Blended film comprising polyamide-imide and polyimide and method for preparing same

Abstract

The present invention provides a blended film with a tensile strength of 130 MPa or more that comprises: a polyamide-imide including, as polymerization units, trimellitic acid anhydride (TMA) and a diisocyanate monomer including at least one selected from the group consisting of methylene diphenyl diisocyanate (MDI), 1,5-naphthalene diisocyanate(NDI), p-phenylene diisocyanate(PPDI), m-phenylene diisocyanate(MPDI), 2,4-toluene diisocyanate(TDI), 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diphenylisopropylidene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, dianisidine diisocyanate, tolidine diisocyanate(TODI), and hexamethylene diisocyanate; and a polyimide including, as polymerization units, a dianhydride monomer including at least one selected from the group consisting of pyromellitic dianhydride(PMDA), biphenyl tetracarboxylic dianhydride(BPDA), and benophenone tetracarboxylic dianhydride(BTDA), and a diamine monomer including at least one selected from the group consisting of 4,4'-diaminodiphenylether (ODA), 4,4'-methylenedianiline (MDA), metaphenylenediamine (MPD), paraphenylenediamine (PPD), and m-tolidine.

Description

Mixed film containing polyamideimide and polyimide and method for manufacturing the same

[0001] The present invention relates to a mixed film comprising polyamideimide and polyimide and a method for manufacturing the same. More specifically, by mixing polyamideimide and polyimide, the invention relates to a mixed film having excellent mechanical properties and peelability and a method for manufacturing the same.

[0002] Polyimide (PI) is a polymer material based on imide rings with excellent chemical stability and a rigid aromatic main chain, possessing the highest levels of heat resistance, chemical resistance, electrical insulation, chemical resistance, and weather resistance among organic materials. In particular, due to its outstanding insulation properties—specifically excellent electrical characteristics such as low dielectric constant—it is gaining attention as a high-performance polymer material in fields ranging from electrical and electronic to optical. However, polyimide films have faced issues such as high cost, limited processability, and brittleness.

[0003] Meanwhile, polyamideimide has properties similar to polyimide, but includes amide bonds, exhibiting superior processability and flexibility compared to polyimide. In addition, it possesses excellent chemical resistance and electrical insulation properties, making it suitable for use as electrical insulation materials, coating materials, and adhesives in high-temperature environments.

[0004] Therefore, there is a need to develop a hybrid film that combines the advantages of polyimide and polyamideimide, which can compensate for the disadvantages of each material and realize excellent characteristics through mutual synergy.

[0005] The present invention provides a mixed film comprising polyamideimide and polyimide having excellent mechanical properties and peelability, and a method for manufacturing the same.

[0006] The present invention is capable of various modifications and may have various embodiments, and specific embodiments are to be illustrated and described in detail. However, this is not intended to limit the invention to specific embodiments, and it should be understood that the invention includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the invention.

[0007] The terms used in this application are used merely to describe specific embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, terms such as "comprising" or "having" are intended to specify the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0008] Where in this specification, when a quantity, concentration, or other value or parameter is given as an enumeration of a range, a preferred range, a preferred upper limit, and a preferred lower limit, it should be understood that any pair of any upper range limit or preferred value and any lower range limit or preferred value are specifically disclosed, regardless of whether the range is disclosed separately.

[0009] Where a range of numerical values ​​is mentioned in this specification, unless otherwise stated, the range and the scope of the parent invention within that range are not intended to be limited to the specific value mentioned when defining the range.

[0010] In this specification, "dianhydride" is intended to include its precursor or derivative, and is also referred to as "dianhydride," "dianhydride," or "acid dianhydride." Although these may not technically be dianhydrides, they will nevertheless react with a diamine to form a polyamic acid, which can then be converted into a polyimide.

[0011] In this specification, "diamine" is intended to include its precursors or derivatives, which may not technically be diamines but nevertheless will react with dianhydrides to form polyamic acids, which can then be converted into polyimides.

[0012] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the present invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in this application. Specific details for the implementation of the above invention are described below.

[0013] The present invention relates to a mixed film comprising polyamideimide and polyimide having excellent mechanical properties and peelability, and a method for manufacturing the same.

