Polyimide film having low dielectric properties and high heat resistance, and method for manufacturing the same

Abstract

The present invention provides a polyimide film obtained by imidizing a polyamic acid solution containing a dianhydride acid component including two or more selected from the group consisting of biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and p-phenylene bis(trimellitate anhydride) (TAHQ), and a diamine component including one or more selected from the group consisting of oxydianiline (ODA), paraphenylenediamine (PPD), and m-tolidine (mTD), and the polyimide film has a dielectric loss factor (Df) of 0.0025 or less and a glass transition temperature (Tg) of 240° C. or more.

Description

Technical Field

[0001] The present invention relates to a polyimide film having excellent low dielectric and heat resistance properties.

Background Art

[0002] Polyimide (PI) is a polymer material with an imide ring having extremely excellent chemical stability along with a rigid aromatic main chain, and has the highest level of heat resistance, chemical resistance, electrical insulation, chemical resistance, and weather resistance among organic materials.

[0003] In particular, due to its excellent insulating properties, that is, excellent electrical properties such as a low dielectric constant, it has attracted attention as a high-functional polymer material in fields such as electricity, electronics, and optics.

[0004] Recently, with the miniaturization and weight reduction of electronic products, highly integrated and flexible thin circuit boards have been actively developed.

[0005] Such thin circuit boards tend to utilize a structure in which a circuit including a metal foil is formed on a polyimide film that has excellent heat resistance, low temperature resistance, and insulating properties and is easy to bend.

[0006] As such thin circuit boards, flexible metal foil laminates are mainly used. As an example, a flexible copper clad laminate (FCCL) using a thin copper plate for the metal foil is included. In addition, polyimide is also utilized as a protective film, insulating film, etc. of a thin circuit board.

[0007] On the other hand, recently, as various functions are incorporated into electronic devices, high computing speed and communication speed are required for the electronic devices. To meet this requirement, thin circuit boards capable of high-speed communication at high frequencies have been developed.

[0008] To realize high-frequency, high-speed communication, an insulator with high impedance that can maintain electrical insulation even at high frequencies is necessary. Since impedance is inversely proportional to the frequency and dielectric constant (Dk) formed in the insulator, the dielectric constant must be as low as possible to maintain insulation even at high frequencies.

[0009] However, in the case of ordinary polyimides, the dielectric properties are not currently at a level that is good enough to maintain sufficient insulation for high-frequency communication.

[0010] Furthermore, it is known that the lower the dielectric properties of an insulator, the more it is possible to reduce the generation of unwanted stray capacitance and noise in thin circuit boards, thereby largely eliminating the causes of communication delay.

[0011] Therefore, polyimide with low dielectric properties is currently recognized as the most important factor in the performance of thin circuit boards.

[0012] In particular, in the case of high-frequency communication, dielectric dissipation due to polyimide inevitably occurs. The dielectric dissipation factor (Df) represents the degree of electrical energy wasted by the thin circuit board and is closely related to the signal transmission delay that determines the communication speed. Therefore, maintaining the dielectric dissipation factor of polyimide as low as possible is recognized as an important factor in the performance of thin circuit boards.

[0013] Furthermore, the more moisture a polyimide film contains, the larger its dielectric constant becomes, and the higher its dielectric loss rate. While polyimide films are suitable as materials for thin circuit boards due to their excellent inherent properties, they are relatively vulnerable to moisture due to the polar imide groups, which can lead to a decrease in their insulating properties.

[0014] Therefore, the current need is to develop polyimide films with improved dielectric properties, particularly low dielectric loss, while maintaining the unique mechanical, thermal, and high-adhesion surface properties of polyimide at a certain level. [Prior art documents] [Patent Documents]

[0015] [Patent Document 1] Republic of Korea Patent Publication No. 10-2021-0055230 [Overview of the Initiative] [Problems that the invention aims to solve]

[0016] Therefore, in order to solve the above problems, the objective is to provide a polyimide film that possesses excellent low dielectric properties and heat resistance. [Means for solving the problem]

[0017] To achieve the above objective, one embodiment of the present invention comprises a dianhydride acid component comprising two or more selected from the group consisting of biphenyltetracarboxylic dianehydride (BPDA), pyromellitic dianehydride (PMDA), and p-phenylenebis (trimellitate anhydride) (TAHQ), The present invention provides a polyimide film produced by imidizing a polyamic acid solution containing a diamine component comprising two or more selected from the group consisting of oxydianiline (ODA), paraphenylenediamine (PPD), and m-tolidine (mTD).

