Dicarbonyl halides, polymer compositions and films made therefrom

Abstract

To provide dicarbonyl halides, polymer compositions and films made therefrom.SOLUTION: In a first aspect, a dicarbonyl halide includes an alicyclic group. In a second aspect, a polymer composition is derived from the dicarbonyl halide, a dianhydride and a diamine, where the polymer composition is a poly(amide-imide) or a poly(amide-ester-imide), and the poly(amide-ester-imide) is further derived from a polyol. In a third aspect, a polymer film includes the polymer composition. In a fourth aspect, an electronic device includes the polymer film. In a fifth aspect, a metal-clad laminate includes the polymer film.SELECTED DRAWING: None

Description

[Technical field]

[0001] The field of this disclosure is dicarbonyl halides, polymer compositions and films made therefrom. [Background technology]

[0002] Polymer films, such as polyimide films, are used in a wide range of applications in the electronics industry to take advantage of the various mechanical, electrical and optical properties they can provide, as well as the beneficial thermal and chemical durability required during the processing of various electronic components and during the use of electronic devices. Polymer films can be used in the manufacture of flexible circuits and copper clad laminates, as well as in display devices, such as cover windows, touch sensor panels and other device layers. However, achieving the desired combination of properties in a single film can be difficult.

[0003] Polymer films with high temperature stability, high tensile modulus and low coefficient of thermal expansion (CTE) are required for flexible display applications, such as for thin film transistor (TFT) substrates in organic light emitting diode (OLED) displays, touch sensor panels (TSPs) for electronic paper (E-paper) and displays.

[0004] Polyimide films can potentially replace rigid glass cover sheets and other substrates currently used in display applications such as organic light-emitting diode (OLED) displays. In addition to having high transmittance and low haze, for polyimide films to be used in display applications, the polyimide film also needs to be neutral in color. Typical specifications require that both a* and b* be less than or equal to neutral (0) to 1 color unit in the CIE L*, a*, b* color space coordinates, i.e., the absolute values ​​of a* and b* should be less than 1. The three coordinates of CIE L*, a*, b* represent (1) the lightness of a color (L*=0 produces black and L*=100 indicates diffuse white), (2) its location between red / magenta and green (negative a* values ​​indicate green, while positive values ​​indicate magenta), and (3) its location between yellow and blue (negative b* values ​​indicate blue and positive values ​​indicate yellow).

[0005] Typical aromatic polyimides using fluorinated monomers are nearly colorless, but absorb light at blue or violet wavelengths (400-450 nm), which gives the film a yellow appearance in transmission. The color of polyimide films arises primarily from charge-transfer absorption due to HOMO-LUMO transitions that can potentially occur both within and between polymer chains. Various approaches have been used to modify the HOMO-LUMO transition energy or prevent interchain interactions. Fluorinated monomers have been used to modify the HOMO-LUMO transition energy of aromatic polyimide polymers, but these polyimide films exhibit some residual yellow color. Therefore, depending on the monomer composition of the polyimide, b* may be greater than 1. It is more difficult to achieve a neutral appearance in thick films, such as those above 25 μm, since the CIE L*, a*, and b* color measurements of the film also depend on its thickness.

[0006] In addition to having excellent optical properties, polyimide films used in these applications must maintain excellent mechanical properties, such as a high modulus. The modulus of the polyimide film can be increased by incorporating more rigid monomers into the polyimide backbone. However, in the case of rigid aromatic monomers, charge transfer absorption as described above leads to greater color in polyimides incorporating these monomers. In addition, rigid non-aromatic monomers may have poor thermal stability at high temperatures, such as typical imidization temperatures, leading to monomer decomposition and increased color. These are just two examples of the mechanisms by which the use of more rigid monomers can increase the color of polyimides while improving mechanical properties.

[0007] Cycloaliphatic and aliphatic monomers, when incorporated into the polyimide structure, can suppress color by modifying the electronic structure and charge transport properties of the polymer. These monomers, by themselves, will not participate in any charge transport transitions. However, the process in which the film is formed by casting a polyamic acid solution and curing the resulting film produces significant color. If the curing is carried out in air, the color development is more pronounced, suggesting that a secondary color formation mechanism is occurring. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Pat. No. 5,166,308 [Patent Document 2] U.S. Pat. No. 5,298,331 [Patent Document 3] U.S. Patent No. 2,801,185 [Patent Document 4] U.S. Pat. No. 4,522,958 [Patent Document 5] U.S. Pat. No. 5,648,407 [Patent Document 6] Patent No. 4406921 [Patent Document 7] Patent No. 4031624 [Patent Document 8] US Patent Application Publication No. 2015 / 0159044 [Patent Document 9] US Patent Application Publication No. 2017 / 0369654 [Patent Document 10] U.S. Patent No. 7,790,347 [Patent Document 11] U.S. Patent No. 6,391,999 [Patent Document 12] U.S. Pat. No. 4,742,099 [Patent Document 13] U.S. Patent No. 5,227,244 [Patent Document 14] U.S. Patent No. 5,218,034 [Patent Document 15] U.S. Pat. No. 5,543,222 Summary of the Invention [Means for solving the problem]

[0009] In a first embodiment, the dicarbonyl halide has formula I:

[0010] [ka]

[0011] During the ceremony, X and Y are the same or different in each occurrence and are independently selected from the group consisting of fluorine, chlorine, and bromine; R1-R4 are the same or different in each occurrence and are independently selected from the group consisting of hydrogen and alkyl, wherein alkyl is C1-12 and linear or branched; B and B' are the same or different in each occurrence and are alicyclic or aromatic groups, provided that at least one of B and B' is an alicyclic group; x and y are the same or different and are integers from 0 to 12; and n is an integer from 0 to 4.

[0012] In a second embodiment, the polymer composition is derived from the dicarbonyl halide, a dianhydride, and a diamine, and the polymer composition is a poly(amide-imide) or a poly(amide-ester-imide), the poly(amide-ester-imide) being further derived from a polyol.

[0013] In a third embodiment, a polymeric film comprises the polymeric composition.

[0014] In a fourth embodiment, an electronic device comprises the polymer film.

[0015] In a fifth embodiment, a metal clad laminate comprises the polymer film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Depending on the context, as used herein, "diamine" is intended to mean (i) the unreacted form (i.e., the diamine monomer); (ii) the partially reacted form (i.e., one or more portions of an oligomer or other polymer precursor derived or otherwise derived from the diamine monomer), or (iii) the fully reacted form (one or more portions of a polymer derived or otherwise derived from the diamine monomer). The diamine can be functionalized at one or more sites, depending on the particular embodiment selected in the practice of the invention.

[0017] Indeed, the term "diamine" is not intended to be limiting (or to be taken literally) with respect to the number of amine moieties in the diamine component. For example, (ii) and (iii) above include polymeric materials that may have two, one, or zero amine moieties. Instead, the diamine may be functionalized with additional amine moieties (in addition to the amine moieties at the ends of the monomers that react with the dianhydride to grow the polymer chain). Such additional amine moieties could be used to crosslink the polymer or to provide other functional groups to the polymer.

[0018] Similarly, as used herein, the term "dianhydride" is intended to mean a (complementary) component that reacts with a diamine, which can react in combination to form an intermediate that can then be hardened into a polymer. Depending on the context, as used herein, "anhydride" can refer not only to the anhydride moiety itself, but also to a precursor of an anhydride moiety, such as (i) a pair of carboxylic acid groups, which can be converted to an anhydride by dehydration or similar type of reaction; or (ii) an acid halide (e.g., chloride) ester functional group (or any other functional group now known or developed in the future) that can be converted to an anhydride functional group.

[0019] Depending on the context, "dianhydride" can mean (i) the unreacted form (i.e., the dianhydride monomer, whether the anhydride functionality is in true anhydride form or in a precursor anhydride form as discussed in the preceding paragraph above); (ii) the partially reacted form (i.e., one or more portions of an oligomer or other partially reacted or precursor polymer composition reacted from or otherwise derived from the dianhydride monomer), or (iii) the fully reacted form (one or more portions of a polymer derived from or otherwise derived from the dianhydride monomer).

[0020] The dianhydride may be functionalized with one or more sites, depending on the particular embodiment selected in the practice of the invention. Indeed, the term "dianhydride" is not intended to be limiting (or to be taken literally) with respect to the number of anhydride sites in the dianhydride component. For example, (i), (ii) and (iii) (in the paragraph above) include organic materials that may have two, one or zero anhydride sites, depending on whether the anhydride is in a precursor state or in a reacted state. Instead, the dianhydride component may be functionalized with additional anhydride-type sites (in addition to the anhydride site that reacts with the diamine to give the polymer). Such additional anhydride sites could be used to crosslink the polymer or to give other functional groups to the polymer.

[0021] The polymer film can be prepared using any one of several polymer manufacturing processes. It would be impossible to discuss or describe all possible manufacturing processes useful in the practice of the present invention. It should be understood that the monomer system of the present invention can impart the above-mentioned advantageous properties in a variety of manufacturing processes. The composition of the present invention can be manufactured as described herein, or can be readily manufactured in any of the many (possibly countless) ways by one skilled in the art, using any conventional or non-conventional manufacturing technique.