[0014] Mixed film containing polyamideimide and polyimide

[0015] Specifically, the present invention comprises a diisocyanate comprising trimellitic acid anhydride (TMA) and one or more selected from the group consisting of methylene diphenyl diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), m-phenylene diisocyanate (MPDI), 2,4-toluene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diphenylisopropylidene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, dianisidine diisocyanate, tolidine diisocyanate (TODI), and hexamethylene diisocyanate. A mixed film is provided comprising: a polyamideimide containing a monomer as a polymerization unit; and a polyimide containing a dianhydride monomer selected from the group consisting of pyromellitic dianhydride (PMDA), biphenyl tetracarboxylic dianhydride (BPDA), and benzophenone tetracarboxylic dianhydride (BTDA), and a diamine monomer selected from the group consisting of 4,4'-diaminodiphenyl ether (ODA), 4,4'-methylenedianiline (MDA), metaphenylenediamine (MPD), paraphenylenediamine (PPD), and m-tolidine as a polymerization unit, wherein the tensile strength is 130 MPa or higher.

[0016] In addition, with respect to 100 wt% of the above mixed film, it may comprise 40 to 99 wt% of the polyamideimide; and 1 to 60 wt% of the polyimide; and preferably, it may comprise 45 to 85 wt% of the polyamideimide; and 15 to 55 wt% of the polyimide. By including polyamideimide and polyimide within the above ratio range, excellent mechanical properties and peeling characteristics can be achieved, and there is a cost reduction effect compared to conventional polyimide films.

[0017] Specifically, the lower limit of the polyamideimide content may be 43 wt% or more, 45 wt% or more, 48 wt% or more, or 50 wt% or more, and the upper limit may be 95 wt% or less, 90 wt% or less, 85 wt% or less, 80 wt% or less, 75 wt% or less, 70 wt% or less, or 65 wt% or less. In addition, the lower limit of the polyimide content may be 5 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, 25 wt% or more, 30 wt% or more, or 35 wt% or more, and the upper limit may be 57 wt% or less, 55 wt% or less, 52 wt% or less, or 50 wt% or less.

[0018] In one embodiment, with respect to 100 wt% of the mixed film, the polyamideimide may comprise 45 to 75 wt%; and 25 to 55 wt% of the polyimide; and preferably may comprise 50 to 65 wt% of the polyamideimide; and 35 to 50 wt% of the polyimide.

[0019] The above polyamideimide may include trimellitic acid anhydride (TMA) and methylene diphenyl diisocyanate (MDI) as polymerization units.

[0020] The above polyamideimide generally forms amide (-NHCO-) ​​and imide (-CO-N-CO-) bonds through the reaction of isocyanate (-NCO) and acid (-COOH) or anhydride (-CO-O-CO-) components, passing through the reaction intermediate carbamate (-OC(=O)-NH-) to generate carbon dioxide as an byproduct. TMA possesses both carboxyl groups (-COOH) and anhydride groups (-CO-O-CO-), enabling reactions with various functional groups, and its asymmetric structure increases flexibility. MDI possesses two isocyanate groups (-NCO), exhibiting high reactivity, and acts as a crosslinking agent between polyamideimide chains, contributing to improved mechanical strength and increased thermal stability.

[0021] The above polyimide may include, as a polymerization unit, a dianhydride monomer comprising pyromellitic dianhydride (PMDA) or biphenyl tetracarboxylic dianhydride (BPDA), and a diamine monomer comprising one or more, preferably two or more, selected from the group consisting of 4,4'-diaminodiphenyl ether (ODA), paraphenylenediamine (PPD), 4,4'-methylenedianiline (MDA), and m-tolidine.

[0022] The dianhydric monomer of the above polyimide may include pyromellitic dianhydride (PMDA) or biphenyl tetracarboxylic dianhydride (BPDA).

[0023] The diamine monomer of the polyimide may comprise a first diamine comprising 4,4'-diaminodiphenyl ether (ODA) or 4,4'-methylenedianiline (MDA), and may further comprise a second diamine comprising paraphenylenediamine (PPD) or m-tolidine. Preferably, the diamine monomer of the polyimide may be 4,4'-diaminodiphenyl ether (ODA) alone, a combination of 4,4'-diaminodiphenyl ether (ODA) and paraphenylenediamine (PPD), a combination of 4,4'-diaminodiphenyl ether (ODA) and m-tolidine, or a combination of 4,4'-methylenedianiline (MDA) and paraphenylenediamine (PPD).