[0018] However, the dianhydride acid component of the polyimide film must include biphenyltetracarboxylic dianehydride and p-phenylenebis(trimellitate anhydride).

[0019] Another embodiment of the present invention provides a polyimide film in which, based on a total content of 100 mol% of the dianhydride acid components, the content of biphenyltetracarboxylic dianehydride (BPDA) is 30 mol% or more and 70 mol% or less, the content of pyromeretic dianehydride (PMDA) is 40 mol% or less, and the content of p-phenylenebis(trimellitate anhydride) (TAHQ) is 15 mol% or more and 35 mol% or less.

[0020] A further embodiment of the present invention provides a polyimide film in which, based on a total content of 100 mol% of the diamine components, the content of oxydianiline (ODA) is 35 mol% or less, the content of paraphenylenediamine (PPD) is 55 mol% or less, and the content of m-tolidine is 45 mol% or more.

[0021] Yet another embodiment of the present invention provides a polyimide film comprising a block copolymer consisting of two or more blocks.

[0022] A further embodiment of the present invention provides a polyimide film comprising a block copolymer comprising a first block obtained by imidizing a dianhydride component containing p-phenylenebis(trimellitate anhydride) (TAHQ) with a diamine component containing m-tolidine (mTD) and oxydianiline (ODA), and a second block obtained by imidizing a dianhydride component containing biphenyltetracarboxylic dianehydride (BPDA) and pyromeretic dianehydride (PMDA) with a diamine component containing m-tolidine (mTD) and paraphenylenediamine (PPD).

[0023] A further embodiment of the present invention provides a polyimide film having a dielectric loss rate (Df) of 0.0025 or less and a glass transition temperature (Tg) of 240°C or higher.

[0024] Still other embodiments of the present invention provide a method for manufacturing a polyimide film, comprising: polymerizing a dianhydride acid component containing two or more selected from the group consisting of biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and p-phenylenebis(trimellitate anhydride) (TAHQ), and a diamine component containing two or more selected from the group consisting of oxydianiline (ODA), paraphenylenediamine (PPD), and m-tolidine (mTD) to produce a polyamic acid solution; and imidizing the polyamic acid solution.

[0025] The dianhydride acid component in the method for manufacturing the polyimide film necessarily contains biphenyltetracarboxylic dianhydride and p-phenylenebis(trimellitate anhydride).

[0026] Still other embodiments of the present invention provide a method for manufacturing a polyimide film, wherein, based on 100 mol% of the total content of the dianhydride acid component, the content of biphenyltetracarboxylic dianhydride (BPDA) is 30 mol% or more and 70 mol% or less, the content of pyromellitic dianhydride (PMDA) is 40 mol% or less, and the content of p-phenylenebis(trimellitate anhydride) (TAHQ) is 15 mol% or more and 35 mol% or less.

[0027] Still other embodiments of the present invention provide a method for manufacturing a polyimide film, wherein, based on 100 mol% of the total content of the diamine component, the content of oxydianiline (ODA) is 35 mol% or less, the content of paraphenylenediamine (PPD) is 55 mol% or less, and the content of m-tolidine is 45 mol% or more. A method for manufacturing a polyimide film is provided.

[0028] A further embodiment of the present invention provides a method for producing a polyimide film having a dielectric loss rate (Df) of 0.0025 or less and a glass transition temperature (Tg) of 240°C or higher.

[0029] Yet another embodiment of the present invention provides a multilayer film comprising the polyimide film.

[0030] Yet another embodiment of the present invention provides a multilayer film comprising the polyimide film and a thermoplastic resin layer.

[0031] Yet another embodiment of the present invention provides a flexible metal foil laminate comprising the polyimide film and an electrically conductive metal foil.