[0022] Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

[0023] When an amount, concentration or other value or parameter is given as a range, a preferred range or a list of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed from any pair of any upper range or preferred value and any lower range or preferred value, whether or not the ranges are separately disclosed. When a range of numerical values ​​is recited herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within the range. The scope of the present invention is not intended to be limited to the specific values ​​recited when defining the range.

[0024] It should be understood that when describing particular polymers, applicants may refer to the polymers by the monomers used to make them or the amounts of monomers used to make them. Such descriptions may not include the particular nomenclature used to describe the final polymer, or may not include product-by-process terminology, but any such reference to monomers and amounts should be interpreted to mean that the polymer is made from those monomers or amounts of monomers, and the corresponding polymers and their compositions.

[0025] The materials, methods, and examples herein are illustrative only and, except as specifically stated, are not intended to be limiting.

[0026] As used herein, the terms "comprise," "includes," "includes," "including," "having," "having" or any other variations thereof are intended to cover non-exclusive inclusions. For example, a method, process, article, or apparatus that includes a list of elements is not necessarily limited to only those elements and may include other elements not expressly listed or inherent to such method, process, article, or apparatus. Furthermore, unless expressly stated to the contrary, "or" means an inclusive or, not an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and A and B are both true (or exist).

[0027] The use of "a" or "an" is also used to describe elements and components of the present invention. This is done merely for convenience and to give a general sense of the invention. The description should be read to include one or at least one, and the singular also encompasses the plural unless it is clear that this is meant otherwise.

[0028] Although terms such as first, second, third, etc. may be used herein to describe various elements, components, regions, layers, and / or sections, it will be understood that these elements, components, regions, layers, and / or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, and / or section from another element, component, region, layer, and / or section. Thus, a first element, component, region, layer, and / or section may be referred to as a second element, component, region, layer, and / or section without departing from the teachings of the present invention. Similarly, the terms "top" and "bottom" are only relative to each other. If elements, components, layers, etc. are reversed, it will be fully understood that what was "bottom" before being reversed will be "top" after being reversed, and vice versa. When an element is said to be "on" or "disposed on" another element, it means that it is located above or below the object part, but does not inherently mean that it is located on the upper side of the object part based on the direction of gravity; it may be directly on the other element, or there may be intervening elements in between. In contrast, when an element is said to be "directly on" or "directly disposed on" another element, there are no intervening elements present.

[0029] Furthermore, when an element, component, region, layer and / or region is said to be "between" two elements, components, regions, layers and / or regions, it will be understood that it may be the only element, component, region, layer and / or region between the two elements, components, regions, layers and / or regions or that one or more intervening elements, components, regions, layers and / or regions may also be present.

[0030] Organic solvents Useful organic solvents for the synthesis of the polymers of the present invention are preferably capable of dissolving the polymer precursor materials. Such solvents should also have a relatively low boiling point, such as less than 225°C, so that the polymers can be dried at moderate (i.e., more convenient and less costly) temperatures. Boiling points less than 210, 205, 200, 195, 190, or 180°C are preferred.

[0031] Useful organic solvents include N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), methyl ethyl ketone (MEK), dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetramethylurea (TMU), glycol ethyl ether, diethylene glycol diethyl ether, 1,2-dimethoxyethane (monoglyme), diethylene glycol dimethyl ether (diglyme), 1,2-bis(2-methoxyethoxy)ethane (triglyme), gamma-butyrolactone and bis(2-methoxyethyl)ether, tetrahydrofuran (THF), ethyl acetate, hydroxyethyl acetate glycol monoacetate, acetone and mixtures thereof. In one embodiment, preferred solvents include N-methylpyrrolidone (NMP) and dimethylacetamide (DMAc).

[0032] Dicarbonyl Halides In one embodiment, a dicarbonyl halide suitable for forming the polymer can have Formula I:

[0033] [ka]

[0034] During the ceremony, X and Y are the same or different in each occurrence and are independently selected from the group consisting of fluorine, chlorine, and bromine; R1-R4 are the same or different in each occurrence and are independently selected from the group consisting of hydrogen and alkyl, wherein alkyl is C1-12 and linear or branched; B and B' are the same or different in each occurrence and are alicyclic or aromatic groups, provided that at least one of B and B' is an alicyclic group; x and y are the same or different and are integers from 0 to 12; and n is an integer from 0 to 4.

[0035] In one embodiment, the alicyclic groups of B and B' can include a phenyl group having two connecting bonds, which can be in the ortho, meta, or para positions relative to each other, for example, as follows:

[0036] [ka]

[0037] In one embodiment, the alicyclic groups of B and B' can include a saturated carbocyclic ring structure having 3 to 16 carbons (C3-C16) and two connecting bonds, each of which can be attached to any carbon on the ring, for example, as follows:

[0038] [ka]

[0039] In certain embodiments, n=0 and B is a saturated C4-C9 alicyclic group. In more specific embodiments, n=0 and B is a saturated C6 alicyclic group.

[0040] In one embodiment, the alicyclic groups of B and B' can include an unsaturated carbocyclic ring structure having 5-22 carbons (C5-C22), one or more unsaturated bonds anywhere in the ring structure (provided that the ring structure is non-aromatic), and two connecting bonds, each of which can be attached to any carbon on the ring, for example, as follows:

[0041] [ka]

[0042] In one embodiment, the alicyclic groups of B and B' can include bicyclic groups such as, for example, saturated or unsaturated structures having seven or eight carbons (C7 or C8) as follows:

[0043] [ka]

[0044] The term "non-aromatic," as used herein to describe an alicyclic carbocyclic ring structure, is intended to mean that at least one carbon in the ring has two single bonds to adjacent carbons in the ring, i.e., the ring has at least one quaternary carbon.

[0045] In one embodiment, to prepare dicarbonyl chlorides (i.e., X=Y=chlorine), dicarboxylic acids in dichloromethane (DCM) can be treated with a chlorinating reagent such as oxalyl chloride or thionyl chloride, followed by catalytic amounts of dimethylformamide (DMF). The mixture can be heated at a sufficient external temperature (e.g., 63° C.) for a sufficient time (e.g., several hours), after which the reaction can be concentrated in vacuo to obtain a solid. Recrystallization from a suitable solvent (e.g., hexane) provides the purified product. In another embodiment, a brominating reagent such as phosphorus tribromide or dibromotriphenylphosphorane can be used in place of the chlorinating reagent to generate dicarbonyl bromides (i.e., X=Y=bromine). In yet another embodiment, a fluorinating reagent such as 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride or (diethylamino)sulfur trifluoride can be used to generate dicarbonyl fluorides (i.e., X=Y=fluorine).

[0046] Diamine In one embodiment, suitable diamines for forming the polymer can include aliphatic diamines such as 1,2-diaminoethane, 1,6-diaminohexane (HMD), 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane (DMD), 1,11-diaminoundecane, 1,12-diaminododecane (DDD), 1,16-hexadecamethylenediamine, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, trans-1,4-diaminocyclohexane (CHDA), isophoronediamine (IPDA), bicyclo[2.2.2]octane-1,4-diamine, and combinations thereof. Other aliphatic diamines suitable for the practice of the present invention include those having 6 to 12 carbon atoms or combinations of long and short chain diamines, so long as both the malleability and flexibility of the polymer are maintained. Long chain aliphatic diamines may provide increased flexibility.

[0047] In one embodiment, suitable diamines for forming the polymer can include alicyclic diamines (which can be fully or partially saturated) such as cyclobutane diamines (e.g., cis- and trans-1,3-diaminocyclobutane, 6-amino-3-azaspiro[3.3]heptane and 3,6-diaminospiro[3.3]heptane), bicyclo[2.2.1]heptane-1,4-diamine, isophorone diamine and bicyclo[2.2.2]octane-1,4-diamine. Other alicyclic diamines can include cis-1,4-cyclohexanediamine, trans-1,4-cyclohexanediamine, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine) and bis(aminomethyl)norbornane.

[0048] In one embodiment, suitable diamines for forming the polymer include 2,2'-bis(trifluoromethyl)benzidine (TFMB), trifluoromethyl-2,4-diaminobenzene, trifluoromethyl-3,5-diaminobenzene, 2,2'-bis(4-aminophenyl)hexafluoropropane, 4,4'-diamino-2,2'-trifluoromethyldiphenyloxide, 3,3'-diamino-5,5'-trifluoromethyldiphenyloxide, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-trifluoromethyldiphenyloxide, 5,5 ... 4,4'-Oxy-bis[(2-trifluoromethyl)benzenamine] (1,2,4-OBABTF), 4,4'-Oxy-bis[(3-trifluoromethyl)benzenamine], 4,4'-Thio-bis[(2-trifluoromethyl)benzenamine], 4,4'-Thiobis[(3-trifluoromethyl)benzenamine], 4,4'-Sulfoxyl-bis[(2-trifluoromethyl)benzenamine], 4,4'-Sulfoxyl-bis[(3-trifluoromethyl)benzenamine] , 4,4'-keto-bis[(2-trifluoromethyl)benzenamine], 1,1-bis[4'-(4''-amino-2''-trifluoromethylphenoxy)phenyl]cyclopentane, 1,1-bis[4'-(4''-amino-2''-trifluoromethylphenoxy)phenyl]cyclohexane, 2-trifluoromethyl-4,4'-diaminodiphenyl ether, 1,4-(2'-trifluoromethyl-4',4''-diaminodiphenoxy)benzene, 1,4-bis(4'-aminophenoxy)-2-[(3',5'-dito 1,4-bis[2'-cyano-3'(''4-aminophenoxy)phenoxy]-2-[(3',5'-ditrifluoromethyl)phenyl]benzene (6FC-diamine), 3,5-diamino-4-methyl-2',3',5',6'-tetrafluoro-4'-trifluoromethyldiphenyloxide, 2,2-bis[4'(4''-aminophenoxy)phenyl]phthalein-3',5'-bis(trifluoromethyl)anilide (6FADAP) and 3,3',5,5'-tetrafluoro-4,Fluorinated aromatic diamines such as 4'-diamino-diphenylmethane (TFDAM) are also included.

