JP2024537040A - Polyimide film having improved mechanical strength and heat resistance and method for producing same - Google Patents

Abstract

The present invention relates to a polyimide film produced by imidizing a polyamic acid solution containing a dianhydride acid component including biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA) and benzophenonetetracarboxylic dianhydride (BTDA) and a diamine component including oxydianiline (ODA), paraphenylenediamine (PPD) and 4,4'-diaminobenzanilide (DABA), and a method for producing the same.

Description

The present invention relates to a polyimide film having excellent mechanical strength and heat resistance, and a method for producing the same.

Polyimide (PI) is a polymeric material that has the highest levels of chemical resistance, electrical insulation, chemical resistance, and weather resistance among organic materials, based on imide rings that have excellent chemical stability along with a rigid aromatic main chain.
In particular, due to its excellent electrical properties such as excellent insulating properties, i.e., low dielectric constant, it has been attracting attention as a highly functional polymer material in the electrical, electronic and optical fields.
2. Description of the Related Art Recently, with the trend towards lighter and smaller electronic products, flexible thin circuit boards with high integration density have been actively developed.

Such thin circuit boards tend to have a structure in which a circuit containing metal foil is formed on a polyimide film that has excellent heat resistance, low temperature resistance and insulating properties, but is also easily flexible.
Flexible metal clad laminates are mainly used for such thin circuit boards, and an example of such a laminate is a flexible copper clad laminate (FCCL) that uses a thin copper plate as a metal foil. In addition, polyimide is used as a protective film, an insulating film, etc. for thin circuit boards.
In particular, as electronic devices have recently been equipped with a variety of functions, there has been a demand for high calculation and communication speeds in the electronic devices. To meet this demand, thin circuit boards capable of high-speed communication at high frequencies have been developed.

However, conventional polyimide films have the disadvantage of being relatively low in heat resistance, making them unsuitable for use in the latest circuit boards. Various previous studies have been conducted to improve the heat resistance of these films, but the improvement in heat resistance has been accompanied by a decrease in thermal properties such as mechanical strength and glass transition temperature.
Therefore, there is still a need to develop polyimide films that have improved heat resistance while maintaining the inherent thermal properties of polyimide, such as mechanical strength and glass transition temperature.

Korean Patent No. 10-1004429

An object of the present invention is to provide a polyimide film having both excellent heat resistance and mechanical properties, and a method for producing the same.
In particular, an object of the present invention is to provide a polyimide film having high high-temperature stability and excellent elastic modulus, tensile strength and elongation properties, and a method for producing the same.
Therefore, it is a substantial object of the present invention to provide specific embodiments thereof.

In order to achieve the above object, one embodiment of the present invention is a method for producing a 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride).
dianhydride acid components including 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), pyromellitic dianhydride (PMDA), and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA);
The present invention provides a polyimide film produced by imidizing a polyamic acid solution containing a diamine component including oxydianiline (ODA), paraphenylenediamine (PPD), and 4,4'-diaminobenzanilide (DABA).

In one embodiment, based on 100 mol% of the total content of the diamine components, the content of the oxydianiline may be 23 mol% or more and 43 mol% or less, the content of the paraphenylenediamine may be 50 mol% or more and 60 mol% or less, and the content of the 4,4'-diaminobenzanilide may be 10 mol% or more and 30 mol% or less.
In addition, based on 100 mol% of the total content of the dianhydride acid components, the content of the biphenyltetracarboxylic dianhydride may be 15 mol% or more and 30 mol% or less, the content of the pyromellitic dianhydride may be 50 mol% or more and 65 mol% or less, and the content of the benzophenonetetracarboxylic dianhydride may be 10 mol% or more and 35 mol% or less.
Meanwhile, the polyimide film may include a block copolymer having two or more blocks.