[0032] Yet another embodiment of the present invention provides an electronic component including the flexible metal foil laminate. [Effects of the Invention]

[0033] As described above, the present invention provides a polyimide film manufactured by imidizing a polyamic acid solution consisting of specific components and a specific composition ratio, and having low dielectric properties and high heat resistance properties. Therefore, it can be usefully applied to a variety of fields where such properties are required, particularly to electronic components such as flexible metal foil laminates. [Modes for carrying out the invention]

[0034] Embodiments of the present invention will be described in more detail below.

[0035] Prior to this, terms and words used in this specification and in the claims should not be interpreted in a manner limited to their ordinary or dictionary meanings, but rather in a manner consistent with the technical idea of ​​the present invention, in accordance with the principle that inventors may appropriately define the concepts of terms in order to best describe their invention.

[0036] Therefore, the configurations of the embodiments described herein represent only one of the most preferred embodiments of the present invention and do not represent the entire technical concept of the invention. It should be understood that, at the time of filing, there are various equivalents and modifications that can be substituted for these embodiments.

[0037] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “includes,” “equip,” or “have” are intended to specify the existence of an implemented feature, number, stage, component, or combination thereof, and should be understood not to preemptively exclude the possibility of the existence or addition of one or more other features, numbers, stages, components, or combinations thereof.

[0038] Wherever a quantity, concentration, or other value or parameter is given in this specification as an enumeration of ranges, preferred ranges, preferred upper limits, and preferred lower limits, it should be understood that all ranges formed by any pair of limits or preferred values ​​of any upper range and any limits or preferred values ​​of any lower range are specifically disclosed, regardless of whether the ranges are disclosed separately.

[0039] Where a range of numbers is referred to herein, unless otherwise specified, that range is intended to include its endpoint and all integers and fractions within that range. The scope of the present invention is not intended to be limited to the specific values ​​referred to when defining a range.

[0040] In this specification, “dianhydric acid” is intended to include its precursors or derivatives, which may not be technically dianhydric acids, but nevertheless should react with diamines to form polyamic acids, which are then converted back to polyimides.

[0041] In this specification, “diamine” is intended to include its precursors or derivatives, which may not be technically diamines, but nevertheless should react with dianehydrides to form polyamic acids, which are then converted back to polyimides.

[0042] The polyimide film according to the present invention can be produced by imidizing a polyamic acid solution containing a dianhydride acid component comprising two or more selected from the group consisting of biphenyltetracarboxylic dianehydride (BPDA), pyromeretic dianehydride (PMDA), and p-phenylenebis(trimellitate anhydride) (TAHQ), and a diamine component comprising two or more selected from the group consisting of oxydianiline (ODA), paraphenylenediamine (PPD), and m-tolidine (mTD).

[0043] However, the dianhydride acid component may always include biphenyltetracarboxylic dianehydride and p-phenylenebis(trimellitate anhydride).

[0044] For example, (1) a polyimide film produced by imidizing a polyamic acid containing a dianhydride acid component consisting of p-phenylenebis(trimellitate anhydride) (TAHQ) and biphenyltetracarboxylic dianehydride (BPDA), and a diamine component consisting of m-tolidine (mTD), oxydianiline (ODA), and paraphenylenediamine (PPD); (2) a polyimide film produced by imidizing a polyamic acid containing a dianhydride acid component consisting of p-phenylenebis(trimellitate anhydride) (TAHQ), biphenyltetracarboxylic dianehydride (BPDA), and pyromeretic dianehydride (PMDA), and a diamine component consisting of m-tolidine (mTD) and paraphenylenediamine (PPD); or (3) p-phenylene (4) A polyimide film may be produced by imidizing a polyamic acid containing a dianhydride acid component consisting of bis(trimellitate anhydride) (TAHQ), biphenyltetracarboxylic dianehydride (BPDA), and pyromellitic dianehydride (PMDA), and a diamine component consisting of m-tolidine (mTD) and oxydianiline (ODA), or (4) a polyimide film may be produced by imidizing a polyamic acid containing a dianhydride acid component consisting of p-phenylenebis(trimellitate anhydride) (TAHQ), biphenyltetracarboxylic dianehydride (BPDA), and pyromellitic dianehydride (PMDA), and a diamine component consisting of m-tolidine (mTD), oxydianiline (ODA), and paraphenylenediamine (PPD).