[0049] Other diamines useful for forming polymers include p-phenylenediamine (PPD), m-phenylenediamine (MPD), 2,5-dimethyl-1,4-diaminobenzene, 2,5-dimethyl-1,4-phenylenediamine (DPX), 2,2-bis(4-aminophenyl)propane, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 4,4'-diaminobiphenyl, 4,4''-diaminoterphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminophenyl benzoate, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane (MDA), 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone (BAPS), 4,4'-bis(aminophenoxy)biphenyl (BAPB), 4,4'-diaminodiphenyl ether (ODA), 3,4'-di Aminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-isopropylidenedianiline, 2,2'-bis(3-aminophenyl)propane, N,N-bis(4-aminophenyl)-n-butylamine, N,N-bis(4-aminophenyl)methylamine, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, m-aminobenzoyl-p-aminoanilide, 4-aminophenyl-3-aminobenzoate, N,N-biphenyl Examples of suitable diamines include bis(4-aminophenyl)aniline, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,4-diamine-5-chlorotoluene, 2,4-diamine-6-chlorotoluene, 2,4-bis-(β-amino-t-butyl)toluene, bis-(p-β-amino-t-butylphenyl)ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, m-xylylenediamine and p-xylylenediamine.

[0050] Other useful diamines for forming the polymer include 1,2-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene (RODA), 1,2-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1-(4-aminophenoxy)-3-(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1-(4-aminophenoxy)-4-(3-aminophenoxy)benzene, 2,2-bis(4-[4-aminophenoxy]phenyl)propane (BAPP), 2,2'-bis(4-phenoxyaniline)isopropylidene, 2,4,6-trimethyl-1,3-diaminobenzene, and 2,4,6-trimethyl-1,3-diaminobenzene.

[0051] dianhydride In one embodiment, any number of suitable dianhydrides can be used to form the polymer. The dianhydrides can be used in their tetraacid form (or as mono-, di-, tri- or tetraesters of the tetraacid) or as their diester acid halides (chlorides). However, in some embodiments, the dianhydride forms can be preferred, as they are generally more reactive than the acids or esters.

[0052] Examples of suitable dianhydrides include 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2-(3',4'-dicarboxyphenyl)-5,6-dicarboxybenzimidazole dianhydride, 2-(3',4'-dicarboxyphenyl)-5,6-dicarboxybenzoxazole dianhydride, and 2-(3',4'-dicarboxyphenyl)-5,6-dicarboxybenzoxazole dianhydride. dianhydride, 2-(3',4'-dicarboxyphenyl)-5,6-dicarboxybenzothiazole dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, bicyclo[2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic acid-2,3,5,6-dianhydride, 4,4'-thiodiphthalic anhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)sulfoxide dianhydride (DSDA), bis(3,4-dicarboxyphenyloxadiazole-1,3,4)-p-phenylene dianhydride, bis(3,4-dicarboxyphenyl)-2,5-oxadiazole-1,3,4- Dianhydride, Bis-2,5-(3',4'-dicarboxydiphenyl ether)-1,3,4-oxadiazole dianhydride, 4,4'-oxydiphthalic anhydride (ODPA), Bis(3,4-dicarboxyphenyl)thioether dianhydride, Bisphenol A dianhydride (BPADA), Bisphenol S dianhydride, Bis-1,3-isobenzofuran dione, 1,4-bis(4,4'-oxyphthalic anhydride)benzene, Bis(3,4-dicarboxyphenyl cyclopentadienyl tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, pyromellitic dianhydride (PMDA), tetrahydrofuran tetracarboxylic dianhydride, 1,3-bis(4,4'-oxydiphthalic anhydride)benzene, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride Examples of suitable dianhydrides include tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride and thiophene-2,3,4,5-tetracarboxylic dianhydride.

[0053] In one embodiment, suitable dianhydrides may include alicyclic dianhydrides such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA), hexahydro-4,8-ethano-1H,3H-benzo[1,2-c:4,5-c']difuran-1,3,5,7-tetrone (BODA), 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic 1,4:2,3-dianhydride (TCA), and meso-butane-1,2,3,4-tetracarboxylic dianhydride. In one embodiment, the alicyclic dianhydride may be present in an amount up to about 70 mole percent, based on the total dianhydride content of the polymer.

[0054] In one embodiment, suitable dianhydrides for forming the polymer can include fluorinated dianhydrides such as 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 9,9-bis(trifluoromethyl)-2,3,6,7-xanthenetetracarboxylic dianhydride.

[0055] In one embodiment, when the polymer further comprises an additional aromatic amide component, suitable additional dicarbonyl chlorides for forming the polymer can include terephthaloyl chloride (TPCI), isophthaloyl chloride (IPCI), biphenyldicarbonyl chloride (BPCI), naphthalene dicarbonyl chloride, terphenyldicarbonyl chloride, 2-fluoro-terephthaloyl chloride, and trimellitic anhydride.

[0056] In one embodiment, poly(amide-ester-imide)s can be formed from polyols that can be reacted with carboxylic acids or ester acid halides to form ester linkages.

[0057] The dihydric alcohol component can be almost any alcoholic diol that contains two esterifiable hydroxyl groups. It can also include mixtures of suitable diols. Diols suitable for use herein include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and the like.

[0058] The polyhydric alcohol component can be almost any polyhydric alcohol that contains at least three hydroxyl groups that can be esterified to provide the advantages of the above-mentioned synthesis process of the present invention. Mixtures of such polyhydric alcohols can be suitably used. Suitable polyhydric alcohols include, for example, tris(2-hydroxyethyl)isocyanurate, glycerin, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, and mixtures thereof.

[0059] In some cases, useful diamine and dianhydride monomers contain ester groups. Examples of these monomers include diamines such as 4-aminophenyl-4-aminobenzoate and 4-amino-3-methylphenyl-4-aminobenzoate, and dianhydrides such as p-phenylene bis(trimellitate) dianhydride.

[0060] In some cases, useful diamine and dianhydride monomers contain amide groups. Examples of these monomers include diamines such as 4,4'-diaminobenzamide (DABAN) and dianhydrides such as N,N'-(2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diyl)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide) and N,N'-(9H-fluoren-9-ylidene-4,1-phenylene)bis[1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxamide].

[0061] Higher order copolymers having imide groups can include any of the above monomers.

[0062] Polymer Film Polymer films made from the poly(amide-imide) and poly(amide-ester-imide) compositions of the present invention may have improved properties compared to polyimide films and may be useful in a wide range of applications. For example, improved mechanical properties may be the result of interchain interactions of the amide-containing polymer backbone. One such interaction is hydrogen bonding between amide protons on one chain and sites on an adjacent chain. These interactions typically result in improved modulus and may possibly result in lower coefficient of thermal expansion (CTE), improved tear resistance and improved resistance to microcracking. Improved modulus and CTE are particularly useful, for example, in flexible printed circuits, solar cell substrates and thin film transistor substrates. The use of alicyclic groups, which can disrupt charge transfer that can result in coloration, combined with low temperature processing, may further improve the optical properties of these compositions and may be very useful for colorless TFT substrates, cover windows and touch sensor panel substrate applications in foldable displays.

[0063] In one embodiment, a polymer film comprising a poly(amide-imide) composition can be produced by combining a dicarbonyl halide, a diamine, and a dianhydride (in the form of a monomer or other polymer precursor) together with a solvent to form a poly(amide-amic) acid solution. The molecular weight of the poly(amide-amic acid) formed therefrom can be controlled by adjusting the molar ratio of the dicarbonyl halide and dianhydride to the diamine. In one embodiment, a polymer film comprising a poly(amide-ester-imide) composition can be produced by combining a dicarbonyl halide, a polyol, a diamine, and a dianhydride (in the form of a monomer or other polymer precursor) together with a solvent to form a poly(amide-ester-amic) acid solution.

[0064] In one embodiment, the poly(amide-amic) acid casting solution is derived from a poly(amide-amic) acid solution. The poly(amide-amic) acid casting solution and / or the poly(amide-amic) acid solution can be optionally combined with a conversion chemical such as (i) one or more dehydrating agents, such as fatty acid anhydrides (such as acetic anhydride) and / or aromatic acid anhydrides; and (ii) one or more catalysts, such as aliphatic tertiary amines (such as triethylamine), aromatic tertiary amines (such as N,N-dimethylaniline), and heterocyclic tertiary amines (such as pyridine, picoline, isoquinoline). The anhydride dehydrating material is often used in molar excess compared to the amount of amic acid groups of the poly(amide-amic) acid. The amount of acetic anhydride used is typically about 2.0 to 4.0 moles per equivalent (repeating unit) of poly(amide-amic) acid. Generally, an equivalent amount of tertiary amine catalyst is used.

