Low Viscosity Composition Comprising Polyamide-imide Polymer

Abstract

A low-toxicity solvent-based composition, particularly a low viscosity coating formulation, is disclosed, which comprises a polyamideimide polymer having a well-defined molecular weight distribution.

Description

[Technical field]

[0001] This application claims priority to European Patent Application No. 21306153.4, filed August 26, 2021, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to low viscosity formulations, in particular coating formulations, containing polyamideimide polymers and low toxicity solvents, and to polyamideimide polymers for their preparation. [Background technology]

[0003] Polyamide-imide and polyamic acid polymers (hereafter collectively referred to as PAIs) are well-known thermally stable polymers that are used in many high performance coating applications due to their excellent adhesion, heat resistance, and high strength. PAIs are commonly utilized as protective coatings for metal substrates exposed to harsh environments such as temperature, abrasion, abrasion, and chemical exposure.

[0004] Typically, polar aprotic solvents, generally N-methylamide type solvents, especially N-methylpyrrolidone (NMP), are used to dissolve the polymer and prepare the coating composition. After being applied onto the substrate, the composition undergoes a thermal curing process to remove the solvent and increase the molecular weight to achieve the optimum desired properties of the material. A significant drawback of this approach is that NMP is known to be toxic. Therefore, it is necessary to find other suitable solvents. Alternative solvents such as tetrahydrofuran, methyl ethyl ketone, γ-butyrolactone, or dimethyl sulfoxide have drawbacks such as low polymer solubility and poor storage stability, which may alter the properties of the polymer and its application performance, as well as other practical considerations.

[0005] Biodegradable and less hazardous alternatives to solvents such as NMP are available such as NBP (Nn-butyl-2-pyrrolidone), available from Eastman under the trade name Tamisolv® NxG, and methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, available from Solvay under the trade name Rhodiasolv® PolarClean. The main challenge in using these alternative solvents is that, although they may be successful in producing homogeneous polymer solutions in some cases, they tend to have insufficient solvency, resulting in high viscosities that are generally unsuitable for coating applications.

[0006] WO 2015 / 161107 A1 and WO 2015 / 161131 A1 (FUJIFILM Holdings Corporation) attempt to address this problem. These documents disclose a method for the preparation of PAI resins by the isocyanate route using a mixture of solvents and co-solvents, and a PAI-containing coating composition comprising a PAI resin in a mixture of solvents and co-solvents. The mixture of solvents and co-solvents comprises at least one aprotic dialkylamide solvent and at least one co-solvent selected from the group consisting of methyl acetate, n-propyl acetate, t-butyl acetate, isobutyl acetate, ethyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, t-butyl lactate, cyclohexanone, cyclopentanone, n-butyl acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-acetylmorpholine, e-caprolactone, and methylcyclohexane. The coating compositions disclosed in WO 2015 / 161107 A1 and WO 2015 / 161131 A1 are characterized by suitable viscosities, but require the use of more complex solvent mixtures for industrial handling.

[0007] It has now surprisingly been found that by controlling the molecular weight distribution of the polyamic acid precursor to the polyamideimide polymer within specific ranges, it is possible to obtain compositions which are characterized by an optimal combination of the amount of polymer present in the composition and its viscosity, and which contain low toxicity solvents, which are highly suitable for coating applications. Summary of the Invention

[0008] Therefore, the first object of the present invention is to provide a method for producing a polymer having a molecular weight distribution M w / M n The aromatic polyamic / polyamide-imide polymer [polymer (PAI)] is characterized in that the molecular weight distribution M is 2.00 to 3.40. w / M n may be 3.35 or less, or even 3.30 or less.

[0009] In one embodiment, the polymer (PAI) is obtained by an acid halide process.

[0010] The second object of the present invention is to provide a polymer having a molecular weight distribution M w / M n The present invention relates to a method for preparing a polymer having a formula (PAI), the method comprising polycondensation reacting at least one aromatic polycarboxylic acid halide monomer with at least one aromatic diamine monomer in the presence of an excess of the aromatic polycarboxylic acid halide monomer relative to the aromatic diamine monomer.