[0045] In one embodiment, based on a total content of 100 mol% of the dianhydride acid components, the content of biphenyltetracarboxylic dianehydride (BPDA) may be 30 mol% or more and 70 mol% or less, the content of pyromellitic dianehydride (PMDA) may be 40 mol% or less, and the content of p-phenylenebis(trimellitate anhydride) (TAHQ) may be 15 mol% or more and 35 mol% or less. Preferably, the content of biphenyltetracarboxylic dianehydride (BPDA) may be 35 mol% or more and 65 mol% or less, the content of pyromellitic dianehydride (PMDA) may be 35 mol% or less, and the content of p-phenylenebis(trimellitate anhydride) (TAHQ) may be 20 mol% or more and 35 mol% or less.

[0046] The polyimide chain derived from the biphenyltetracarboxylic dianehydride (BPDA) has a structure called a charge transfer complex (CTC), which is a regular linear structure in which electron donors and electron acceptors are located in close proximity to each other, thereby enhancing intermolecular interactions.

[0047] This structure has the effect of preventing hydrogen bonding with moisture, thus influencing the reduction of the moisture absorption rate and maximizing the effect of reducing the hygroscopicity of the polyimide film.

[0048] For a polyimide film to simultaneously satisfy appropriate elasticity and moisture absorption, the content ratio of dianhydrides is particularly important. For example, the lower the content ratio of biphenyltetracarboxylic dianehydride (BPDA), the less likely it is to achieve the low moisture absorption rate due to the CTC structure.

[0049] Furthermore, while biphenyltetracarboxylic dianehydride (BPDA) contains two benzene rings corresponding to the aromatic moiety, pyromeretic dianehydride (PMDA) contains one benzene ring corresponding to the aromatic moiety.

[0050] The pyromeretic dianehydride (PMDA) is preferred because, as a dianhydride acid component having a relatively rigid structure, it can impart appropriate elasticity to the polyimide film.

[0051] The increase in the pyromeretic dianehydride (PMDA) content can be understood as an increase in the number of imide groups within the molecule, relative to the same molecular weight. This can be understood as the ratio of imide groups derived from pyromeretic dianehydride (PMDA) to imide groups derived from biphenyltetracarboxylic dianehydride (BPDA) in the polyimide polymer chain increasing relatively.

[0052] In other words, an increase in the pyromeretic dianehydride content can be considered a relative increase in imide groups for the polyimide film as a whole, making it difficult to expect a low moisture absorption rate.

[0053] If the content of biphenyltetracarboxylic dianehydride (BPDA) exceeds 70 mol%, the heat resistance of the polyimide film may decrease when manufacturing flexible metal foil laminates.

[0054] Conversely, if the content of biphenyltetracarboxylic dianehydride (BPDA) is less than 30 mol% or the content of pyromeretic dianehydride (PMDA) is more than 40 mol%, it may be difficult to achieve appropriate levels of dielectric constant, low dielectric loss characteristics, and glass transition temperature.

[0055] Furthermore, if the p-phenylenebis(trimellitate anhydride) (TAHQ) content exceeds 35 mol%, achieving the glass transition temperature becomes difficult, and if it is less than 15 mol%, achieving low dielectric loss characteristics may become difficult.

[0056] In other embodiments, based on a total content of 100 mol% of the diamine components, the content of oxydianiline (ODA) may be 35 mol% or less, the content of paraphenylenediamine (PPD) may be 55 mol% or less, and the content of m-tolidine may be 45 mol% or more. Preferably, the content of oxydianiline (ODA) may be 30 mol% or less, the content of paraphenylenediamine (PPD) may be 50 mol% or less, and the content of m-tolidine may be 50 mol% or more.

[0057] The aforementioned oxydianiline (ODA) or paraphenylenediamine (PPD) may be completely omitted.

[0058] Furthermore, the aforementioned diamine component must always include the aforementioned m-tolidine, and the content of the aforementioned m-tolidine may be, for example, 90 mol% or less, or 85 mol% or less.

[0059] The aforementioned m-tolidine, in particular, has a hydrophobic methyl group, which contributes to the low moisture absorption properties of the polyimide film.