In one embodiment, the polyimide film may have an elastic modulus of 5 GPa or more, a strength of 340 MPa or more, a glass transition temperature (Tg) of 360° C. or more, and an elongation of 60% or more.
Another embodiment of the present invention is a method for producing a polyamic acid by polymerizing a dianhydride component including biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA) and benzophenonetetracarboxylic dianhydride (BTDA) and a diamine component consisting of oxydianiline (ODA), paraphenylenediamine (PPD) and 4,4'-diaminobenzanilide (DABA) in an organic solvent;
(b) imidizing the polyamic acid.
A method for producing a polyimide film is provided.
Yet another embodiment of the present invention provides a multilayer film comprising the polyimide film, or a multilayer film comprising the polyimide film and a thermoplastic resin layer.
Yet another embodiment of the present invention provides a flexible metal foil laminate comprising the polyimide film and an electrically conductive metal foil, and an electronic component comprising the flexible metal foil laminate.

The polyimide film according to the embodiment of the present invention can have excellent heat resistance and mechanical properties at the same time by using a specific dianhydride acid component and a specific diamine component in combination in a specific molar ratio, and can also improve adhesive strength.
Meanwhile, the present invention includes the polyimide film as described above and can be effectively applied to electronic parts such as flexible metal foil laminates.

Hereinafter, the embodiments of the present invention will be described in more detail, in the order of "polyimide film" and "method for producing polyimide film" according to the present invention.
Prior to this, the terms and words used in this specification and claims should not be interpreted limited to their ordinary or dictionary meanings, but should be interpreted with a meaning and concept that corresponds to the technical idea of the present invention, in accordance with the principle that an inventor can appropriately define the concept of a term in order to explain his/her invention in the best possible way.
Therefore, it should be understood that the configuration of the embodiment described in this specification is merely one of the most preferred embodiments of the present invention and does not fully represent the technical ideas of the present invention, and that there may be various equivalents and modifications that can replace them at the time of this application.
In this specification, the singular expression includes the plural expression unless the context clearly indicates otherwise. It should be understood that in this specification, the terms "comprise", "comprise", "have" and the like are intended to specify the presence of embodied features, numbers, steps, components, or combinations thereof, and do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

Whenever an amount, concentration, or other value or parameter is given herein as a range, a preferred range or a list of an upper preferred value and a lower preferred value, it should be understood to specifically disclose all ranges formed by any pair of any upper range limit or preferred value, and any lower range limit or preferred value, regardless of whether a range is otherwise disclosed.
Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining the range.

As used herein, "dianhydride acid" is intended to include precursors or derivatives thereof, which may not technically be dianhydrides, but which nevertheless must react with a diamine to form a polyamic acid, which is then converted back to a polyimide.
As used herein, "diamine" is intended to include precursors or derivatives thereof, which may not technically be diamines, but which nevertheless must react with a dianhydride to form a polyamic acid, which is then converted back to a polyimide.

The polyimide film according to the present invention is made of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA) and 3,3',4,4'-benzophenonetetracarboxylic dianhydride. It is produced by imidizing a polyamic acid solution containing a dianhydride component including 4,4'-oxydianiline (ODA), paraphenylenediamine (PPD), and 4,4'-diaminobenzanilide (DABA).

In one embodiment, based on 100 mol% of the total content of the diamine components, the content of the oxydianiline may be 23 mol% or more and 43 mol% or less, the content of the paraphenylenediamine may be 50 mol% or more and 60 mol% or less, and the content of the 4,4'-diaminobenzanilide may be 10 mol% or more and 30 mol% or less.
The 4,4'-diaminobenzanilide contains an amide group and contributes greatly to improving the excellent heat resistance and mechanical properties of the polyimide film of the present invention within the content range of the present invention.
In one embodiment, based on a total content of the dianhydride acid components of 100 mol%, the content of the biphenyltetracarboxylic dianhydride may be 15 mol% or more and 30 mol% or less, the content of the pyromellitic dianhydride may be 50 mol% or more and 65 mol% or less, and the content of the benzophenonetetracarboxylic dianhydride may be 10 mol% or more and 35 mol% or less.

The polyimide chain derived from biphenyltetracarboxylic dianhydride has a structure called a charge transfer complex (CTC), i.e., a regular linear structure in which an electron donor and an electron acceptor are located close to each other, and thus the intermolecular interaction is strengthened.
In addition, benzophenone tetracarboxylic dianhydride, which has a carbonyl group, also contributes to the expression of CTC, similar to biphenyl tetracarboxylic dianhydride.