[0024] By using the monomers of the above combination, it is possible to achieve excellent peel strength and mechanical properties.

[0025] In one embodiment, the polyimide may include a dianhydride monomer comprising pyromellitic dianhydride (PMDA) and a diamine monomer comprising 4,4'-diaminodiphenyl ether (ODA) as polymerization units.

[0026] In one embodiment, the polyimide may include a dianhydride monomer comprising pyromellitic dianhydride (PMDA) and a diamine monomer comprising 4,4'-diaminodiphenyl ether (ODA) and paraphenylenediamine (PPD) as polymerization units.

[0027] In one embodiment, the polyimide may include a dianhydride monomer comprising pyromellitic dianhydride (PMDA) and a diamine monomer comprising 4,4'-diaminodiphenyl ether (ODA) and m-tolidine as polymerization units.

[0028] In one embodiment, the polyimide may include a dianhydride monomer comprising pyromellitic dianhydride (PMDA) and a diamine monomer comprising 4,4'-methylenedianiline (MDA) and paraphenylenediamine (PPD) as polymerization units.

[0029] In one embodiment, the polyimide may include a dianhydride monomer comprising biphenyl tetracarboxylic dianhydride (BPDA) and a diamine monomer comprising 4,4'-diaminodiphenyl ether (ODA) and paraphenylenediamine (PPD) as polymerization units.

[0030] With respect to the total diamine monomer of the polyimide, the content of the first diamine, namely 4,4'-diaminodiphenyl ether (ODA) or 4,4'-methylenedianiline (MDA), may be 50 mol% to 100 mol%, preferably 50 mol% to 95 mol%, more preferably 60 mol% to 85 mol%, and even more preferably 70 mol% to 80 mol%.

[0031] If the above first diamine monomer is below the above range, the elongation decreases and the desired elongation is not achieved, and if it exceeds the above range, thermal properties such as tensile strength decrease and / or CTE increase may deteriorate.

[0032] In addition, with respect to the total diamine monomer of the polyimide, the content of the second diamine, namely paraphenylenediamine (PPD) or m-tolidine, may be 0 mol% to 50 mol%, preferably greater than 0 mol% and 50 mol% or less. Here, 0 mol% may mean that the second diamine, namely paraphenylenediamine (PPD) or m-tolidine, is not included in the polyimide. More specifically, the content of the second diamine may be 0.1 mol% to 50 mol%, preferably 5 mol% to 50 mol%, more preferably 10 mol% to 40 mol%, and even more preferably 20 mol% to 30 mol%.

[0033] If the above second diamine monomer is below the above range, the tensile strength decreases, and if it exceeds the above range, the elongation decreases, causing the film to become brittle and break.

[0034] In addition, the polyimide may contain 90 to 110 mol% of the dianhydride monomer, preferably 95 to 105 mol%, more preferably 98 to 102 mol%, and even more preferably 100 mol%.

[0035] In addition, the polyimide may contain 90 to 110 mol% of the diamine monomer, preferably 95 to 105 mol%, more preferably 98 to 102 mol%, and even more preferably 100 mol%.

[0036] The molar ratio of the above dianhydride monomer to the above diamine monomer may be 1:2 to 2:1, and preferably 1:1.

[0037] The above-mentioned mixed film may have a tensile strength of 130 MPa or higher, preferably with a lower limit of 130.5 MPa or higher, 131 MPa or higher, 131.5 MPa or higher, 132 MPa or higher, 133 MPa or higher, 134 MPa or higher, or 135 MPa or higher, and the upper limit is not specifically limited but may be 400 MPa or lower. At this time, the tensile strength was measured using the ASTM D-882 method under speed conditions (200 mm / min) by preparing a sample with a length of 50 mm and a width of 15 mm using an INSTRON Instron 5564 UTM instrument.