[0065] In one embodiment, the conversion chemical can be an imidization catalyst (sometimes called an "imidization promoter") that can help lower the imidization temperature and shorten the imidization time. Typical imidization catalysts can range from bases such as imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, benzimidazole, isoquinoline, methylpyridine, substituted pyridines such as lutidine, and trialkylamines, as well as hydroxy acids such as isomers of hydroxybenzoic acid. The ratio of these catalysts and their concentrations in the poly(amide-amic) acid layer will affect the imidization reaction rate and film properties.

[0066] In one embodiment, the poly(amide-amic) acid solution and / or the poly(amide-amic) acid casting solution is dissolved in an organic solvent at a concentration of from about 5.0 or 10% by weight to about 15, 20, 25, 30, 35, or 40% by weight.

[0067] The solvated mixture (poly(amide-amic) acid casting solution) can then be cast or coated onto a support such as an endless belt or rotating drum to obtain a film. Alternatively, it can be cast onto a polymeric support such as PET, other forms of Kapton® polyimide film (e.g., Kapton® HN or Kapton® OL film) or other polymeric support. The solvent-containing film can then be converted into a self-supporting film by heating at an appropriate temperature (thermal curing). The film can then be separated from the support, stretched, such as by tentering, and continued heating (drying and curing) to obtain a polymeric film.

[0068] Useful methods for producing polymeric films comprising poly(amide-imide) or poly(amide-ester-imide) can be found in U.S. Pat. No. 5,399,433 and U.S. Pat. No. 5,499,463, which are incorporated herein by reference for all their teachings. Various modifications are possible and can be used in the present invention, such as the following: (a) The diamine component, the dianhydride component and the dicarbonyl halide component are premixed together and then added portionwise to the solvent while the mixture is being stirred. (b) A method (as opposed to (a) above) in which a solvent is added to a stirred mixture of the diamine, anhydride and dicarbonyl halide components. (c) A method in which the diamine is dissolved exclusively in a solvent and then the dianhydride and dicarbonyl halide components are added thereto in a ratio which makes it possible to control the reaction rate. (d) A method in which the dianhydride component and the dicarbonyl halide component are dissolved or dispersed exclusively in a solvent and then the amine component is added thereto in a ratio which makes it possible to control the reaction rate. (e) A process in which the diamine component, the dianhydride component and the dicarbonyl halide component are dissolved or dispersed separately in a solvent and then these solutions are mixed in a reactor. (f) A process in which a poly(amide-amic) acid containing an excess of an amine component and another poly(amide-amic) acid containing an excess of a dianhydride or dicarbonyl halide component are preformed and then reacted with each other in a reactor in a manner that allows, inter alia, to form nonrandom or block copolymers. (g) A particular portion of the amine, dianhydride or dicarbonyl halide components is reacted first and then the remaining diamine components are reacted, or vice versa. (h) A method in which a conversion chemical (catalyst) is mixed with a poly(amide-amic) acid to form a poly(amide-amic) acid casting solution which is then cast to form a gel film. (i) A process in which the ingredients are added, either partially or as a whole, in any order, either in some or all of the solvent, and any or all of the ingredients may be added as a solution in some or all of the solvent. (j) A method in which one of the dianhydride and dicarbonyl halide components is first reacted with one of the diamine components to give a first poly(amide-amic) acid, and then another dianhydride and dicarbonyl halide component is reacted with another amine component to give a second poly(amide-amic) acid, which are then combined in any one of several ways prior to film formation.

[0069] In one embodiment, the poly(amide-amic) acid solution can be heated, optionally in the presence of an imidization catalyst, to partially or fully imidize the poly(amide-amic) acid and convert it to a polymer having imide groups. The temperature, time, and concentration and selection of the imidization catalyst can affect the degree of imidization of the poly(amide-amic) acid solution. Preferably, the solution should be fully imidized. In one embodiment, in a fully polymerized solution, more than 85%, more than 90%, or more than 95% of the amic acid groups are converted to a polymer having imide groups, as determined by infrared spectroscopy.

[0070] In one embodiment, the solvated mixture (fully imidized solution) can be cast to form a polymer film. In another embodiment, the solvated mixture (first fully imidized solution) can be precipitated with a poor solvent such as water or alcohol (e.g., methanol, ethanol, isopropyl alcohol), and a solid polymer resin can be isolated. For example, isolation can be achieved by filtration, decantation, centrifugation and decantation of the supernatant, distillation or gas phase solvent removal, or other known methods for separating a solid precipitate from a slurry. In one embodiment, the precipitate can be washed to remove the catalyst. After washing, the precipitate can be sufficiently dried, but need not be completely dried. The polymer precipitate can be redissolved in a second solvent, such as methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), ethyl acetate, methyl acetate, ethyl formate, methyl formate, tetrahydrofuran, acetone, DMAc, NMP, and mixtures thereof, to form a second fully imidized solution (casting solution), which can be cast to form a polymer film.

[0071] In one embodiment, fully polymerized solutions are formed using monomers (diamines, dianhydrides or dicarbonyl halides) that have structural features important for solubility, including, but not limited to, flexible linkages such as aliphatic spacers, ethers, thioethers, substituted amines, amides, esters and ketones, weak intermolecular interactions, bulky substituents, non-resonant, non-linear and asymmetric.

[0072] In one embodiment, the solvated mixture (fully imidized solution) can be mixed with a crosslinked precursor and a colorant, such as a pigment or dye, and then cast to form a polymer film. In one embodiment, the colorant can be low conductivity carbon black. In another embodiment, the solvated mixture (first fully imidized solution) can be precipitated with a poor solvent, such as water or an alcohol (e.g., methanol, ethanol, isopropyl alcohol). In one embodiment, the precipitate can be washed to remove the catalyst. After washing, the precipitate can be dried thoroughly, but not completely. The polymer precipitate can be redissolved in a second solvent, such as methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), tetrahydrofuran (THF), cyclopentanone, ethyl acetate, acetone, DMAc, NMP, and mixtures thereof, to form a second fully imidized solution (cast solution). A crosslinked precursor and a colorant can be added to the second fully imidized solution and then cast to form a polymer film. In one embodiment, the polymer film comprises in the range of about 80 to about 99% by weight of crosslinked polymer. In some embodiments, the polymer film comprises between about 80, 85, 90, 95, and 99 weight percent crosslinked polymer, inclusive, hi yet other embodiments, the polymer film comprises between about 91 and about 98 weight percent crosslinked polymer.

[0073] In one embodiment, the fully imidized polymer solution can be cast or coated onto a support such as an endless belt or rotating drum to form a film. Alternatively, it can be cast onto a polymeric support such as PET, other forms of Kapton® polyimide film (e.g., Kapton® HN or Kapton® OL film) or other polymeric support. The solvent-containing film can then be converted to a film by heating to partially or completely remove the solvent. In some aspects of the invention, the film is separated from the support before being completely dried. A final drying step can be performed along with dimensional support or stabilization of the film. In other aspects, the film is heated directly on the support.

[0074] The casting solution may further include any one of several additives, such as processing aids (e.g., oligomers), antioxidants, light stabilizers, flame retardant additives, antistatic agents, heat stabilizers, UV absorbers, inorganic fillers, or various reinforcing agents. Inorganic fillers may include thermally conductive fillers, conductive fillers such as metal oxides, inorganic nitrides, and metal carbides, as well as metals. Common inorganic fillers are alumina, silica, diamond, clay, talc, sepiolite, boron nitride, aluminum nitride, titanium dioxide, dicalcium phosphate, and fumed metal oxides. Low color organic fillers, such as polydialkylfluorenes, may also be used. Common organic fillers include polyaniline, polythiophenes, polypyrroles, polyphenylenevinylenes, polydialkylfluorenes, carbon black, graphite, multi-walled and single-walled carbon nanotubes, and carbon nanofibers. In one embodiment, nanoparticle fillers and nanoparticle colloids may be used.

[0075] In one embodiment, the conductive filler is carbon black. In one embodiment, the conductive filler is selected from the group consisting of acetylene black, ultra-abrasive furnace black, conductive furnace black, conductive channel type black, carbon nanotubes, carbon fibers, fine thermal black, and mixtures thereof. As described above for low conductivity carbon black, oxygen complexes on the surface of carbon particles act as an electrical insulating layer. Therefore, low volatile content is generally desirable for high conductivity. However, the difficulty of dispersing carbon black must also be considered. Surface oxidation aids in the deagglomeration and dispersion of carbon black. In some embodiments, when the conductive filler is carbon black, the carbon black has a volatile content of 1% or less.