[0011] The third object of the present invention is to provide a polymerizable composition having a low toxicity solvent and a molecular weight distribution M of 2.00 to 3.40. w / M n The composition preferably contains 15 to 40% by weight of the polymer (PAI) based on the total weight of the composition.

[0012] In one embodiment, the composition has a viscosity of 1000 to 10000 cPoise.

[0013] A fourth object of the present invention is a method for the manufacture of an article, comprising a step of coating the composition on a substrate.

[0014] definition The use of parentheses around a symbol or number identifying a compound, chemical formula, or part of a formula has the sole purpose of better distinguishing that symbol or number from the rest of the text, and therefore, said parentheses may be omitted.

[0015] Any description, even if made in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the invention.

[0016] Any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited range, as well as the endpoints of the range and equivalents thereof.

[0017] According to a first object of the present invention, there is provided a repeating unit comprising at least one aromatic ring and at least one amic acid group and / or imide group [repeating unit (R PAI The polymer (PAI) has a molecular weight distribution M of 2.00 to 3.40. w / M n The molecular weight distribution M w / M n may be 3.35 or less, or even 3.30 or less.

[0018] In some embodiments, the molecular weight distribution M w / M n The molecular weight distribution M may be 2.50 or more, or even 2.80 or more. w / M n may advantageously be between 2.50 and 3.40.

[0019] Number average molecular weight (M n) is advantageously at least 1000, preferably at least 1500 and more preferably at least 2000.

[0020] Number average molecular weight (M n ) is advantageously at most 20 000, preferably at most 15 000.

[0021] Molecular weight of polymer (PAI) (M w and M n ) can be determined using gel permeation chromatography (GPC) using polystyrene standards as detailed below.

[0022] Repeating unit (R PAI )teeth, [ka] wherein: - the symbol → denotes in each formula that in any repeat unit in the aromatic polyamic acid structure, the radicals pointed to by the arrows may be present as shown or in interchanged positions; Ar is an aromatic tetravalent radical, which may contain one or more aromatic rings, preferably [ka] (X is -O-, -C(O)-, -S-, -SO2-, -CH2-, -C(CF3)2-, -(CF2) n - (n=0, 1, 2, 3, 4, or 5) selected from the group consisting of; R is an aromatic divalent group, which may contain one or more aromatic rings, preferably [ka] (Y is -O-, -C(O)-, -S-, -SO2-, -CH2-, -C(CF3)2-, -(CF2) n- (n=0, 1, 2, 3, 4, or 5) [ka] is selected from the group consisting of:

[0023] Repeating unit (R PAI ) preferably comprises units (i), (ii) and (iii) as detailed below: [ka] and / or the corresponding imide group-containing repeat unit: [ka] (wherein the attachment of the two amide groups to the aromatic ring shown in (ia) is understood to represent 1,3 and 1,4 polyamide-amic acid configurations); [ka] and / or the corresponding imide group-containing repeat unit: [ka] wherein the attachment of the two amide groups to the aromatic ring shown in (ii-a) is understood to represent a 1,3 and 1,4 polyamide-amic acid configuration; and [ka] and / or the corresponding imide group-containing repeat unit: [ka] (wherein the attachment of the two amide groups to the aromatic ring shown in (iii-a) is understood to represent a 1,3 and 1,4 polyamide-amic acid configuration.) is selected from the group consisting of:

[0024] Repeating unit (R PAI) is preferably the repeat unit (i) or a mixture of repeat units (ii) and (iii).

[0025] Preferably, the polymer (PAI) comprises more than 90 mol % of repeat units (R PAI Even more preferably, it comprises the repeating unit (R PAI ) does not contain any repeating units other than those.

[0026] Excellent results have been obtained with polymers (PAI) consisting of repeating units (i) or a mixture of repeating units (ii) and (iii).

[0027] The amount of repeat units containing amico groups can be determined by any suitable technique, in particular spectroscopic or titration techniques well known to those skilled in the art.