[0038] The above mixed film may have an elongation of 22% or more, and preferably, the lower limit may be 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, or 27% or more. The upper limit is not specifically limited but may be 100% or less. At this time, the elongation was measured by preparing a sample with a length of 50mm and a width of 15mm using an INSTRON Instron 5564 UTM instrument and measuring the elongation according to ASTM D-882 standards.

[0039] The above mixed film may have an elastic modulus of 2.5 GPa or higher, and preferably, the lower limit may be 2.6 GPa or higher, 2.65 GPa or higher, 2.7 GPa or higher, 2.8 GPa or higher, 2.85 GPa or higher, 2.9 GPa or higher, 2.95 GPa or higher, or 3.0 GPa or higher. The upper limit is not specifically limited, but may be 10 GPa or lower. At this time, the elastic modulus was measured using the ASTM D-882 method under speed conditions (200 mm / min) by preparing a sample with a length of 50 mm and a width of 15 mm using an INSTRON Instron 5564 UTM instrument.

[0040] The thickness of the above-mentioned mixed film can be appropriately selected considering the application, usage environment, and physical properties of the polyimide film. For example, the thickness of the mixed film may be 5 to 300 μm, preferably 10 to 200 μm, more preferably 15 to 100 μm, and even more preferably 20 to 50 μm, but is not limited thereto.

[0041] The mixed film of the present invention comprises polyamideimide and polyimide, and by combining them with optimal monomers and mixing them in appropriate proportions, it is possible to reduce costs and form a gel-like self-supporting film that secures mechanical properties above a certain level as imidization proceeds on a support, and finally, the mechanical properties and peelability of the mixed film can be improved. Accordingly, it can be usefully applied in product fields where conventional polyimide films were used.

[0042] Method for manufacturing a mixed film

[0043] In another aspect of the present invention, (a) one or more selected from the group consisting of trimellitic acid anhydride (TMA) and methylene diphenyl diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), m-phenylene diisocyanate (MPDI), 2,4-toluene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diphenylisopropylidene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, dianisidine diisocyanate, tolidine diisocyanate (TODI), and hexamethylene diisocyanate. (b) a step of preparing a polyamideimide precursor composition comprising a diisocyanate monomer as a polymerization unit; (b) a step of preparing a polyimide precursor composition comprising a dianhydride monomer comprising one or more selected from the group consisting of pyromellitic dianhydride (PMDA), biphenyl tetracarboxylic dianhydride (BPDA), and benzophenone tetracarboxylic dianhydride (BTDA), and a diamine monomer comprising one or more selected from the group consisting of 4,4'-diaminodiphenyl ether (ODA), 4,4'-methylenedianiline (MDA), metaphenylenediamine (MPD), paraphenylenediamine (PPD), and m-tolidine as a polymerization unit; (c) a step of preparing a mixed solution by mixing the polyamideimide precursor composition and the polyimide precursor composition; and (d) a step of reacting the above-mentioned mixed solution to produce a mixed film comprising polyamideimide and polyimide; and a method for producing a mixed film having a tensile strength of 130 MPa or more.

[0044] In this case, the content of polyamideimide, polyimide, dianhydride, diamine, each monomer, tensile strength, elongation, and modulus of elasticity are applied in the same manner as the contents of the aforementioned mixed film.

[0045] With respect to 100 wt% of the above mixed film, it may comprise 40 to 99 wt% of the polyamideimide; and 1 to 60 wt% of the polyimide; and preferably may comprise 45 to 85 wt% of the polyamideimide; and 15 to 55 wt% of the polyimide.

[0046] The above polyamideimide precursor composition and polyimide precursor composition can be prepared in the presence of a solvent.

[0047] The above solvent may include one or more selected from the group consisting of N,N'-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N,N'-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), diethylacetamide (DEAc), N-ethyl-2-pyrrolidone (NEP), N,N'-diethylformamide (DEF), dimethylpropanamide (DMPA), and gamma-butyrolactone (GBL), and preferably N,N'-dimethylformamide (DMF) may be used.

[0048] In step (a), using the isocyanate method to prepare the polyamideimide precursor composition prevents the generation of water during the reaction process, thereby preventing the polymer from being hydrolyzed.