[0076] The filler may have a size of less than 550 nm in at least one dimension. In other embodiments, the filler may have a size of less than 500, less than 450, less than 400, less than 350, less than 300, less than 250, or less than 200 nm (fillers may have a variety of shapes in any dimension, and filler shapes may vary along any dimension, so "at least one dimension" is intended to be a numerical average along that dimension). The average aspect ratio of the filler may be 1 or greater. In some embodiments, the submicron filler is selected from the group consisting of acicular fillers (acicular), fibrous fillers, platelet-like fillers, polymeric fibers, and mixtures thereof. In one embodiment, the submicron filler is substantially non-agglomerated. The submicron filler may be hollow, porous, or solid. In one embodiment, the submicron fillers of the present disclosure exhibit an aspect ratio of at least 1, at least 2, at least 4, at least 6, at least 8, at least 10, at least 12, or at least 15 to 1.

[0077] In some embodiments, the size of the submicron filler is 100 nm or less. In some embodiments, the filler is spherical or ellipsoidal in shape and is a nanoparticle. In one embodiment, the submicron filler can include inorganic oxides such as oxides of silicon, aluminum and titanium, hollow (porous) silicon oxide, antimony oxide, zirconium oxide, indium tin oxide, antimony tin oxide, mixed titanium / tin / zirconium oxide, and binary, ternary, quaternary and higher composite oxides of one or more cations selected from silicon, titanium, aluminum, antimony, zirconium, indium, tin, zinc, niobium and tantalum. In one embodiment, nanoparticle composites (e.g., single or multiple core / shell structures) can be used, in which one oxide encapsulates another oxide in one particle.

[0078] In one embodiment, the submicron fillers can include boron nitride, aluminum nitride, ternary or higher compounds containing boron, aluminum and nitrogen, gallium nitride, silicon nitride, aluminum nitride, zinc selenide, zinc sulfide, zinc telluride, silicon carbide, and combinations thereof or other ceramic compounds such as higher compounds containing multiple cations and multiple anions.

[0079] In one embodiment, the solid silicon oxide nanoparticles can be produced from a silicon oxide sol (e.g., a colloidal dispersion of solid silicon oxide nanoparticles in a liquid medium), particularly a sol of amorphous, semicrystalline and / or crystalline silica. Such sols can be prepared by various techniques and in various forms, such as hydrosols (i.e., water serves as the liquid medium), organosols (i.e., an organic liquid serves as the liquid medium), and mixed sols (i.e., the liquid medium includes both water and an organic liquid). See, for example, the descriptions of the techniques and forms disclosed in (Patent Document 3), (Patent Document 4), and (Patent Document 5). In one embodiment, the nanoparticles are suspended in a polar aprotic solvent, such as DMAc or other solvents that are compatible with poly(amide-amic) acids. In another embodiment, the solid nanosilica particles are prepared from, for example, DMAC-ST (Nissan Chemical America Corporation, Houston TX), which contains less than 0.5 percent water, has 20-21 wt. % SiO2, and has a median diameter d of the nanosilica particles. 50 It can be obtained commercially as a colloidal dispersion or sol dispersed in a polar aprotic solvent, such as a solid silica colloid in dimethylacetamide, having a diameter of about 16 nm.

[0080] In one embodiment, the submicron filler may be porous and may have pores of any shape. One example is when the pores include voids (e.g., voids containing air) of lower density and lower refractive index formed in a shell of an oxide such as silicon oxide, i.e., hollow silicon oxide nanoparticles. The thickness of the shell of the submicron filler affects the strength of the submicron filler. As the hollow silicon oxide particles are brought into a state with a reduced refractive index and increased porosity, the shell thickness decreases, resulting in a decrease in the strength (i.e., fracture resistance) of the submicron filler. Methods for producing such hollow silicon oxide nanoparticles are known, for example, as described in (Patent Document 6) and (Patent Document 7). Hollow silicon oxide nanoparticles can be obtained from JGC Catalysts and Chemicals Co., Ltd., Japan.

[0081] In one embodiment, the submicron filler can be coated with a coupling agent. For example, the nanoparticles can be coated with an acrylic or methacrylic coupling agent derived from aminosilane, phenylsilane, or the corresponding alkoxysilane. A trimethylsilyl surface capping agent can be introduced to the nanoparticle surface by reaction of the submicron filler with hexamethyldisilazane. In one embodiment, the submicron filler can be coated with a dispersing agent. In one embodiment, the submicron filler can be coated with a combination of a coupling agent and a dispersing agent. Alternatively, the coupling agent, dispersing agent, or a combination thereof can be directly incorporated into the polymer film and not necessarily coated on the submicron filler.

[0082] In some embodiments, a coextrusion process can be used to form a multilayer polymer film having an inner core layer sandwiched between two outer layers. In this process, the finished poly(amide-amic) acid solution is filtered and pumped to a slot die, where the flow is split in such a way as to form the first and second outer layers of the three-layer coextruded film. In some embodiments, the second flow of polymer is filtered and then pumped to a casting die in such a way as to form the central core layer of the three-layer coextruded film. The flow rate of the solution can be adjusted to achieve the desired layer thickness. In one embodiment, the polymers in all three layers can be the same or different.

[0083] In some embodiments, the multilayer film is prepared by co-extruding the first outer layer, the core layer, and the second outer layer. In some embodiments, the layers are extruded through a single-cavity or multiple-cavity extrusion die. In another embodiment, the multilayer film is produced using a single-cavity die. If a single-cavity die is used, the laminar flow of the stream should be of high enough viscosity to prevent mixing of the streams and provide uniform stratification. In some embodiments, the multilayer film is prepared by casting from a slot die onto a moving stainless steel belt. In one embodiment, the belt is then passed through a convection oven to evaporate the solvent and partially imidize the polymer to provide a "green" film. The green film can be stripped from the casting belt and wound up. The green film can then be passed through a tenter oven to provide a fully cured polymer film. In some embodiments, shrinkage can be minimized during tentering by restraining the film along the edges (i.e., using clips or pins).

[0084] The thickness of the polymer film can be adjusted depending on the intended purpose or end use specifications of the film. In one embodiment, the polymer film has a total thickness in the range of about 10 to about 80 μm, or about 10 to about 25 μm, or about 15 to about 25 μm.

[0085] In one embodiment, the polymer film has a tensile modulus of at least 4.0 GPa, or at least 4.5 GPa, or at least 5.0 GPa, or at least 5.5 GPa, or at least 6.0 GPa, or at least 6.5 GPa.

[0086] In one embodiment, the polymer film has a coefficient of thermal expansion (CTE) of 50 ppm / °C or less, or 45 ppm / °C or less, or 40 ppm / °C or less, or 35 ppm / °C or less, or 30 ppm / °C or less over a temperature range of 50 to 250°C.

[0087] In one embodiment, the polymeric film has a b* of less than about 1.25, or less than about 1.0, or less than about 0.8 at a film thickness of about 25 μm when measured in full transmission mode over the wavelength range of 360-780 nm on a dual beam spectrophotometer using D65 illumination and a 10° observer. In one embodiment, the polymeric film has a yellowness index (YI) of less than about 2.25, or less than about 2.0, or less than about 1.75 at a film thickness of about 25 μm when measured using the procedure set forth in ASTM E313.

[0088] In one embodiment, the curable resin coating composition can be applied to a polymer film layer. In some embodiments, the curable resin coating composition can be applied to an article comprising a polymer film layer and an inorganic substrate, where the curable resin coating composition is applied to the polymer film layer on the side opposite the surface of the inorganic substrate. In one embodiment, the curable resin coating composition comprises at least one curable oligomer and at least one organic coating solvent. A suitable curable oligomer is any curable oligomer that forms a hard coat layer upon curing. As used herein, the term "hard coat" refers to a material, coating, or layer on a substrate that forms a film upon curing having a pencil hardness greater than that of the substrate. Such a hard coat layer protects the underlying substrate from mechanical abrasion and abrasion, and optionally enhances the self-cleaning properties of the surface.

[0089] Suitable curable oligomers useful in the curable resin coating composition include, but are not limited to, (meth)acrylate oligomers, urethane oligomers, (meth)acrylate-urethane oligomers, siloxane oligomers, and combinations thereof. Liquid curable oligomers are preferred. Suitable (meth)acrylate oligomers include, but are not limited to, oligomers that contain one or more (meth)acrylate monomers as polymerized units selected from aliphatic monofunctional (meth)acrylate monomers and aliphatic multifunctional (meth)acrylate monomers. The curable oligomer is preferably selected from (meth)acrylate oligomers, (meth)acrylate-urethane oligomers, siloxane oligomers, and combinations thereof, more preferably from (meth)acrylate-urethane oligomers and siloxane oligomers.

[0090] In some embodiments, the curable resin coating composition can include a siloxane oligomer. Suitable siloxane oligomers are those disclosed in U.S. Patent Nos. 5,991, 6,133, 6,141, 6,151, 6,162, 6,171, 6,182, 6,193, 7,146, 7,196, 7,197, 7,198, 7,

[0091] metal clad laminate In one embodiment, the conductive layer of the present invention comprises: i. Metal sputtering (optionally followed by electroplating); ii. foil lamination; and / or iii. Any conventional or non-conventional method for applying a thin metal layer to a substrate. can be brought about by

[0092] Metal clad laminates can be formed as single-sided or double-sided laminates by any number of well-known processes. In one embodiment, a lamination process can be used to form a metal clad laminate with a polymer film or multi-layer polymer film. In one embodiment, a first outer layer comprising a first thermoplastic polymer is placed between a first conductive layer and a core layer, and a second outer layer comprising a second thermoplastic polymer is placed on the opposite side of the core layer. In one embodiment, a second conductive layer is placed in contact with the second outer layer on the opposite side of the core layer. One advantage of this type of construction is that the lamination temperature of the multi-layer film is reduced to the lamination temperature required for the thermoplastic polyimide of the outer layer to bond to the conductive layer. In one embodiment, the conductive layer is a metal layer.