[0028] Repeating unit (R PAI ) is calculated using the formula (R PAI -A), (R PAI -B), (R PAI -C), (R PAI -D), (R PAI -E), and a repeating unit (R PAI ) can be expressed as:

number

[0029] In a preferred embodiment, less than 25 mol %, even less than 20 mol %, even less than 15 mol %, preferably less than 10 mol % of repeat units (R PAI ) contains at least one amic acid group.

[0030] The acid number (milligrams of KOH / gram) of the polymer (PAI) is advantageously less than 50, preferably less than 25.

[0031] The intrinsic viscosity of the polymer (PAI) is at least 0.30, preferably at least 0.50 dL / g, and typically does not exceed 0.75 dL / g, measured as a 0.5 wt % solution in NMP at 25°C.

[0032] The polymer (PAI) can be produced in particular by a process comprising a polycondensation reaction between at least an aromatic polycarboxylic acid halide monomer and at least an aromatic diamine in the presence of an excess of the aromatic polycarboxylic acid halide monomer relative to the aromatic diamine monomer.

[0033] The aromatic polycarboxylic acid halide monomer is typically present in at least a 5% molar excess, or even at least a 7% molar excess, relative to the equimolar concentration of the aromatic diamine monomer. The aromatic polycarboxylic acid halide monomer is typically present in up to a 15% molar excess, relative to the equimolar concentration of the aromatic diamine monomer. Good results have been obtained with a 10-15% molar excess, relative to the equimolar concentration of the aromatic diamine monomer.

[0034] For clarity, the excess is calculated taking into account the total amount of all aromatic polycarboxylic acid halide monomers relative to the total amount of all aromatic diamine monomers used in the polycondensation process.

[0035] The aromatic polycarboxylic acid halide monomer is selected from the group consisting of terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, and acid halide derivatives of trimellitic anhydride.Preferably, it is selected from trimellitic anhydride monoacid halides.Of the trimellitic anhydride monoacid halides, trimellitic anhydride monoacid chloride is preferred.

[0036] In some embodiments, dicarboxylic anhydride monomers can be used in combination with polycarboxylic acid halide monomers.Suitable dicarboxylic anhydride monomers include pyromellitic anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, and trimellitic anhydride.When dicarboxylic anhydride monomers are used in the process, the excess amount of acid halide monomers relative to the equimolar concentration of aromatic diamine monomers is calculated by considering the total moles of acid halide and dicarboxylic anhydride monomers.

[0037] The aromatic diamine monomers are 4,4'-diaminodiphenyl ether (ODA), p-phenylenediamine (PDA), m-phenylenediamine (MPDA), diphenyldimethylmethanediamine (DMMDA), 1,3-bis(3-aminophenoxy)benzene (BAPB), 4,4'-bisphenol A ether diamine (BAPP), 4,4'-bis(4-aminophenoxy)diphenyl sulfone (BAPS), 4,4'-bis(4-aminophenoxy)diphenyl ether (BAPE), diaminodiphenyl(methyl)ketone (DABP), 4,4'-diaminodiphenyl ether (DAPE ... diaminodiphenylamine (DATPA), 4,4'-diaminodiphenylmethane (MDA), diaminodiphenylsulfone (DDS), 3,4'-diaminodiphenylether (3,4'-ODA), 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MDI), 4,4'-diamino-diphenoxy-1",4"-benzene, 4,4'-diamino-diphenoxy-1",3"-benzene, 3,3'-diamino-diphenoxy-1",3"-benzene, 4,4'-diamino-diphenyl-4",4-phenyl-isopropylpropane.

[0038] The aromatic diamine monomer is preferably selected from the group consisting of 4,4'-diaminodiphenyl ether (ODA), 4,4'-diaminodiphenyl methane (MDA), p-phenylenediamine (PDA), and m-phenylenediamine (MPDA), and mixtures thereof.

[0039] The polycondensation reaction is advantageously carried out under substantially anhydrous conditions, in a polar solvent, at a temperature below 150° C., using a stoichiometric excess of the acid halide monomer.