[0049] Specifically, step (a) can be carried out by continuously reacting trimellitic acid anhydride (TMA) and the diisocyanate monomer in the presence of a solvent at a temperature of 30 to 100°C for 1 to 3 hours and at a temperature of 100 to 200°C for 1 to 5 hours, and then releasing carbon dioxide as a byproduct.

[0050] The above polyamideimide precursor composition may be advantageous in terms of productivity if the solid content concentration is 15 to 50 weight%, preferably 25 to 40 weight%, and may be desirable in terms of improving heat resistance while maintaining an appropriate viscosity for film formation if the weight-average molecular weight is 10,000 to 100,000 g / mol.

[0051] Additionally, step (b) can be carried out by reacting the dianhydride monomer and the diamine monomer in the presence of a solvent at a temperature of 5 to 50°C for 4 to 8 hours.

[0052] The above polyimide precursor composition may be advantageous in terms of increasing productivity if the solid content concentration is 10 to 35 weight%.

[0053] In step (c), the mixed solution may further include an imidizing agent, and the imidizing agent may include a catalyst and a dehydrating agent. Preferably, the imidizing agent may include a combination of a dehydrating agent represented by an acid anhydride such as acetic anhydride and an imidizing catalyst represented by tertiary amines such as isoquinoline, β-picoline, and pyridine. More preferably, the imidizing agent may include a dehydrating agent, a catalyst, and a diluent solvent, and the diluent solvent may be NMP, DMF, DAMc, etc. It is desirable to add the imidizing agent appropriately considering the film formation characteristics.

[0054] The above mixed solution is at a temperature of 23℃ and 1s -1 A viscosity of 10,000 to 300,000 cP measured under shear rate conditions may be advantageous when considering smooth discharge of the mixed solution and flatness of the discharged solution.

[0055] Step (d) may include (d-1) a step of preparing a mixed gel film by applying and drying the mixed solution on a support; and (d-2) a step of preparing a mixed film by peeling the mixed gel film from the support and heat treating it.

[0056] In step (d-1), the drying may be performed at a temperature of 100 to 160°C for 3 to 30 minutes.

[0057] In step (d-2), the heat treatment may be performed at a temperature of 200 to 400°C for 3 to 30 minutes. Specifically, in step (d-2), the remaining polyamic acid of the polyimide precursor composition may be imidized to produce the mixed film of the present invention.

[0058] The above mixed film may have a tensile strength of 130 MPa or more, an elongation of 22% or more, and an elastic modulus of 2.5 GPa or more.

[0059] The mixed film and the method for manufacturing the same according to the present invention, by including polyamideimide and polyimide, can obtain a mixed film having excellent mechanical properties (particularly tensile strength and elongation) and excellent peelability, and has the effect of reducing costs.

[0060] In addition, the mixed film according to the present invention and the method for manufacturing the same can be usefully applied in product fields where conventional polyimide films were applied.

[0061] Figure 1 is a photograph confirming the peeling characteristics of Example 1 and Comparative Example 1.

[0062] Examples are provided to aid in understanding the present invention. The following examples are provided merely to facilitate a better understanding of the invention, and the scope of the invention is not limited by these examples.

[0063] <Example>

[0064] Preparation Example 1: Preparation of a polyamideimide precursor composition (TMA+MDI)

[0065] A polyamideimide precursor composition (PAI) was prepared by introducing the solvent dimethylformamide (DMF) into a 500 ml reactor equipped with a stirrer and a nitrogen injection / discharge pipe, adding 100.1 mol% of trimellitic anhydride (TMA) and 100 mol% of methylene diphenyl diisocyanate (MDI), and reacting continuously at 70°C for 2 hours and at 160°C for 3 hours (solid content 35 wt%, viscosity at 23°C 30,000~60,000 cP).

[0066] Preparation Example 2: Preparation of a polyimide precursor composition (PMDA+ODA)

[0067] A 500 ml reactor equipped with a stirrer and a nitrogen inlet / outlet pipe was prepared by adding the solvent dimethylformamide (DMF), a dianhydride monomer containing 100 mol% of pyromellitic dianhydride (PMDA), and a diamine monomer containing 100 mol% of 4,4'-diaminodiphenyl ether (ODA), and reacting at 25°C for 3 hours to prepare a polyimide precursor composition (PI) (solid content 20 wt%, viscosity at 23°C 200,000 cP).