[0093] For example, the polymer film can be subjected to a pretreatment process before the process of applying the polymer film onto the metal foil. The pretreatment process can include heat treatment, corona treatment, plasma treatment under atmospheric pressure, plasma treatment under reduced pressure, treatment with coupling agents such as silanes and titanates, sandblasting, alkali treatment, acid treatment, and coating with polyamic acid. In order to improve the adhesive strength, it is also generally possible to add various metal compounds, such as those disclosed in (Patent Document 12); (Patent Document 13); (Patent Document 14); and (Patent Document 15), which are incorporated herein by reference.

[0094] In addition, conductive metal surfaces may be treated (for the purpose of improving adhesion) with a variety of organic and inorganic treatments, including the use of silanes, imidazoles, triazoles, oxide and reduced oxide treatments, tin oxide treatments, and surface cleaning / roughening with acid or alkaline reagents (called microetching).

[0095] In further embodiments, the poly(amide-amic) acid precursor (of the polymer film of the present invention) can be coated onto a fully cured polymer base film or directly onto a metal substrate and then imidized by heat treatment. The polymer base film can be prepared by either a chemical or thermal conversion process and can be surface treated to improve adhesion, for example, by chemical etching, corona treatment, laser etching, etc.

[0096] As used herein, the terms "conductive layer" and "conductive foil" refer to a metal layer or foil (a thin composition having at least 50% of the conductivity of high-grade copper). The conductive foil is typically a metal foil. Metal foils do not have to be used as elements in pure form, they can also be used as metal foil alloys, such as copper alloys containing nickel, chromium, iron and other metals. The conductive layer can be an alloy of metals and is typically applied to the polymer of the present invention by a sputtering step followed by an electroplating step. In these types of processes, a metal seed coat layer is first sputtered onto the polymer film. Finally, a thicker coating of metal is applied to the seed coat by electroplating or electrodeposition. Such sputtered metal layers can be hot pressed even above the glass transition temperature of the polymer for enhanced peel strength.

[0097] Particularly suitable metal substrates are rolled annealed copper or rolled annealed copper alloy foils. It has been found to be advantageous in many cases to pretreat the metal substrate before coating. This pretreatment may include, but is not limited to, electrodeposition or immersion deposition onto the metal of thin layers of copper, zinc, chromium, tin, nickel, cobalt, other metals and alloys of these metals. The pretreatment may consist of a chemical or mechanical roughening treatment. It has been found that this pretreatment allows the adhesion and therefore the peel strength of the polyimide layer to be further increased. Apart from roughening the surface, the chemical pretreatment may also result in the formation of metal oxide groups, which also allows for a further increase in the adhesion of the metal to the polymer layer. This pretreatment may be applied to both sides of the metal, allowing for enhanced adhesion to the substrate on both sides.

[0098] In one embodiment, the metal clad laminate may include a polymer film, which may be a monolayer film or a multilayer film, and a first metal layer bonded to the outer surface of a first outer layer of the multilayer film. In one embodiment, the metal clad laminate may include a second metal layer bonded to the outer surface of a second outer layer of the multilayer film. In one embodiment, the first metal layer, the second metal layer, or both metal layers may be copper. In one embodiment, the metal clad laminate of the present invention, including double-sided copper clad, may be prepared by laminating copper foil to both sides of a monolayer or multilayer film.

[0099] Purpose In one embodiment, the high tensile strength and low CTE polymeric films can be used in electronic device applications such as flexible device layers for electronic devices or coverlays for printed circuit boards or other electronic components in electronic devices, providing protection from physical damage, oxidation and other contaminants that can adversely affect the functionality of the electronic components. In one embodiment, the polymeric films can be used in flexible display applications such as thin film transistor (TFT) substrates in organic light emitting diode (OLED) displays, touch sensor panels (TSPs) for electronic paper (E-paper) and displays.

[0100] In one embodiment, the polymer film with subdued color and high tensile strength can be used for many layers in electronic device applications, such as organic electronic devices, where a combination of excellent optical and mechanical properties is desired. Non-limiting examples of such layers include device substrates, touch panels, substrates for color filter sheets, cover films, etc. The specific material property requirements for each application are unique and can be addressed by the appropriate composition and processing conditions for the polymer films disclosed herein. Organic electronic devices that can benefit from having a coated film include, but are not limited to, (1) devices that convert electrical energy to radiation (e.g., light emitting diodes, light emitting diode displays, lighting devices, luminaires, or diode lasers), (2) devices that detect signals by electronic processes (e.g., photodetectors, photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes, infrared detectors, biosensors), (3) devices that convert radiation to electrical energy (e.g., photovoltaic devices or solar cells), (4) devices that convert light of one wavelength to light of a longer wavelength (e.g., down-converting phosphor devices); and (5) devices that include one or more electronic components that include one or more organic semiconductor layers (e.g., transistors or diodes).

[0101] In one embodiment, the metal clad laminates with polymer films are particularly useful for flexible printed interconnects or die pad bonding of semiconductor devices or packaging materials for CSP (chip scale package), COF (chip on film), COL (chip on lead), LOC (lead on chip), MCM (multi-chip module), BGA (ball grid array or micro ball grid array) and / or TAB (tape automated bonding).

[0102] In another embodiment, the polymer film is useful for wafer level integrated circuit packaging, where a composite material is fabricated using a polymer film placed between a conductive layer (typically metal) having a thickness of less than 100 μm and a wafer containing multiple integrated circuit dies. In one (wafer level integrated circuit packaging) embodiment, the conductive vias are connected to the dies by conductive vias such as wire bonds, conductive metal or solder bumps, etc.

[0103] The advantageous properties of this invention can be seen by reference to the following examples, which illustrate, but do not limit, the invention. All parts and percentages are by weight unless otherwise specified. EXAMPLES

[0104] Test Method CIE L*, a*, b* color measurements Color measurements were made using a ColorQuest® XE Dual Beam Spectrophotometer (Hunter Associates Laboratory, Inc., Reston, VA) in full transmission mode over the wavelength range of 380-780 nm with D65 illumination and a 10° observer. Haze and transmittance were also measured using this instrument.

[0105] yellowness Yellowness index (YI) was measured using the procedure set forth in ASTM E313.

[0106] Glass transition temperature The glass transition temperature (Tg) is measured using dynamic mechanical analysis (Q800 DMA, TA Instrument) and is determined by tan delta peak.

[0107] Thermal expansion coefficient The coefficient of thermal expansion (CTE) or linear expansion coefficient was measured using dynamic mechanical analysis (Q800 DMA, TA Instrument). CTE was measured in both machine direction (MD) and transverse direction (TD) over a temperature range of 50-250°C. In each case, the samples were cycled through the temperature range twice and the CTE of the second cycle was reported for measurement.

[0108] Tensile Modulus Tensile modulus was measured using the ASTM D882 test method.

[0109] Thickness Film thickness was determined by measuring five locations across the film profile using a contact-type FISCHERSCOPE MMS PC2 Modular Measurement System thickness gauge (Fisher Technology Inc., Windsor, CT).

[0110] Example 1 Cyclohexanedicarbonyl chloride (CHDC) monomer was prepared. To 24.00 g of trans-1,4-cyclohexanedicarboxylic acid in 200 ml of dichloromethane (DCM) in a 1 L round bottom flask fitted with a 20 inch Vigreaux column in a drybox, 300 ml of 2 M oxalyl chloride in DCM was added followed by 2.0 ml of dimethylformamide (DMF). The mixture was heated at 55.5°C. After 23 hours, the reaction was allowed to cool slowly to room temperature. The orange reaction was removed from the glovebox and concentrated in vacuo to give a dark brown orange solid. The crude product was recrystallized (inside the drybox) from 310 ml of hexane. The copper colored undissolved solid was filtered off prior to crystallization. The product was filtered and washed with approximately 100 ml of hexane to give the product as very light tan needles, which were allowed to dry overnight in the anteroom. Yield: 15.2 g (51.5%) of product as very light tan needles.