[0040] To control the molecular weight and improve the stability of the polymer, monofunctional reactants can be used as end-capping agents, as known to those skilled in the art.

[0041] The polymer (PAI) is advantageously isolated in solid form by coagulation or precipitation from the polar reaction solvent under mild conditions, preferably by addition of a miscible non-solvent such as, for example, water or a lower alkyl alcohol. Optionally, the solid resin may then be recovered, washed extensively with water, and centrifuged or pressed to further reduce the water content of the solid without the application of heat. Non-solvents other than water and lower alkyl alcohols are known and used in the art to precipitate polymers (PAI) from solutions including, for example, ethers, aromatic hydrocarbons, ketones, and the like.

[0042] In a further aspect of the present invention, there is provided a composition comprising a polymer (PAI) and a non-toxic solvent [solvent (S)]. The expression "non-toxic solvent" is used herein to refer to a solvent that is not recognized as harmful to human health.

[0043] The solvent (S) is usually selected from the group consisting of at least one of N-butylpyrrolidone, N-acetylpyrrolidone, methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, dimethyldecanamide, 2-hydroxy-N,N-dimethylpropanamide, isosorbide dimethyl ether, 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol, γ-valerolactone, a mixture comprising ethyl lactate and an ethyl ester derived from soybean oil or corn oil, dimethyl glutarate, dimethyl succinate, dimethyl adipate, a mixture of dimethyl glutarate, dimethyl succinate, dimethyl adipate and dimethyl 2-methylglutarate.

[0044] Preferably, the solvent (S) is selected from the group consisting of at least one of N-butylpyrrolidone, N-acetylpyrrolidone, methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, dimethyldecanamide, 2-hydroxy-N,N-dimethylpropanamide, isosorbide dimethyl ether, 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol, cyclopentanone, γ-valerolactone.

[0045] More preferably, the solvent (S) is selected from the group consisting of at least one of N-butylpyrrolidone and methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate.

[0046] The composition of the present invention typically comprises less than 5.0% by weight, less than 2.0% by weight, preferably less than 1.0% by weight, or even less than 0.5% by weight, or even less than 0.1% by weight, of a solvent different from the solvent (S).

[0047] The composition of the invention advantageously contains at least 1% by weight of polymer (PAI) relative to the total weight of the composition, preferably at least 5% by weight and more preferably at least 10% by weight.

[0048] The composition of the invention advantageously contains at most 55% by weight, preferably at most 50% by weight and more preferably at most 45% by weight of polymer (PAI) relative to the total weight of the composition.

[0049] Polymer compositions containing 10-45% by weight of polymer (PAI) relative to the total weight of the composition gave very satisfactory results.

[0050] It has been unexpectedly found that compositions comprising polymer (PAI) in an amount of 10-45% by weight, typically 15-40% by weight, have a viscosity suitable for use of said compositions in the manufacture of coatings.

[0051] Advantageously, compositions containing the polymer (PAI) in an amount of 10-45% by weight have a viscosity measured at 25° C. of 500-10000 cPoise, typically 1000-8000 cPoise, making them suitable for coating applications.

[0052] The composition may further comprise the usual ingredients of coating compositions, in particular: (i) dispersants; (ii) pigments such as carbon black, silicates, metal oxides and sulfides; (iii) additives such as coating aids or flow promoters; (iv) inorganic fillers such as carbon fibres, glass fibres, metal sulphates such as BaSO4 and CaSO4, oxides such as Al2O3 and SiO2, zeolites, mica, talc, kaolin; (v) organic fillers, preferably heat stable polymers such as PTFE; (vi) film hardeners such as metal silicates, silicate compounds such as aluminium silicate, and metal oxides such as titanium dioxide; (vii) adhesion promoters such as colloidal silica and phosphate compounds such as metal phosphates, e.g. phosphates of Zn, Mn or Fe.

[0053] A further aspect of the present invention is a method for the manufacture of an article comprising coating the composition of the present invention on a substrate. Coating can be carried out by any suitable coating process such as spin coating, slit spin coating, roll coating, die coating or curtain coating. The coating step is typically followed by a step of curing the applied composition by pre-baking the obtained film at a temperature comprised between 120 and 400°C, preferably between 120 and 350°C, in order to volatilize the solvent.