[0068] Preparation Example 3: Preparation of a polyimide precursor composition (PMDA+ODA+PPD)

[0069] A polyimide precursor composition (PI) was prepared in the same manner as in Preparation Example 2, except that 75 mol% of 4,4'-diaminodiphenyl ether (ODA) and 25 mol% of paraphenylenediamine (PPD) were used instead of 100 mol% of 4,4'-diaminodiphenyl ether (ODA) as in Preparation Example 2.

[0070] Preparation Example 4: Preparation of a polyimide precursor composition (PMDA+ODA+m-TD)

[0071] A polyimide precursor composition (PI) was prepared in the same manner as in Preparation Example 2, except that 75 mol% of 4,4'-diaminodiphenyl ether (ODA) and 25 mol% of 2,2'-dimethylbenzidine (m-TD) were used instead of 100 mol% of 4,4'-diaminodiphenyl ether (ODA) in Preparation Example 2.

[0072] Preparation Example 5: Preparation of a polyimide precursor composition (PMDA+MDA+PPD)

[0073] A polyimide precursor composition (PI) was prepared in the same manner as in Preparation Example 2, except that 75 mol% of 4,4'-methylenedianiline (MDA) and 25 mol% of paraphenylenediamine (PPD) were used instead of 100 mol% of 4,4'-diaminodiphenyl ether (ODA) in Preparation Example 2.

[0074] Preparation Example 6: Preparation of a polyimide precursor composition (BPDA+ODA+PPD)

[0075] A polyimide precursor composition (PI) was prepared in the same manner as in Preparation Example 2, except that 100 mol% of biphenyl tetracarboxylic dianhydride (BPDA) was used instead of 100 mol% of pyromellitic dianhydride (PMDA) in Preparation Example 2, and 75 mol% of 4,4'-diaminodiphenyl ether (ODA) and 25 mol% of paraphenylenediamine (PPD) were used instead of 100 mol% of 4,4'-diaminodiphenyl ether (ODA).

[0076] Example 1: Preparation of mixed film (PAI+PI)

[0077] A polyamideimide precursor composition according to Preparation Example 1 and a polyimide precursor composition according to Preparation Example 3 were mixed in a weight ratio (wt%) of 62.5:37.5 to prepare 100g of a mixed solution. An imidizing agent comprising the solvent dimethylformamide (DMF), the catalyst beta-picoline (BP), and the dehydrating agent acetic anhydride (AA) was added to the mixed solution, and the resulting solution was extruded from a die and flexibly coated onto a support (SUS Plate), and dried at 160°C for about 3 minutes to produce a self-supporting mixed gel film.

[0078] Next, the self-supporting mixed gel film was peeled off from the support and heat-treated at 200°C for about 4 minutes and at 300°C for about 3 minutes to prepare a mixed film containing polyamideimide and polyimide (thickness: 25 μm).

[0079] Examples 2 to 11 and Comparative Example 1

[0080] A mixed film was prepared in the same manner as in Example 1, except that the composition of PAI and PI and the content ratio of PAI and PI were adjusted as shown in Table 1 below.

[0081]

[0082] The composition and content ratio of polyamideimide (PAI) and polyimide (PI) used when preparing the mixed films according to Examples 1 to 11 and Comparative Example 1 are listed in Table 1.

[0083] Mixed Film (PAI+PI) Composition Content Ratio PAIPIPAI:PI (wt%) Example 1 Preparation Example 1 (TMA+MDI) Preparation Example 3 (PMDA+ODA+PPD) 62.5 : 37.5 Example 2 50 : 50 Example 3 75 : 25 Example 4 Preparation Example 4 (PMDA+ODA+m-TD) 62.5 : 37.5 Example 5 50 : 50 Example 6 Preparation Example 5 (PMDA+MDA+PPD) 62.5 : 37.5 Example 7 50 : 50 Example 8 Preparation Example 6 (BPDA+ODA+PPD) 62.5 : 37.5 Example 9 50 : 50 Example 10 Preparation Example 2 (PMDA+ODA) 62.5 : 37.5 1150 : 50 Comparative Example 1-100 : 0

[0084] <Experimental Example>

[0085] Experimental Example 1: Evaluation of Peeling Characteristics

[0086] The peeling characteristics of the mixed gel films according to Examples 1 to 11 and Comparative Example 1 were visually observed while peeling them from the support, and the results are shown in FIG. 1 and Table 2.