[0111] In Example 1 (E1), poly(amide-amic) acid was prepared with a monomer composition of CHDC 0.5 / 6FDA 0.5 / / TFMB 1.0. A 1 L four-necked reaction vessel equipped with a PTFE stirring shaft, o-rings, and bearing assembly was heated overnight in a 159°C oven under vacuum and with a nitrogen sweep. The reactor assembly was removed from the oven, assembled while hot, purged with nitrogen, and allowed to cool to room temperature while passing a stream of nitrogen through the assembly. A solution of 34.925 g of 2,2'-bis(trifluoromethyl)benzidine (TFMB, Seika Co., Ltd., Wakayama Seika Kogyo Co., Ltd., Japan) in 454 g of dimethyl acetate anhydride (DMAc) was added to the reaction assembly and heated to 40°C. After the thermometer reached an external temperature of 42.2°C, a solution of 11.288g of CHDC (prepared above) and 23.985g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA, Daikin America, Orangeburg, NY) in 114g of anhydrous DMAc was added dropwise via the addition funnel. After heating for 1 hour, the reaction was stirred at room temperature. After stirring overnight, an additional 0.192g of 6FDA in 2.66g of DMAc was added. After stirring overnight, an additional 0.096g of 6FDA in 0.96g of DMAc was added. After stirring overnight, an additional 0.192g of 6FDA in 1.6g of DMAc was added. After 4 days, an additional 706mg of 6FDA was added. The reaction was 101.4% dicarbonyl-containing monomer. After 2 days, the viscosity was 3,437 centipoise.

[0112] The solution was cast onto a glass substrate at 25° C. to produce a film of approximately 2 mils. A doctor blade was used with a clearance of 40 mm to produce a film of approximately 2 mils after curing. The film on the glass substrate was heated to 50° C. for 30 minutes on a hot plate, then to 90° C. for 30 minutes, after which it was cooled to room temperature. The film was peeled off using a razor, mounted on a 4×8 inch pin frame, and placed in an oven (Carbolite Gero, Sheffield, UK). The oven was then purged with nitrogen and heated according to the following temperature protocol: 25°C to 90°C (7°C / min), hold at 90°C for 5 min; 90°C to 150°C (7°C / min), hold at 150°C for 10 min; 150°C to 320°C (7°C / min), hold at 320°C for 5 min; After heating to 320° C. for 5 minutes, the film was removed from the oven and allowed to cool in air.

[0113] Example 2 In Example 2 (E2), a fully imidized solution was formed by the following procedure: 200 g of the poly(amido-amic) acid solution described in E1 was mixed with 8.87 g of β-picoline (Aldrich Chemicals, St. Louis, Mo.) and 9.72 g of acetic anhydride (Aldrich). The solution was heated to 80° C. for 2 hours and then allowed to cool to room temperature.

[0114] The solution was precipitated by mixing 200 g of the above solution with 500 ml of methanol and washing with methanol. The material was ground in a blender, filtered, and washed twice with an equal amount of methanol. The final powder was dried under vacuum at 50° C. for 24 hours.

[0115] The polymer resin was mixed with DMAc to form a 16.2 wt% solution for casting. The solution was cast onto a glass substrate and heated on a hot plate as described above for E1. The film was peeled off using a razor, attached to a 4×8 inch pin frame, and placed in an oven. The oven was then purged with nitrogen and heated according to the following temperature protocol: 25°C to 90°C (7°C / min), hold at 90°C for 5 min; 90°C to 150°C (7°C / min), hold at 150°C for 10 min; 150°C to 250°C (7°C / min), hold at 250°C for 20 min; After heating to 250° C. for 20 minutes, the film was removed from the oven and allowed to cool in air.

[0116] Example 3 Example 3 (E3) used the polymer resin described above for E2. It was reacted with trimethoxyphenylsilane to form a nanocolloid of silicon oxide of about 30% by weight in DMAc. 2.5 g of the colloid was mixed with a solution of 2.25 g of dry polymer and 16.4545 g of DMAc.

[0117] The solution was cast onto a glass substrate and heated on a hot plate as described above for E1. The film was peeled off using a razor, mounted on a 4x8 inch pin frame, and placed in an oven. The oven was then purged with nitrogen and heated to a final temperature of 250°C as described above for E2. After 20 minutes at 250°C, the film was removed from the oven and allowed to cool in air.

[0118] Example 4 CHDC monomer was prepared. To 31.72 g of trans-1,4-cyclohexanedicarboxylic acid in 500 ml of DCM in a 1 L round bottom flask fitted with a 20 inch Vigreaux column in a drybox, 100 g of oxalyl chloride was added followed by 1.4 ml of DMF. The mixture was heated at 40° C. for 2 hours 35 minutes, then at 45° C. for 2 hours, and allowed to cool to room temperature overnight. The pale yellow reaction was concentrated in vacuo to give an off-white solid. This was recrystallized in a glovebox from approximately 700 ml of hexane (some undissolved solids were present). The deep orange undissolved solids were filtered off while hot, and the filtrate was allowed to cool. The product was filtered and washed with 100 ml of hexane to give off-white crystals. The product was dried overnight at room temperature in the glovebox antechamber, then dried at 50° C. under house vacuum for 17.5 hours. Yield: 15.77g (41%) of product as a light pink / tan off-white solid.

[0119] In Example 4 (E4), a poly(amide-amic) acid was prepared with a monomer composition of CHDC 0.7 / 6FDA 0.3 / / TFMB 1.0. All glassware was dried at 160° C. overnight. In a nitrogen purged drybox and 250 ml reaction vessel, 5 g TFMB was mixed with 60.3 g DMAc. In four portions over 1 hour, 2.258 g CHDC and 2.056 g 6FDA were added along with an additional 15.1 g DMAc. An additional 0.028 g 6FDA dissolved in 0.5 g DMAc was added. After 24 hours, the viscosity of the solution was 92 poise.

[0120] 84.67 g of poly(amide-amic) acid solution was used. An additional 20 g of DMAc was added to the solution heated to 40° C. along with 3.99 g of acetic anhydride and 3.64 g of β-picoline. The solution was then heated to 80° C. for 2 hours. After the solution was allowed to cool to room temperature, it was precipitated in methanol, washed, and dried to produce the polyimide resin.

[0121] The solution was precipitated by mixing 200 g of the above solution with 500 ml of methanol and washing with methanol. The material was ground in a blender, filtered, and washed twice with an equal amount of methanol. The final powder was dried under vacuum at 50° C. for 24 hours.

[0122] A film was cast using a 14 wt% solution of the polymer resin in DMAc. The solution was cast onto a glass substrate at 25°C to produce a film of approximately 2 mils. A doctor blade was used with a clearance of 25 mm to produce a film of approximately 2 mils after curing. The film on the glass substrate was heated to 50°C for 30 minutes on a hot plate, then heated to 90°C for 30 minutes, followed by cooling to room temperature. The film was peeled off using a razor, mounted on a 4x8 inch pin frame, and placed in an oven. The oven was then purged with nitrogen and heated to a final temperature of 250°C as described above for E2. After 20 minutes at 250°C, the film was removed from the oven and allowed to cool in air.

[0123] Example 5 The CHDC monomer described above in E4 was used.

[0124] In Example 5 (E5), a poly(amide-amic) acid was prepared with a monomer composition of CHDC 0.8 / 6FDA 0.2 / TFMB 1.0. All glassware was dried at 160° C. overnight. In a nitrogen purged drybox and 250 ml reaction vessel, 3.0 g TFMB was mixed with 34.8 g DMAc. In four portions over 1 hour, 1.548 g CHDC and 0.822 g 6FDA were added along with an additional 8.7 g DMAc. An additional 0.028 g 6FDA dissolved in 0.5 g DMAc was added. After 24 hours, the viscosity of the solution was 310 poise.

[0125] 40 g of DMAc was added to the polymer solution to form a 10 wt % solids solution.

[0126] The solution was cast onto a PET substrate at 25°C to produce a film of approximately 2 mils. A doctor blade was used with a clearance of 20 mm to produce a film of approximately 2 mils after curing. The film on the PET substrate was heated to 50°C on a hot plate for 30 minutes, then to 90°C for 30 minutes, after which it was cooled to room temperature. The film was peeled off using a razor, mounted on a 4x8 inch pin frame, and placed in an oven. The oven was then purged with nitrogen and heated according to the following temperature protocol: 25°C to 90°C (7°C / min), hold at 90°C for 5 min; 90°C to 150°C (7°C / min), hold at 150°C for 10 min; 150°C to 300°C (7°C / min), hold at 300°C for 5 min; After heating to 300° C. for 5 minutes, the film was removed from the oven and allowed to cool in air.

[0127] Example 6 Example 6 (E6) used the same poly(amide-amic) acid solution as described above for E5.

[0128] 48.82 g of poly(amide-amic) acid solution was used. An additional 56.0 g of DMAc was added to the solution heated to 40° C. along with 3.83 g of acetic anhydride and 3.49 g of β-picoline. The solution was then heated to 80° C. for 2 hours. After the solution was allowed to cool to room temperature, it was precipitated in methanol, washed, and dried to produce the polyimide resin.

[0129] The solution was precipitated by mixing with water and washed with methanol by adding 100 g of the polymer solution to the blender. 200 g of methanol was used as anti-solvent. Additional methanol was used to wash the precipitate and allowed to dry on a Buchner funnel.

[0130] Films were cast using an 11 wt % solution of the resin in DMAc.

[0131] The solution was cast onto a glass substrate at 25°C to produce a film of approximately 2 mils. A coating solution of the composition was cast onto a glass substrate at 25°C using a doctor blade with a clearance of 40 mm to produce a film of approximately 2 mils after curing. The film on the glass substrate was heated to 65°C for 20 minutes on a hot plate and then to 85°C for 30 minutes. The film was allowed to cool to room temperature. The film was peeled off using a razor, mounted on a 4x8 inch pin frame, and placed in an oven. The oven was then purged with nitrogen and heated to a final temperature of 250°C as described above for E2. After 20 minutes at 250°C, the film was removed from the oven and allowed to cool in air.