[0054] The thickness of the coating can vary depending on the intended purpose, and is preferably in the range of 0.1 to 100 microns, preferably 1 to 50 microns, more preferably 5 to 20 microns, and even more preferably the thickness is about 10 microns.

[0055] In particular, compositions containing the polymer (PAI) can be used for coating cookware, for coating oil and gas pipelines, for the manufacture of aerospace parts and flexible electronic components, as dry film lubricants, as heat resistant inks, and for xerography and can coatings, and in other applications. The compositions of the present invention may be useful in wire coating applications such as enamels or base coats, particularly in the manufacture of magnet wire or wire for electric motors in general.

[0056] In particular, the polymeric PAI can be used in coating solutions that include, but are not limited to, polytetrafluoroethylene (PTFE).

[0057] The compositions of the present invention may also be advantageously used to prepare NMP-free battery binder formulations, particularly Li-ion battery binder formulations.

[0058] The present invention will now be described with reference to the following examples, the purposes of which are merely illustrative and not limiting of the invention.

[0059] raw materials Trimellitic anhydride (TMA), trimellitic acid chloride (TMAC), oxydianiline (ODA), m-phenylenediamine (MPDA), and N-methylpyrrolidone (NMP) are available from Sigma Aldrich. Methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate is supplied by Solvay under the trade name Rhodiasolv® Polarclean. N-butylpyrrolidone (NBP) is available from Eastman under the trade name Tamisolv® NxG.

[0060] method solution viscosity The viscosity of the polymer was measured using a Brookfield viscometer in NMP at 25° C. at a polymer concentration of 23 wt %.

[0061] Molecular weight determination using GPC method GPC conditions: Pump: Waters 515 solvent delivery system or equivalent Detector: Waters 2487 series UV / VIS detector or equivalent (270 nm) Software: Waters Empower3 Pro gel permeation chromatography software or equivalent Injector: Waters717 Wisp autosampler or equivalent Flow rate: 0.3ml / min UV detection: 270nm Column temperature: 45℃ Columns: 2 PLgel 5μm MiniMix-D, 250×4.6mm columns, Agilent, part number PL1510-5504; 1 PLgel 5μm MiniMix-D Guard, 50×4.6mm, Agilent, part number PL1510-1504 Injection volume: 10 microliters Run Time: 30 minutes Eluent: N,N-dimethylacetamide / 0.1M lithium bromide Calibration Standards: 10 polystyrene narrow calibration standards (Agilent part number PL2010-060). Eight of these 10 standards could be resolved in the range of Mp 364,000 to 2790 g / mol. Concentration of calibration standard: 6mg / mL Calibration curve: Type: Relative, calibration with narrow calibration standards Fit: Cubic regression. Integration and Calculations: Data, calibration, and molecular weight calculations are obtained using Empower3 Pro GPC software from Waters. Peak integration start and end points are determined manually from significant differences across the baseline. Sample preparation: 24 mg of polymer was dissolved in 4 mL of eluent by heating to 100° C. for 20 min with magnetic stirring. After cooling, the solution was filtered using a 0.22 μm PTFE syringe filter, and the resulting solution was passed through a GPC column according to the GPC conditions described above.

[0062] Example 1-M w / M n Polymer PAI-1 <3.40 ODA (0.201 mol) and MPDA (0.086 mol) were placed in a jacketed 4-neck round bottom flask equipped with an overhead mechanical stirrer. NMP (270 g) was placed in the flask and the mixture was cooled to 10 °C with gentle stirring under a nitrogen atmosphere. The flask was fitted with a heated addition funnel into which TMAC (0.316 mol) was placed and heated to a minimum of 100 °C. The molten TMAC was added to the solution of diamine in NMP with vigorous stirring at a rate sufficient to not exceed 40 °C. After addition was complete, external heat was applied to maintain 35-40 °C for 2 hours. Additional NMP (50 g) was added and the reaction mixture was drained into a 500 mL beaker. The polymer solution was slowly added to water (4000 mL) in a stainless steel high shear mixer. The precipitated polymer was filtered and washed multiple times with water to remove residual solvent and acid by-products. The solid polymer was dried at 260 °C for at least 2 hours. Residual NMP solvent was determined to be less than 0.1% by GC analysis.