In particular, the dianhydride component may further include pyromellitic dianhydride, which is a dianhydride component having a relatively rigid structure and is preferred in that it can impart appropriate elasticity to the polyimide film.
In addition, biphenyl tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride contain two benzene rings corresponding to the aromatic moiety, whereas pyromelitic dianhydride contains one benzene ring corresponding to the aromatic moiety.
An increase in the content of pyromellitic dianhydride in the dianhydride acid component can be understood as an increase in the imide groups in the molecule when the molecular weight is taken as the same standard, and this can be understood as a relative increase in the ratio of imide groups derived from the pyromellitic dianhydride in the polyimide polymer chain compared to the imide groups derived from biphenyltetracarboxylic dianhydride and benzophenonetetracarboxylic dianhydride.

If the content ratio of the pyromellitic dianhydride is reduced too much, the components having a relatively rigid structure are reduced, and the mechanical properties of the polyimide film may be reduced below a desired level.
For this reason, when the content of the biphenyltetracarboxylic dianhydride and the benzophenonetetracarboxylic dianhydride exceeds the above range, the mechanical properties of the polyimide film are deteriorated.

In one embodiment, the polyimide film may include a block copolymer consisting of two or more blocks.
At least one block of the block copolymer can include a bond between a pyromellitic dianhydride and a 4,4'-diaminobenzanilide.
By adjusting the blocks of the block copolymer in this way, the glass transition temperature of the polyimide film can be increased, thereby ensuring the high temperature stability of the polyimide film.

In one embodiment, the polyimide film may have an elastic modulus of 5 GPa or more and a strength of 340 MPa or more.
The polyimide film may have a glass transition temperature (Tg) of 360° C. or higher and an elongation of 60% or higher.
In particular, physical properties such as elongation are generally difficult to achieve at a desirable level together with strength, but the composition and composition ratio containing 4,4'-diaminobenzanilide having an amide group of the present invention can exert a desirable level of strength while at the same time acting to suppress the occurrence of a decrease in elongation.

In the present invention, the polyamic acid can be produced, for example, by
(1) A method in which the entire amount of the diamine component is placed in a solvent, and then a dianhydride component is added in an amount substantially equimolar to the diamine component to polymerize the mixture;
(2) A method in which the entire amount of the dianhydride component is placed in a solvent, and then a diamine component is added in an amount substantially equimolar to the dianhydride component to polymerize the mixture;
(3) A method in which a part of the diamine component is placed in a solvent, a part of the dianhydride component is mixed with the reaction components in a ratio of about 95 to 105 mol %, the remaining diamine component is added, and the remaining dianhydride component is added continuously thereto, so that the diamine component and the dianhydride component are polymerized in substantially equimolar amounts;
(4) A method in which a dianhydride component is placed in a solvent, a part of the components in the diamine compound is mixed in a ratio of 95 to 105 mol % relative to the reactive components, and then another dianhydride component is added, followed by the remaining diamine component, so that the diamine component and the dianhydride component are substantially equimolar, thereby polymerizing the mixture;
(5) A method of reacting some diamine components and some dianhydride acid components in a solvent so that one of them is in excess to form a first composition, reacting some diamine components and some dianhydride acid components in another solvent so that one of them is in excess to form a second composition, and then mixing the first and second compositions to complete polymerization, in which if the diamine component is in excess when the first composition is formed, the dianhydride acid component is in excess in the second composition, and if the dianhydride acid component is in excess in the first composition, the diamine component is in excess in the second composition, and the first and second compositions are mixed to polymerize so that the total diamine components and dianhydride acid components used in these reactions are substantially equimolar.
However, the polymerization method is not limited to the above example, and any known method can be used to produce polyamic acid.

