggedized or flexible organic light emitting diode (OLED) displays. No available material exhibits all of these properties.
• the polymer substrate films in the present invention expand the utilization of AMOLEDs in portable devices by improving device electrical efficiency and the consumer experienced robustness of the display.
• the substrate of the present invention will enable the development of the flexible display market.
• These displays can be used for conformable displays that can be integrated onto clothing, flexible e-paper and e-book displays, displays for smartcards, and a host of other new
• the polymer substrate films in the present invention can be used for flexible sensors.
• the new devices produced from the polymer substrate films in the present invention can dramatically impact dail life, by decreasing the cost and increasing accessibility and portability of information.
• the polymers in the present invention can be prepared in a common organic solvent at room temperature (approximately 15 °C to approximately 25 °C). These polymers can be produced in the absence of an inorganic salt. The resulting colorless and homogenous polymer solution can be used directly for subsequent film casting. No special polymerization reactor and no polymer isolation procedure is required.
• the process is amenable to scale-up to metric ton quantities.
• the polymers of the present invention are soluble in polar aprotic solvents without the need for the presence of inorganic salts. They can be solution cast in a batch process, or continuously cast directly from their polymerization mixtures and cured using a roll-to-roll process to yield free standing transparent films with thickness greater than 20 ⁇ . Alternatively, the polymer solutions may be solution cast onto a reinforcing substrate like thin glass or a microelectronic device and cured to form films less than 20 pm.
• the films display high T g s (>300°C), low CTEs ( ⁇ 20 ppm/°C), high transparencies (T>80% between 400 to 750 mn), excellent mechanical properties (tensile strengths >200 MPa), and low moisture absorptions ( ⁇ 2% @ 100% humidity at room temperature). Furthermore, the films show excellent chemical resistance after they are heated to temperatures of at least 90% that of their T g s for short periods of time.
• copolyamides were prepared by polymerizing one or more aromatic diacid dichlorides as shown in the following general structures:
• Ri, R 2 , R3, R4, R5 are selected from the group comprising hydrogen, halogen (fluoride, chloride, bromide, and iodide), alkyl, substituted alkyl such as halogenated alkyls, nitro, cyano, thioalkyl, alkoxy, substituted alkoxy such as a halogenated alkoxy, aryl, or substituted aryl such as halogenated aryls, alkyl ester and substituted alkyl esters, and combinations thereof.
• each Ri can be different
• each R 2 can be different
• each R 3 can be different
• each R4 can be different
• each R5 can be different.
• Gi is selected from a group comprising a covalent bond; a CH 2 group; a C(CH 3 ) 2 group; a C(CF 3 ) 2 group; a C(CX 3 ) 2 group, wherein X is a halogen; a CO group; an O atom; a S atom; a S0 2 group; a Si (CH 3 ) 2 group; 9, 9-fluorene group; substituted 9, 9-fluorene; and an OZO group, wherein Z is a aryl group or substituted aryl group, such as phenyl group, biphenyl group,
• perfluorobiphenyl group 9, 9-bisphenylfluorene group, and substituted 9, 9-bisphenylfluorene.
• halogen fluoride, chloride, bromide, and iodide
• G 2 and G 3 are selected from a group comprising a covalent bond; a CH 2 group; a C(CH 3 )2 group; a C(CF 3 ) 2 group; a C(CX 3 ) 2 group, wherein X is a halogen; a CO group; an O atom; a S atom; a S0 2 group; a Si (CH 3 ) 2 group; 9, 9-fluorene group; substituted 9, 9-fluorene; and an OZO group, wherein Z is a aryl group or substituted aryl group, such as phenyl group, biphenyl group, perfluorobiphenyl group, 9, 9-bisphenyl lluorene group, and substituted 9, 9-bisphenylfluorene.
• the present invention is directed toward transparent films prepared from aromatic copolyamides.
• a polyamide is prepared via a condensation polymerization in a solvent, where the hydrochloric acid generated in the reaction is trapped by a reagent like propylene oxide (PrO).
• PrO propylene oxide
• the film can be made directly from the reaction mixture, without the need for isolating and re-dissolving the polyamide.
• Colorless films can be prepared by casting procedures directly from the polymerization solutions. The product of the reaction of the hydrochloric acid with the PrO is eliminated during the removal of the solvent. These films display low CTEs as cast and do not need to be subjected to stretching.