[0063] Comparative example 1-M w / M n >3.40 Polymer PAI-2 ODA (0.263 mol) and MPDA (0.113 mol), along with TMA (0.019 mol) were placed in a jacketed 4-neck round bottom flask equipped with an overhead mechanical stirrer. NMP (290 g) was placed in the flask and the mixture was cooled to 10 °C with gentle stirring under a nitrogen atmosphere. The flask was fitted with a heated addition funnel into which TMAC (0.377 mol) was placed and heated to a minimum of 100 °C. The molten TMAC was added to the solution of diamine in NMP with vigorous stirring at a rate sufficient to not exceed 40 °C. After addition was complete, external heat was applied to maintain 35-40 °C for 2 hours. Additional NMP (50 g) was added and the reaction mixture was drained into a 500 mL beaker. The polymer solution was slowly added to water (4000 mL) in a stainless steel high shear mixer. The precipitated polymer was filtered and washed multiple times with water to remove residual solvent and acid by-products. The solid polymer was dried for at least 2 hours at 260° C. Residual NMP solvent was determined to be less than 0.1% by GC analysis.

[0064] Table 1 summarizes the molecular weight characteristics of polymers PAI-1 and PAI-2.

[0065] [Table 1]

[0066] Example 2 - Compositions containing polymeric PAI General procedure: A solution containing 23 wt % polymer was prepared by heating a mixture of polymer powder (4.74 g) and selected solvent (S) (15.26 g) at 90° C. for 10 minutes.

[0067] As a comparison, a 25 wt % solution of polymer PAI-2 in NMP was also prepared by heating a mixture of polymer powder (5 g) and NMP (20 g) at 90° C. for 10 min.

[0068] The compositions and their properties are detailed in Table 2.

[0069] [Table 2]

[0070] The results in Table 2 show that M w / M n and a composition comprising a polymer PAI-1 having an M of greater than 3.40 in the same solvent. w / M n This is surprising considering the high molecular weight of the polymer PAI-1.

[0071] Comparing the viscosity of the composition of Test 5 with the viscosity of the compositions of Tests 2 and 4, M w / M n It has been shown that PAI polymers with a viscosity greater than 3.40 provide compositions in NMP with suitable viscosities for coating applications. However, when dissolved in solvents such as methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate or NBP, these polymers produce solutions that are too viscous to be used. This problem can be surprisingly and successfully overcome by using the PAI polymers of the present invention.

Claims

1. An aromatic polyamic acid / polyamideimide polymer [polymer (PAI)] containing more than 50 mol% of repeating units [repeating units (R ＰＡＩ ))], wherein the repeating units [repeating units (R ＰＡＩ )) are 【Chemical 1】 selected from the group consisting of, wherein - The symbol → means isomerism such that in each formula, in any repeating unit within the aromatic polyamic acid structure, the group indicated by the arrow may be present as shown or at an interchanged position; - Ar is an aromatic tetravalent group, which may contain one or more aromatic rings, preferably 【Chemical 2】 (X is selected from the group consisting of -O-, -C(O)-, -S-, -SO ２ -, -CH ２ -, -C(CF ３ ) ２ -, -(CF ２ ) ｎ -(where n = 0, 1, 2, 3, 4, or 5)) selected from the group consisting of; - R is an aromatic divalent group, which may contain one or more aromatic rings, preferably 【Chemical Formula 3】 (Y is selected from the group consisting of -O-, -C(O)-, -S-, -SO ２ -, -CH ２ -, -C(CF ３ ) ２ -, -(CF ２ ) ｎ - (where n = 0, 1, 2, 3, 4, or 5)) 【Chemical 4】 selected from the group consisting of, The aromatic polyamic acid / polyamideimide polymer has a molecular weight distribution M of 2.00 to 3.40 ｗ / M ｎ and the repeating unit (RPAI) has units (i), (ii), and (iii): 【Chemical Formula 5】 and / or the corresponding imide group-containing repeating unit: 【Chemical Formula 6】 (wherein the bonding of the two amide groups to the aromatic ring shown in (i-a) is understood to represent 1,3 and 1,4 polyamide-amic acid arrangements); 【Chemical Formula 7】 and / or the corresponding imide group-containing repeating unit: 【Chemical 8】 (wherein the bonding of the two amide groups to the aromatic ring shown in (ii-a) is understood to represent 1,3 and 1,4 polyamide-amic acid arrangements); and 【Chemical Formula 9】 and / or the corresponding imide group-containing repeating unit: 【Chemical 10】 (wherein the bonding of the two amide groups to the aromatic ring shown in (iii-a) is understood to represent 1,3 and 1,4 polyamide-amic acid arrangements) An aromatic polyamic acid / polyamideimide polymer [polymer (PAI)] selected from the group consisting of.