[0087] Classification Peeling Characteristics Example 1 Excellent Example 2 Excellent Example 3 Excellent Example 4 Excellent Example 5 Excellent Example 6 Excellent Example 7 Excellent Example 8 Excellent Example 9 Excellent Example 10 Excellent Example 11 Excellent Comparative Example 1 Low

[0088] According to Figure 1 and Table 2, it was found that Examples 1 to 11 exhibited excellent peeling levels. However, Comparative Example 1, containing 100 wt% polyamideimide, showed a level where peeling from the support was almost impossible. This indicates that when only polyamideimide is used, the formation of a gel film is impossible, requiring long-term drying, and there is a problem where the polyamideimide film adheres to the support and does not peel off.

[0089]

[0090] Experimental Example 2: Evaluation of Physical Properties of Mixed Film

[0091] (1) Tensile strength

[0092] Samples with a length of 50 mm and a width of 15 mm were prepared using an INSTRON Instron 5564 UTM instrument, and the tensile strength of the polyimide films prepared according to the examples and comparative examples was measured using the ASTM D-882 method under speed conditions of 200 mm / min, and the average of the five samples was calculated. The results are shown in Table 3 below.

[0093] (2) Elongation

[0094] Samples with a length of 50 mm and a width of 15 mm were prepared using an INSTRON Instron 5564 UTM instrument, and the elongation of the polyimide films according to the examples and comparative examples was measured under room temperature conditions using the ASTM D-882 method. The results are shown in Table 3 below.

[0095] (3) Modulus

[0096] Samples with a length of 50 mm and a width of 15 mm were prepared using an INSTRON Instron 5564 UTM instrument, and the tensile strength of the polyimide films prepared according to the examples and comparative examples was measured using the ASTM D-882 method under speed conditions of 200 mm / min, and the average of the five samples was calculated. The results are shown in Table 3 below.

[0097] Classification Tensile Strength (Mpa) Elongation (%) Modulus of Elasticity (GPa) Example 1 138 32.13.00 Example 2 137 27.13.06 Example 3 138 39.72.68 Example 4 134 29.12.89 Example 5 139 38.63.01 Example 6 135 30.53.08 Example 7 139 38.93.11 Example 8 133 33.43.09 Example 9 136 39.63.14 Example 10 131 24.62.87 Example 11 130 24.22.86 Comparative Example 1 11 0 12.62.60

[0098] According to Table 3, the polyamideimide and polyimide mixed films according to Examples 1 to 11 were found to have excellent mechanical properties, satisfying all conditions of a tensile strength of 130 MPa or more, an elongation of 22% or more, and an elastic modulus of 2.5 GPa or more. On the other hand, Comparative Example 1, which contained 100% polyamideimide (PAI), could not be peeled off, and the tensile strength and elongation of the film were very low.

[0099] Accordingly, the mixed film containing polyamideimide / polyimide according to the present invention was able to produce a mixed film with excellent peelability based on a gel film that secures mechanical properties above a certain level, and ultimately excellent mechanical properties (tensile strength and elongation).

[0100]

[0101] The specification omits detailed descriptions of matters that can be sufficiently recognized and inferred by those skilled in the art of the present invention, and various modifications are possible within the scope of not altering the technical concept or essential configurations of the present invention, in addition to the specific examples described in this specification. Accordingly, the present invention may be implemented in a manner different from that specifically described and exemplified in this specification, and this is a matter that can be understood by those skilled in the art.