[0132] Example 7 The CHDC monomer described above in E4 was used.

[0133] In Example 7 (E7), a poly(amide-amic) acid was prepared with a monomer composition of 0.5 CHDC / 0.5 BPDA / / 1.0 TFMB. All glassware was dried at 160°C overnight. In a nitrogen purged drybox and 250 ml reaction vessel, 5.0 g TFMB was mixed with 57.5 g DMAc. In four portions over 1 hour, 1.613 g CHDC and 2.269 g 3,3,4,4-biphenyltetracarboxylic anhydride (BPDA, Mitsubishi Chemicals America, Inc., Charlotte, NC) were added along with an additional 14.4 g DMAc. 0.072 g 6FDA dissolved in 0.5 g DMAc was also added. After 24 hours, the viscosity of the solution was 75 poise.

[0134] 80.75 g of poly(amide-amic) acid solution was used. 6.42 g of acetic anhydride and 5.86 g of β-picoline were added, and the solution was then heated to 80° C. for 2 hours. The solution was allowed to cool to room temperature, after which it was precipitated in methanol, washed, and dried to produce the polyimide resin.

[0135] The solution was precipitated by mixing 200 g of the above solution with 500 ml of methanol and washing with methanol. The material was ground in a blender, filtered, and washed twice with an equal amount of methanol. The final powder was dried under vacuum at 50° C. for 24 hours.

[0136] A 5 wt% solution of the resin in DMAc was prepared. The solution was cast onto a glass substrate at 25°C to produce a film of approximately 2 mils. A coating solution of the composition was cast onto a glass substrate at 25°C using a doctor blade with a clearance of 50 mm to produce a film of approximately 2 mils after curing. The film on the glass substrate was heated to 50°C for 30 minutes on a hot plate and then to 90°C for 30 minutes. The film was allowed to cool to room temperature. The film was peeled off using a razor, mounted on a 4x8 inch pin frame, and placed in an oven. The oven was then purged with nitrogen and heated to a final temperature of 250°C as described above for E2. After 20 minutes at 250°C, the film was removed from the oven and allowed to cool in air.

[0137] Example 8 CHDC monomer was prepared. To 23.9 g of trans-1,4-cyclohexanedicarboxylic acid in 200 ml of DCM in a 1 L round bottom flask fitted with a 20 inch Vigreaux column in a drybox, 300 g of 2M oxalyl chloride in DCM was added, followed by 20 drops of DMF. The mixture was heated at 57° C. for 3 hours, then 54° C. for 3.5 hours, and allowed to cool to room temperature overnight. The gold solution was removed from the drybox and concentrated in vacuo to give a tan solid. After the solid appeared dry, it was left at 62° C. at 40 mbar for 15 minutes. 170 ml was collected in the rotary evaporation collection flask. The crude product was recrystallized from 250 ml of hexane in the drybox. The contents were filtered while hot (a copper colored undissolved solid remained in the reaction flask) and the product precipitated in the filtrate flask as it was filtered. The product (off-white needles) was filtered, washed with about 100 ml of hexane, and then dried overnight in the drybox vestibule. After about 67 hours and 40 minutes, the product was removed from the vestibule. Yield: 15.72 g (54%) of product as off-white needles.

[0138] In Example 8 (E8), a poly(amide-amic) acid was prepared with a monomer composition of CHDC 0.5 / TPC 0.3 / 6FDA 0.2 / / TFMB 1.0. All glassware was dried overnight at 160°C. In a nitrogen purged drybox and 250 ml reaction vessel, 4.0 g of TFMB was mixed with 46.2 g of DMAc. In four portions over 1 hour, 1.290 g of CHDC, 1.096 g of 6FDA, and 0.752 g of terephthaloyl chloride (Aldrich Chemicals, St. Louis, MO) were added along with an additional 11.6 g of DMAc. 40 g of DMAc was added to the solution.

[0139] The above mentioned polymer solution was used for film formation.

[0140] The solution was cast onto a glass substrate and heated on a hot plate as described above for E7. The film was peeled off using a razor, mounted on a 4x8 inch pin frame, and placed in an oven. The oven was then purged with nitrogen and heated to a final temperature of 300°C as described above for E5. After 5 minutes at 300°C, the film was removed from the oven and allowed to cool in air.

[0141] Example 9 The CHDC monomer described above in E8 was used.

[0142] In Example 9 (E9), a poly(amide-amic) acid was prepared with a monomer composition of CHDC 0.5 / CBDA 0.3 / 6FDA 0.2 / TFMB 1.0. All glassware was dried overnight at 160°C. In a nitrogen purged drybox and 500 ml reaction vessel, 30.0 g of TFMB was mixed with 345.3 g of DMAc. In four portions over 1 hour, 9.676 g of CHDC, 8.224 g of 6FDA, and 5.442 g of cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA, Wilshire Technologies, Princeton NJ) were added along with an additional 86.3 g of DMAc. An additional 0.575 g of 6FDA was added in five portions along with about 11 g of DMAc. The final viscosity was about 15 poise.

[0143] 484.92 g of the poly(amide-amic) acid solution was used. 23.78 g of acetic anhydride and 21.69 g of β-picoline were added. The solution was then heated to 80° C. for 2 hours. After the solution was allowed to cool to room temperature, the poly(amide-imide) solution was used for film formation.

[0144] The solution was cast onto PET at 25° C. to produce an approximately 2 mil film. A coating solution of the composition was cast onto a glass substrate at 25° C. using a doctor blade with 10 mm clearance to produce an approximately 2 mil film after curing. The film on the PET substrate was heated on a hot plate to 50° C. for 30 minutes and then to 90° C. for 30 minutes. The film was allowed to cool to room temperature. The film was peeled off using a razor, mounted on a 4×8 inch pin frame, and placed in an oven. The oven was then purged with nitrogen and heated according to the following temperature protocol: 25°C to 90°C (7°C / min), hold at 90°C for 5 min; 90°C to 150°C (7°C / min), hold at 150°C for 10 min; 150°C to 230°C (7°C / min), hold at 230°C for 15 min; After heating to 230° C. for 15 minutes, the film was removed from the oven and allowed to cool in air.

[0145] Table 1 summarizes the optical data of the films prepared in E1 to E9, and Table 2 summarizes the thermal and mechanical properties of the films.

[0146] [Table 1]

[0147] [Table 2]

Claims

1. It is a polymer film, Dicarbonyl halogens having formula I: 【Chemistry 1】 (In the formula, X and Y are either the same or different in each instance, and are independently selected from the group consisting of fluorine, chlorine, and bromine; R 1 ~R 4 These are the same or different in each presence and are independently selected from the group consisting of hydrogen and alkyl, where the alkyl is C1-C12 and linear or branched; B and B' are either the same or different in each presence, and at least one of B and B' is an alicyclic group, provided that they are either an alicyclic group or an aromatic group; x and y are either the same or different, and are integers between 0 and 12; and n is an integer between 0 and 4. A dianhydride selected from the group consisting of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic acid anhydride, 9,9-bis(trifluoromethyl)-2,3,6,7-xanthenetetracarboxylic acid dianhydride and mixtures thereof, A diamine selected from the group consisting of 2,2'-bis(trifluoromethyl)benzidine, p-phenylenediamine, 4,4'-bis-(aminophenoxy)biphenyl, 1,3'-bis(4-aminophenoxy)benzene, trans-1,4-cyclohexanediamine, 1,6-diaminohexane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, and mixtures thereof, It comprises a polymer composition derived from, A polymer film having a thickness of 25 μm and a b* value of 1.25 or less and a yellowness value of 2.25 or less.

2. The polymer film according to claim 1, wherein the alicyclic groups of each B and B' are selected from the group consisting of phenyl groups, saturated C3-C16 alicyclic groups, unsaturated non-aromatic C5-C22 alicyclic groups, and C7-C8 bicyclic groups.

3. The polymer film according to claim 1, wherein X = Y = chlorine.

4. The polymer film according to claim 3, wherein n = 0 and B is a saturated C4-C9 alicyclic group.

5. The polymer film according to claim 4, wherein B is a saturated C6 alicyclic group.

6. The polymer film according to claim 1, wherein the polymer composition is poly(amide-imide) or poly(amide-ester-imide), and the poly(amide-ester-imide) is further derived from a polyol.

7. The polymer film according to claim 1, having a tensile modulus of 4 GPa or higher.

8. The polymer film according to claim 1, having a coefficient of thermal expansion of 50 ppm / °C or less over a temperature range of 50 to 250°C.

9. An electronic device comprising the polymer film described in claim 1.

10. The electronic device according to claim 9, which is a flexible display.

11. A metal-clad laminate containing the polymer film described in claim 1.

12. The polymer composition 0.5 to 0.8 moles of dicarbonyl halogen, 0.2 to 0.5 moles of dianhydrous, 1.0 mole of 2,2'-bis(trifluoromethyl)benzidine and A polymer film according to claim 1, derived from.

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