[0060] If the content of oxydianiline (ODA) exceeds 35 mol%, not only will the glass transition temperature decrease, but the low dielectric loss characteristics may also decrease. If the content of paraphenylenediamine (PPD) exceeds 55 mol%, the low dielectric loss characteristics may decrease. If the content of m-tolidine is less than 45 mol%, the low dielectric loss characteristics may also decrease.

[0061] On the other hand, the polyimide film of the present invention may contain a block copolymer consisting of two or more blocks, and in particular, it may contain two blocks.

[0062] The polyimide film of the present invention may include a first block obtained by imidizing a dianhydride component containing p-phenylenebis(trimellitate anhydride) (TAHQ) with a diamine component containing m-tolidine (mTD) and oxydianiline (ODA), and a second block obtained by imidizing a dianhydride component containing biphenyltetracarboxylic dianehydride (BPDA) and pyromeretic dianehydride (PMDA) with a diamine component containing m-tolidine (mTD) and paraphenylenediamine (PPD).

[0063] By adjusting the blocks of such a block copolymer, the polyimide film can have excellent dielectric loss (Df) characteristics due to the first block, while simultaneously increasing the glass transition temperature and ensuring high-temperature stability due to the second block.

[0064] In one embodiment, the polyimide film may have a dielectric constant (Dk) of 3.5 or less, a dielectric loss rate (Df) of 0.0025 or less, and a glass transition temperature (Tg) of 240°C or higher.

[0065] In this regard, a polyimide film that satisfies all requirements of dielectric constant (Dk), dielectric loss rate (Df), and glass transition temperature can not only be used as an insulating film for flexible metal foil laminates, but its insulating stability can also be ensured and signal transmission delay can be minimized even when the manufactured flexible metal foil laminate is used as an electrical signal transmission circuit that transmits signals at high frequencies of 10 GHz or higher.

[0066] On the other hand, the production of polyamic acids is, for example, (1) A method of polymerization in which the entire amount of the diamine component is placed in a solvent, and then the dianhydride acid component is added in a substantially equimolar manner with the diamine component. (2) A method of polymerization by placing the entire amount of the dianhydride acid component into a solvent, and then adding the diamine component in a substantially equimolar amount to the dianhydride acid component. (3) A polymerization method in which, after adding some of the components of the diamine component to the solvent, some of the components of the dianhydride component are mixed with the reactant in a ratio of approximately 95 to 105 mol%, the remaining diamine component is added, followed by the remaining dianhydride component, until the diamine component and the dianhydride component are substantially equimolar. (4) A method of polymerization in which, after adding the dianhydride acid component to the solvent, a portion of the diamine compound is mixed with the reaction components in a ratio of 95 to 105 mol%, then other dianhydride acid components are added, followed by the addition of the remaining diamine components, so that the diamine components and dianhydride acid components are substantially equimolar. (5) A method of polymerization in which a portion of the diamine component and a portion of the dianhydride acid component are reacted in a solvent such that one of them is in excess to form a first composition, a portion of the diamine component and a portion of the dianhydride acid component are reacted in another solvent such that one of them is in excess to form a second composition, and then the first and second compositions are mixed to complete polymerization, wherein when forming the first composition, if the diamine component is in excess, the dianhydride acid component is in excess in the second composition, and when forming the first composition, if the dianhydride acid component is in excess, the diamine component is in excess in the second composition, and the first and second compositions are mixed so that the total amount of diamine component and dianhydride acid component used in these reactions is substantially equimolar.

[0067] However, the polymerization method is not limited to the examples above, and of course, any known method can be used to produce the first or second polyamic acid.

[0068] In one embodiment, the method for producing a polyimide film according to the present invention comprises the steps of polymerizing a dianhydride acid component comprising two or more selected from the group consisting of biphenyltetracarboxylic dianehydride (BPDA), pyromeretic dianehydride (PMDA), and p-phenylenebis (trimellitate anhydride, TAHQ), and a diamine component comprising two or more selected from the group consisting of oxydianiline (ODA), paraphenylenediamine (PPD), and m-tolidine (mTD) to produce a polyamic acid solution, and imidizing the polyamic acid solution.

[0069] However, the dianhydride acid component may always include biphenyltetracarboxylic dianehydride and p-phenylenebis(trimellitate anhydride).