Claims

1. A diisocyanate comprising one or more selected from the group consisting of trimellitic acid anhydride (TMA) and methylene diphenyl diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), m-phenylene diisocyanate (MPDI), 2,4-toluene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diphenylisopropylidene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, dianisidine diisocyanate, tolidine diisocyanate (TODI), and hexamethylene diisocyanate. Polyamideimide comprising monomers as polymerization units; and A polyimide comprising, as a polymerization unit, a dianhydride monomer comprising one or more selected from the group consisting of pyromellitic dianhydride (PMDA), biphenyl tetracarboxylic dianhydride (BPDA), and benzophenone tetracarboxylic dianhydride (BTDA), and a diamine monomer comprising one or more selected from the group consisting of 4,4'-diaminodiphenyl ether (ODA), 4,4'-methylenedianiline (MDA), metaphenylenediamine (MPD), paraphenylenediamine (PPD), and m-tolidine; A mixed film having a tensile strength of 130 MPa or higher.

2. In claim 1, with respect to 100 wt% of the mixed film, 40 to 99 wt% of the above polyamideimide; and A mixed film comprising 1 to 60 wt% of the above polyimide.

3. In claim 1, with respect to 100 wt% of the mixed film, 45 to 85 wt% of the above polyamideimide; and A mixed film comprising 15 to 55 wt% of the above polyimide.

4. A mixed film according to claim 1, wherein the polyamideimide comprises trimellitic anhydride (TMA) and methylene diphenyl diisocyanate (MDI) as polymerization units.

5. A mixed film according to claim 1, wherein the dianhydride monomer of the polyimide comprises pyromellitic dianhydride (PMDA) or biphenyl tetracarboxylic dianhydride (BPDA).

6. In claim 1, the diamine monomer of the polyimide A mixed film comprising a first diamine comprising 4,4'-diaminodiphenyl ether (ODA) or 4,4'-methylenedianiline (MDA).

7. In claim 6, the diamine monomer of the polyimide A mixed film further comprising paraphenylenediamine (PPD) or m-tolidine (m-tolidine) second diamine.

8. In claim 6, with respect to the total diamine monomer of the polyimide, A mixed film having a content of 50 mol% to 100 mol% of the first diamine.

9. In claim 7, with respect to the total diamine monomer of the polyimide, A mixed film having a second diamine content of 0 mol% to 50 mol% of the polyimide.

10. A mixed film according to claim 1, wherein the elongation of the mixed film is 22% or more.

11. A mixed film according to claim 1, wherein the elastic modulus of the mixed film is 2.5 GPa or higher.

12. (a) Trimellitic acid anhydride (TMA) and one or more selected from the group consisting of methylene diphenyl diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), m-phenylene diisocyanate (MPDI), 2,4-toluene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diphenylisopropylidene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, dianisidine diisocyanate, tolidine diisocyanate (TODI), and hexamethylene diisocyanate A step of preparing a polyamideimide precursor composition comprising a diisocyanate monomer as a polymerization unit; (b) a step of preparing a polyimide precursor composition comprising, as polymerization units, a dianhydride monomer comprising one or more selected from the group consisting of pyromellitic dianhydride (PMDA), biphenyl tetracarboxylic dianhydride (BPDA), and benzophenone tetracarboxylic dianhydride (BTDA), and a diamine monomer comprising one or more selected from the group consisting of 4,4'-diaminodiphenyl ether (ODA), 4,4'-methylenedianiline (MDA), metaphenylenediamine (MPD), paraphenylenediamine (PPD), and m-tolidine; (c) a step of preparing a mixed solution by mixing the above polyamideimide precursor composition and the polyimide precursor composition; and (d) a step of reacting the above mixed solution to produce a mixed film containing polyamideimide and polyimide; comprising, A method for manufacturing a mixed film having a tensile strength of 130 MPa or more.

13. In Clause 12, with respect to 100 wt% of the above mixed film, 40 to 99 wt% of the above polyamideimide; and A method for manufacturing a mixed film comprising 1 to 60 wt% of the above-mentioned polyimide.

14. In Paragraph 12, step (d) (d-1) a step of preparing a mixed gel film by applying and drying the above mixed solution onto a support; and (d-2) A step of peeling the mixed gel film from the support and heat-treating to produce a mixed film; comprising a method for manufacturing a mixed film.

15. A method for manufacturing a mixed film according to claim 12, wherein the elongation of the mixed film is 22% or more.

16. A method for manufacturing a mixed film according to claim 12, wherein the elastic modulus of the mixed film is 2.5 GPa or higher.

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