2. Repeating unit (R ＰＡＩ ) is a repeating unit (i), or a mixture of repeating units (ii) and (iii), the polymer (PAI) according to claim 1.

3. A polymer (PAI) according to claim 1 or 2, comprising a repeating unit (R) in an amount exceeding 90 mol%. ＰＡＩ ​

4. The polymer (PAI) according to claim 1 or 2, having an acid value of less than 50 measured as milligrams of KOH per gram of polymer.

5. 2.50 to 3.40, preferably 2.80 to 3.40, molecular weight distribution M ｗ / M ｎ The polymer (PAI) according to claim 1 or 2, having

6. A method for producing the polymer (PAI) according to claim 1 or 2, comprising performing a polycondensation reaction between at least the aromatic polycarboxylic acid halide monomer and the at least aromatic diamine in the presence of an excess of the aromatic polycarboxylic acid halide monomer with respect to the aromatic diamine monomer.

7. The method according to claim 6, wherein the aromatic polycarboxylic acid halide monomer is present in an excess of at least 5 mol% with respect to the equimolar concentration of the aromatic diamine monomer, preferably in an excess of 10-15 mol% with respect to the equimolar concentration of the aromatic diamine monomer.

8. A composition comprising the polymer (PAI) according to any one of claims 1 or 2 and a non-toxic solvent [solvent (S)], A composition, wherein the solvent (S) is selected from the group consisting of at least one of N-butylpyrrolidone, N-acetylpyrrolidone, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, dimethyldecanamide, 1,3-dimethyl-2-imidazolidinone (DMI), 3-methoxy-N,N-dimethylpropanamide, 2-hydroxy-N,N-dimethylpropanamide, isosorbide dimethyl ether, 2-isobutyl-2-methyl-1,3-dioxolan-4-methanol, γ-butyrolactone, a mixture containing ethyl lactate and an ethyl ester derived from soybean oil or corn oil, dimethyl glutarate, dimethyl succinate, dimethyl adipate, and a mixture of dimethyl glutarate, dimethyl succinate, dimethyl adipate, and dimethyl 2-methylglutarate.

9. The composition according to claim 8, wherein the solvent (S) is selected from the group consisting of at least one of N-butylpyrrolidone and methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate.

10. The composition according to claim 8, containing less than 5.0% by weight, preferably less than 2.0% by weight, more preferably less than 1.0% by weight of a solvent different from the solvent (S).

11. The composition according to claim 8, containing 10 to 45% by weight of the polymer (PAI) based on the total weight of the composition.

12. A method for manufacturing an article, comprising coating the composition according to claim 8 on a substrate.

13. The method according to claim 12, further comprising a step of curing the composition by heating at a temperature included in the range of 120 to 400°C.

14. An article containing the polymer (PAI) according to claim 1 or 2.

15. The article according to claim 14, which is a wire, a cooking utensil, a battery, a flexible electronic component, or a pipe for petroleum or gas.

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