[0070] A polyimide film can be produced by copolymerizing the dianhydride acid component and the diamine component in a predetermined order.

[0071] In one embodiment, based on a total content of 100 mol% of the dianhydride acid components, the content of biphenyltetracarboxylic dianehydride (BPDA) may be 30 mol% or more and 70 mol% or less, the content of pyromellitic dianehydride (PMDA) may be 40 mol% or less, and the content of p-phenylenebis(trimellitate anhydride) (TAHQ) may be 15 mol% or more and 35 mol% or less. Preferably, the content of biphenyltetracarboxylic dianehydride (BPDA) may be 35 mol% or more and 65 mol% or less, the content of pyromellitic dianehydride (PMDA) may be 35 mol% or less, and the content of p-phenylenebis(trimellitate anhydride) (TAHQ) may be 20 mol% or more and 35 mol% or less.

[0072] In other embodiments, based on a total content of 100 mol% of the diamine components, the content of oxydianiline (ODA) may be 35 mol% or less, the content of paraphenylenediamine (PPD) may be 55 mol% or less, and the content of m-tolidine may be 45 mol% or more.

[0073] Preferably, the content of oxydianiline (ODA) is 30 mol% or less, the content of paraphenylenediamine (PPD) is 50 mol% or less, and the content of m-tolidine is 50 mol% or more.

[0074] The aforementioned oxydianiline (ODA) or paraphenylenediamine (PPD) may be completely omitted.

[0075] Furthermore, the aforementioned diamine component must always include the aforementioned m-tolidine, and the content of the aforementioned m-tolidine may be, for example, 90 mol% or less, or 85 mol% or less.

[0076] In the present invention, the polymerization method of polyamic acid as described above may be a random polymerization method, and the polyimide film produced from the polyamic acid of the present invention produced by the process described above is preferably applicable in terms of maximizing the effect of the present invention in reducing dielectric loss rate (Df) and moisture absorption rate.

[0077] However, since the polymerization method described above produces polymers with relatively short repeating units, there may be limitations in exhibiting the excellent properties of the polyimide chains derived from the dianhydride acid component. Therefore, a particularly preferred polymerization method for polyamic acid in the present invention may be a block polymerization method.

[0078] On the other hand, the solvent used to synthesize polyamic acid is not particularly limited; any solvent that can dissolve polyamic acid can be used, but an amide-based solvent is preferred.

[0079] The polyimide film produced by the above-mentioned method for producing a polyimide film may have a dielectric constant (Dk) of 3.5 or less, a dielectric loss rate (Df) of 0.0025 or less, and a glass transition temperature (Tg) of 240°C or higher.

[0080] One embodiment of the present invention provides a multilayer film containing the polyimide film, a multilayer film containing the polyimide film and a thermoplastic resin layer, and a flexible metal foil laminate containing the polyimide film and an electrically conductive metal foil.

[0081] The thermoplastic resin layer can be, for example, a thermoplastic polyimide resin layer.

[0082] The metal foil used is not particularly limited, but when the flexible metal foil laminate of the present invention is used in electronic or electrical equipment applications, it may include, for example, copper or copper alloys, stainless steel or its alloys, nickel or nickel alloys (including 42 alloys), aluminum or aluminum alloys.

[0083] In general flexible metal foil laminates, rolled copper foil and electrolytic copper foil are commonly used, and these can also be preferably used in the present invention. Furthermore, the surface of these metal foils may be coated with a rust-preventive layer, a heat-resistant layer, or an adhesive layer.

[0084] In the present invention, the thickness of the metal foil is not particularly limited, and any thickness that allows it to perform its function adequately depending on the application is acceptable.

[0085] The flexible metal foil laminate according to the present invention may have a structure in which a metal foil is laminated to one surface of the polyimide film, or an adhesive layer containing thermoplastic polyimide is added to one surface of the polyimide film, and the metal foil is laminated while attached to the adhesive layer.

[0086] On the other hand, according to one embodiment of the present invention, the flexible metal foil laminate may be an electronic component that includes an electrical signal transmission circuit. The electrical signal transmission circuit may be an electronic component that transmits signals at a high frequency of at least 2 GHz, more specifically at a high frequency of at least 5 GHz, and even more specifically at a high frequency of at least 10 GHz.