In one embodiment, a method for producing a polyimide film according to the present invention includes the steps of:
The method may include the steps of: (a) polymerizing a dianhydride component including biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and benzophenonetetracarboxylic dianhydride (BTDA) and a diamine component including oxydianiline (ODA), paraphenylenediamine (PPD), and 4,4′-diaminobenzanilide (DABA) in an organic solvent to produce a polyamic acid; and (b) imidizing the polyamic acid.
In one embodiment, based on 100 mol% of the total content of the diamine components, the content of the oxydianiline may be 23 mol% or more and 43 mol% or less, the content of the paraphenylenediamine may be 50 mol% or more and 60 mol% or less, the content of the 4,4'-diaminobenzanilide may be 10 mol% or more and 30 mol% or less, based on 100 mol% of the total content of the dianhydride acid components, the content of the biphenyltetracarboxylic dianhydride may be 15 mol% or more and 30 mol% or less, the content of the pyromellitic dianhydride may be 50 mol% or more and 65 mol% or less, and the content of the benzophenonetetracarboxylic dianhydride may be 10 mol% or more and 35 mol% or less.

The polyimide film may have an elastic modulus of 5 GPa or more, a strength of 340 MPa or more, a glass transition temperature (Tg) of 360° C. or more, and an elongation of 60% or more.
In the present invention, the polymerization method of the polyamic acid as described above can be defined as a random polymerization method, and a polyimide film prepared from the polyamic acid of the present invention prepared by the above process can be preferably applied to the effects of the present invention, which are to improve mechanical properties and heat resistance.
On the other hand, the solvent for synthesizing the polyamic acid is not particularly limited, and any solvent that dissolves the polyamic acid can be used, but an amide-based solvent is preferable.

Specifically, the solvent may be an organic polar solvent, more specifically, an aprotic polar solvent, or may be, for example, one or more selected from the group consisting of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-pyrrolidone (NMP), p-chlorophenol, o-chlorophenol, N-methyl-pyrrolidone (NMP), gamma-butyrolactone (GBL), and diglyme, but is not limited thereto, and may be used alone or in combination of two or more kinds as necessary.

In one example, the solvent is preferably N,N-dimethylformamide or N,N-dimethylacetamide.
In addition, in the manufacturing process of the polyamic acid, fillers other than nanosilica can be added for the purpose of improving various properties of the film such as sliding properties, thermal conductivity, corona resistance, loop hardness, etc. The fillers to be added are not particularly limited, but preferred examples include titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, etc.
The particle size of the filler is not particularly limited and may be determined depending on the film properties to be modified and the type of filler to be added. In general, the average particle size is 0.05 to 100 μm, preferably 0.1 to 75 μm, more preferably 0.1 to 50 μm, and particularly preferably 0.1 to 25 μm.

If the particle size is below this range, the modifying effect is unlikely to be achieved, whereas if it exceeds this range, the surface properties may be significantly damaged and the mechanical properties may be significantly reduced.
The amount of the filler to be added is not particularly limited, and may be determined depending on the film properties to be modified, the particle size of the filler, etc. In general, the amount of the filler to be added is 0.01 to 100 parts by weight, preferably 0.01 to 90 parts by weight, and more preferably 0.02 to 80 parts by weight, based on 100 parts by weight of polyimide.
If the amount of the filler added is less than this range, the modifying effect of the filler is difficult to manifest, and if the amount exceeds this range, the mechanical properties of the film may be significantly damaged. The method of adding the filler is not particularly limited, and any known method may be used.
In the production method of the present invention, the polyimide film is produced by a thermal imidization method and a chemical imidization method.

Alternatively, the imidization method may be a hybrid imidization method in which a thermal imidization method and a chemical imidization method are performed in parallel.
The thermal imidization method is a method in which a chemical catalyst is excluded and the imidization reaction is induced by a heat source such as hot air or an infrared dryer.
The thermal imidization method may involve heat-treating the gel film at a variable temperature in the range of 100 to 600° C. to imidize the amic acid groups present in the gel film, specifically, at 200 to 500° C., more specifically, at 300 to 500° C. to imidize the amic acid groups present in the gel film.
However, even during the process of forming the gel film, a portion of the amic acid (about 0.1 mol % to 10 mol %) is imidized, and therefore the polyamic acid composition can be dried at a variable temperature in the range of 50° C. to 200° C., which also falls within the category of the thermal imidization method.