• the CTEs and T g s of the resulting copolymers and the optical properties of their solution cast films can be controlled. It is particularly surprising that a film can be cured at an elevated temperature when free carboxylic acid side groups exist along the polymer chains. If the reaction of the reagent with the hydrochloric acid does not form volatile products, the polymer is isolated from the polymerization mixture by precipitation and re- dissolved by a polar solvent (without the need for inorganic salts) and cast in the film. If the reaction of the reagent with the hydrochloric acid does form volatile products, the film can be directly east.
• a reagent that forms volatile products is PrO.
• TPC Terephthaloyl dichloride
• IPC Isophthaloyl dichloride
• Example 1 This example illustrates the general procedure for the preparation of a copolymer from TPC, IPC and PFMB (70%/30%/100% mol) via solution condensation.
• Example 2 This example illustrates the general procedure for the preparation of a copolymer from TPC, PFMB, and FDA ( 100%/80%/20% mol) via solution condensation.
• Example 3 This example illustrates the general procedure for the preparation of a copolymer from TPC, IPC, DADP, and PFMB (70%/30%/3%/97% mol) via solution condensation.
• the viscosity of the solution increases until the mixture forms a gel.
• PrO 1.g, 0.024 mol
• the gel is broken up under stirring to form a viscous, homogenous solution.
• the resulting copolymer solution can be directly cast into film.
• Example 4 This example illustrates the general procedure for the preparation of a copolymer from TPC, IPC, DAB, and PFMB (75%/25%/5%/95% mol) via solution condensation.
• PFMB 3.0423g. 0.0095 mol
• DAB 0.076 l g, 0.0005 mol
• DM Ac dried DM Ac
• the temperature provided in the examples is room temperature, the temperature range can be between approximately -20°C to approximately 50°C, and in some embodiments from approximately 0°C to approximately 30°C.
• the polymer solution can be used directly for the film casting after polymerization.
• the solution is poured on a flat glass plate or other substrate, and the film thickness is adjusted by a doctor blade. After drying on the substrate, under reduced pressure, at 60°C for several hours, the film is further dried at 200°C under protection of dry nitrogen flow for 1 hour.
• the film is cured by heating at or near the polymer T g under vacuum or in an inert atmosphere for several minutes. Mechanical removal from the substrate yields a free standing film greater than approximately 10 ⁇ thick.
• the thickness of the free standing films can be adjusted by adjusting the solids content and viscosity of the polymer solution.
• the film can be cured at any temperature between approximately 90% and approximately 1 10% of the T g . It is also understood that the batch process can be modified so that it can be carried out continuously by a roll-to-roll process by techniques known to those skilled in the art.
• the polymer solution may be solution cast onto a reinforcing substrate like thin glass, silica, or a microelectronic device. In this case, the process is adjusted so that the final polyamide film thickness is greater than approximately 5 ⁇ .
• the CTE and T g are measured with a thermal mechanical analyzer (TA Q 400
• the sample film has a thickness of approximately 20 ⁇ , and the load strain is 0.05N. In one embodiment, the free standing film thickness is between approximately 20 ⁇ and approximately 125 ⁇ . In one embodiment, the film is adhered to a reinforcing substrate and the film thickness is ⁇ 20 ⁇ , In one embodiment, the CTE is less than approximately 20 ppm/°C, but it is understood that in other embodiments, the CTE is less than approximately 15 ppm/°C, less than approximately 10 ppm/°C, and less than approximately 5 ppm/°C. It is to be understood that within these embodiments the CTE can be less than approximately 19, 18, 17, 16, 15, 14, 13, 12, 1 1 , 10, 9, 8, 7, 6. or 5 ppm/°C.
• the experimentally derived CTEs are the average of the CTE obtained from room temperature to about 250°C.
• Film transparency is measured by determining the transmittance of a 10 ⁇ thick film from 400 to 750 nm with a UV-Visible spectrometer (Shimadzu UV 2450).
• the solvent resistance of the film is determined by immersing it in a selected solvent for 30 minutes at room temperature.
• the film is considered solvent resistant if it is substantially free of surface wrinkles, swelling, or any other visible damage after immersion.
• the films are useful as substrates for flexible electronic devices.
• Example 4 The composition of a copolymer containing DAB (Example 4), which was determined in an analogous manner, is also shown in Table 4 along with the properties of cured films of this polymer.
• the cured films of this invention are resistant to both inorganic and organic solvents.
• the film solvent resistance can be evaluated quickly by analyzing the resistance to NMP. a commonly used strong solvent. It has been found that films resistant to this solvent are also resistant to other polar solvents.
• DADP 4-

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