[0087] By controlling the high hygroscopicity of the polyimide film, which affects the transmission loss of the electrical signal, it is possible to optimize the transmission loss and achieve a dielectric loss ratio (Df) of 0.0025 or less at frequencies of 10 GHz or higher.

[0088] The aforementioned electronic component may, but is not limited to, a communication circuit for a mobile terminal, a communication circuit for a computer, or a communication circuit for aerospace applications. [Examples]

[0089] The function and effects of the invention will be described in more detail below through specific embodiments of the invention. However, these embodiments are merely presented as examples of the invention and do not define the scope of the invention's rights.

[0090] Manufacturing example (manufacturing of polyimide film) DMF is added to a 500 ml reactor equipped with a stirrer and nitrogen injection / discharge pipes while nitrogen is being injected. After setting the reactor temperature to 30°C, the diamine monomer and the dianhydride acid monomer are added in the specified order, and it is confirmed that they are completely dissolved.

[0091] Subsequently, under a nitrogen atmosphere, the reactor temperature was raised to 40°C and stirring was continued for 120 minutes to produce block copolymerized polyamic acid.

[0092] After preparing a polyimide precursor composition by adding catalysts and dehydrating agents to the polyamic acid produced in this manner, the degassed polyimide precursor composition was applied to a glass substrate using a spin coater. Subsequently, a gel film was produced by drying under a nitrogen atmosphere at 120°C for 30 minutes. The gel film was then heated to 450°C at a rate of 2°C / min, heat-treated at 450°C for 60 minutes, and cooled to 30°C at a rate of 2°C / min to obtain a polyimide film.

[0093] Examples 1-5 and Comparative Examples 1-4 Polyimide films were produced by adjusting the content of the dianhydride acid component and the diamine component in Examples 1-5 and Comparative Examples 1-4, as shown in Table 1 below, using the manufacturing method described earlier.

[0094] [Table 1]

[0095] As shown in Table 1 above, the dielectric constant, dielectric loss rate, and glass transition temperature were measured for the polyimide films produced in Examples 1 to 5 and Comparative Examples 1 to 4, respectively, and are shown in Table 2 below.

[0096] [Table 2]

[0097] The method for measuring the dielectric constant (Dk), dielectric loss rate (Df), and glass transition temperature of the manufactured polyimide film is as follows.

[0098] (1) Measurement of dielectric constant The dielectric constant (Dk) was measured at 10 GHz using a Keysight SPDR detector.

[0099] (2) Measurement of dielectric loss The dielectric loss (Df) was measured using the cavity resonance method (SPDR) with Keysight's ENA (Vector Network Analyzer) on films left for 24 hours in an environment of 23°C / 50%RH.

[0100] (3) Measurement of glass transition temperature The glass transition temperature (Tg) was determined by using DMA to find the loss modulus and storage modulus of each film, and the inflection point in the tangent graph of these moduli was measured as the glass transition temperature.

[0101] As shown in Table 2 above, the polyimide films produced by the embodiments of the present invention not only achieved a dielectric loss rate (Df) of less than 0.0025, but also exhibited excellent thermal stability, with a glass transition temperature (Tg) corresponding to 240°C or higher.

[0102] On the other hand, the dielectric constant (Dk) of the polyimide films of all examples and comparative examples except for Comparative Example 3 of the present invention was 3.5 or less.

[0103] This result is achieved by the components and compositional ratios specified in this application, indicating that the content of each component plays a decisive role.

[0104] On the other hand, the dielectric loss rates of the polyimide films of Comparative Examples 2 to 4 were higher than those of the polyimide films of Examples 1 to 5. Only the polyimide film of Comparative Example 1 had a lower dielectric loss rate than the polyimide films of Examples 1 to 5, but it showed a very low glass transition temperature, confirming a significant decrease in heat resistance.

[0105] From this, we can predict that the polyimide films of Examples 1 to 5, possessing both low dielectric loss characteristics and high heat resistance, will be suitable for actual applications in electronic components.