In the case of the chemical imidization method, a polyimide film can be produced using a dehydrating agent and an imidization agent by a method known in the art. Here, the "dehydrating agent" refers to a substance that promotes a ring-closing reaction by dehydrating polyamic acid, and non-limiting examples thereof include aliphatic acid anhydrides, aromatic acid anhydrides, N,N'-dialkylcarbodiimides, halogenated lower aliphatic acids, halogenated lower fatty acid anhydrides, arylphosphonic dihalides, and thionyl halides. Among them, aliphatic acid anhydrides are preferred from the viewpoint of availability and cost, and non-limiting examples thereof include acetic anhydride (or acetic anhydride, AA), propionic anhydride, and lactic anhydride, which can be used alone or in combination of two or more.

The term "imidizing agent" refers to a substance that has the effect of promoting a ring-closing reaction with polyamic acid, and may be, for example, an imine-based component such as an aliphatic tertiary amine, an aromatic tertiary amine, or a heterocyclic tertiary amine. Among these, heterocyclic tertiary amines are preferred from the viewpoint of reactivity as a catalyst. Non-limiting examples of heterocyclic tertiary amines include quinoline, isoquinoline, β-picoline (BP), pyridine, etc., which can be used alone or in a mixture of two or more kinds.

The amount of the dehydrating agent added is preferably within a range of 0.5 to 5 mol, and more preferably within a range of 1.0 to 4 mol, per mol of amic acid groups in the polyamic acid, while the amount of the imidizing agent added is preferably within a range of 0.05 to 2 mol, and more preferably within a range of 0.2 to 1 mol, per mol of amic acid groups in the polyamic acid.
If the amount of the dehydrating agent and the imidizing agent is less than the above range, the chemical imidization is insufficient, cracks are formed in the polyimide film produced, and the mechanical strength of the film may be reduced.If the amount of the dehydrating agent and the imidizing agent is more than the above range, the imidization proceeds too quickly, which makes it difficult to cast the polyimide film into a film or the polyimide film produced may show brittle properties, which is not preferable.

As an example of the composite imidization method, a dehydrating agent and an imidization agent are added to a polyamic acid solution, which is then heated at 80 to 200° C., preferably 100 to 180° C. to partially harden and dry the solution, and then heated at 200 to 400° C. for 5 to 400 seconds to produce a polyimide film.
The present invention provides a multilayer film comprising the above-mentioned polyimide film and a thermoplastic resin layer, and a flexible metal foil laminate comprising the above-mentioned polyimide film and an electrically conductive metal foil.

As the thermoplastic resin layer, for example, a thermoplastic polyimide resin layer can be used.
The metal foil to be used is not particularly limited, but when the flexible metal foil laminate of the present invention is used for electronic or electrical equipment applications, the metal foil may be, for example, copper or a copper alloy, stainless steel or an alloy thereof, nickel or a nickel alloy (including alloy 42), or aluminum or an aluminum alloy.
In general flexible metal foil laminates, copper foils such as rolled copper foils and electrolytic copper foils are often used, and can be preferably used in the present invention. The surface of these metal foils may be coated with an anticorrosive layer, a heat-resistant layer, or an adhesive layer.

In the present invention, the thickness of the metal foil is not particularly limited, and may be any thickness that can exhibit sufficient function depending on the application.
The flexible metal foil laminate according to the present invention may have a structure in which a metal foil is laminated on one side of the polyimide film, or an adhesive layer containing a thermoplastic polyimide is added to one side of the polyimide film, and the metal foil is laminated in a state of being attached to the adhesive layer.
The present invention further provides an electronic device including the flexible metal foil laminate as an electrical signal transmission circuit.

Below, the functions and effects of the invention will be described in more detail through specific examples of the invention. However, these examples are presented only as examples of the invention and do not define the scope of the invention's rights.

<Production Example>
DMF was added to a 500 ml reactor equipped with a stirrer and nitrogen inlet/outlet tubes while injecting nitrogen, and the temperature of the reactor was set to 30° C., followed by adding oxydianiline (ODA), paraphenylenediamine (PPD), and 4,4′-diaminobenzanilide (DABA) as diamine components, and biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and benzophenonetetracarboxylic dianhydride (BTDA) as dianhydride acid components, and confirming that they were completely dissolved.