[0106] As described above with reference to embodiments of the present invention, a person with ordinary skill in the art to which the present invention belongs will be able to make various applications and modifications within the scope of the present invention based on the above content. [Industrial applicability]

[0107] As described above, the present invention provides a polyimide film manufactured by imidizing a polyamic acid solution consisting of specific components and a specific composition ratio, and having low dielectric properties and high heat resistance properties. Therefore, it can be usefully applied to a variety of fields where such properties are required, particularly to electronic components such as flexible metal foil laminates.

Claims

1. A dianhydride acid component comprising two or more selected from the group consisting of biphenyltetracarboxylic dianehydride (BPDA), pyromeretic dianehydride (PMDA), and p-phenylenebis (trimellitate anhydride), TAHQ, It is produced by imidizing a polyamic acid solution containing a diamine component comprising two or more selected from the group consisting of oxydianiline (ODA), paraphenylenediamine (PPD), and m-tolidine (mTD), Based on a total content of 100 mol% of the aforementioned dianhydride acid components, the content of biphenyltetracarboxylic dianehydride (BPDA) is 30 mol% or more and 65 mol% or less, the content of pyromellitic dianehydride (PMDA) is 40 mol% or less, and the content of p-phenylenebis(trimellitate anhydride) (TAHQ) is 15 mol% or more and 35 mol% or less, and Based on a total content of 100 mol% of the diamine components, the content of oxydianiline (ODA) is 35 mol% or less, the content of paraphenylenediamine (PPD) is 55 mol% or less, and the content of m-tolidine (mTD) is 45 mol% or more. Polyimide film. (However, the dianhydride acid component must contain biphenyltetracarboxylic dianehydride and p-phenylenebis(trimellitate anhydride), and the diamine component must contain m-tolidine.)

2. A block copolymer comprising two or more blocks, The polyimide film according to claim 1.

3. A first block obtained by imidizing a dianhydride component containing the aforementioned p-phenylenebis(trimellitate anhydride) (TAHQ) with a diamine component containing m-tolidine (mTD) and oxydianiline (ODA), The material comprises a block copolymer comprising a second block obtained by imidizing a dianhydride component containing biphenyltetracarboxylic dianehydride (BPDA) and pyromeretic dianehydride (PMDA) with a diamine component containing m-tolidine (mTD) and paraphenylenediamine (PPD), The polyimide film according to claim 1.

4. The dielectric loss ratio (Df) of the polyimide film is 0.0025 or less. The glass transition temperature (Tg) is 240°C or higher. The polyimide film according to claim 1.

5. A step of producing a polyamic acid solution by polymerizing a dianhydride acid component comprising two or more selected from the group consisting of biphenyltetracarboxylic dianehydride (BPDA), pyromeretic dianehydride (PMDA), and p-phenylenebis(trimellitate anhydride) (TAHQ), and a diamine component comprising two or more selected from the group consisting of oxydianiline (ODA), paraphenylenediamine (PPD), and m-tolidine (mTD), The step includes imidizing the polyamic acid solution, Based on a total content of 100 mol% of the aforementioned dianhydride acid components, the content of biphenyltetracarboxylic dianehydride (BPDA) is 30 mol% or more and 65 mol% or less, the content of pyromellitic dianehydride (PMDA) is 40 mol% or less, and the content of p-phenylenebis(trimellitate anhydride) (TAHQ) is 15 mol% or more and 35 mol% or less, and Based on a total content of 100 mol% of the diamine components, the content of oxydianiline (ODA) is 35 mol% or less, the content of paraphenylenediamine (PPD) is 55 mol% or less, and the content of m-tolidine (mTD) is 45 mol% or more. A method for manufacturing polyimide film. (However, the dianhydride acid component must contain biphenyltetracarboxylic dianehydride and p-phenylenebis(trimellitate anhydride), and the diamine component must contain m-tolidine.)

6. The dielectric loss ratio (Df) of the polyimide film is 0.0025 or less. The glass transition temperature (Tg) is 240°C or higher. A method for producing a polyimide film according to claim 5.

7. A polyimide film comprising the polyimide film according to any one of claims 1 to 4, Multilayer film.

8. The thermoplastic resin layer is additionally included. The multilayer film according to claim 7.

9. A polyimide film according to any one of claims 1 to 4, Includes an electrically conductive metal foil, Flexible metal foil laminate.

10. Includes the flexible metal foil laminate described in claim 9, Electronic components.

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