Thereafter, the temperature of the reactor was raised to 40° C. under a nitrogen atmosphere, and stirring was continued for 120 minutes to produce polyamic acid.
A catalyst and a dehydrating agent were added to the polyamic acid thus produced, and the mixture was rotated at a high speed of 1,500 rpm to remove air bubbles, and then coated on a glass substrate using a spin coater.
Thereafter, the resultant was dried at 120° C. for 30 minutes under a nitrogen atmosphere to prepare a gel film, which was then heated to 450° C. at a rate of 2° C./min, heat-treated at 450° C. for 60 minutes, and then cooled again to 30° C. at a rate of 2° C./min to obtain a final polyimide film, which was then peeled off from the glass substrate by dipping in distilled water.
The thickness of the polyimide film was 15 μm, which was measured using an Anritsu Electric Film Thickness Tester.

<Examples 1 to 4 and Comparative Examples 1 to 3>
The above-described preparation example was used to prepare the resin, and the contents of the diamine monomer and the dianhydride monomer were adjusted as shown in Table 1.

Experimental Example: Evaluation of Elastic Modulus, Strength, Elongation and Glass Transition Temperature As shown in Table 1, the elastic modulus, strength, elongation and glass transition temperature of the polyimide films prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were measured and the results are shown in Table 2.
(1) Elastic modulus, strength and elongation
Modulus, strength and elongation were measured using an Instron 3365SER instrument according to ASTM D882 measurement method.
(2) Measurement of glass transition temperature
The glass transition temperature (T _g ) was measured by determining the loss modulus and storage modulus of each film using DMA, and taking the inflection point in the tangent graph of these as the glass transition temperature.

As can be seen from Table 2, the polyimide films prepared according to the examples of the present invention not only had excellent mechanical strength with an elastic modulus of 5 GPa or more and a strength of 340 MPa or more, but also had excellent thermal stability with a glass transition temperature (Tg) of 360° C. or more.
Moreover, the elongation corresponds to 60% or more, and both excellent mechanical strength and excellent elongation could be achieved.

Such results are achieved by the components and composition ratios specified in this application, and it is understood that the content of each component plays a decisive role.
In contrast, the polyimide films of Comparative Examples 1-3 were measured to have a higher elastic modulus than the polyimide films of Examples 1-4.
However, it was confirmed that the strength and elongation of the polyimide films of Comparative Examples 1 to 3 were lower than those of the polyimide films of Examples 1 to 4, and in particular, the polyimide films of Comparative Examples 2 and 3 also had lower glass transition temperatures than the polyimide films of Examples 1 to 4.
From this, it was predicted that the polyimide films of the comparative examples would be difficult to actually apply to electronic parts.

The present invention has been described above with reference to examples, but anyone with ordinary knowledge in the field to which the present invention pertains would be able to make various applications and modifications within the scope of the present invention based on the above content.

The polyimide film according to the embodiment of the present invention can have excellent heat resistance and mechanical properties at the same time by using a specific dianhydride acid component and a specific diamine component in combination in a specific molar ratio, and can also improve adhesive strength.
Meanwhile, the present invention includes the polyimide film as described above and can be effectively applied to electronic parts such as flexible metal foil laminates.

Claims (13)

dianhydride acid components including biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA) and benzophenonetetracarboxylic dianhydride (BTDA);
A polyamic acid solution containing a diamine component including oxydianiline (ODA), paraphenylenediamine (PPD) and 4,4'-diaminobenzanilide (DABA) was imidized.
Polyimide film. the content of the oxydianiline is from 23 mol % to 43 mol %, the content of the paraphenylenediamine is from 50 mol % to 60 mol %, and the content of the 4,4'-diaminobenzanilide is from 10 mol % to 30 mol %, based on 100 mol % of the total content of the diamine components;
The polyimide film according to claim 1 . With respect to 100 mol% of the total content of the dianhydride acid components, the content of the biphenyl tetracarboxylic dianhydride is 15 mol% or more and 30 mol% or less, the content of the pyromellitic dianhydride is 50 mol% or more and 65 mol% or less, and the content of the benzophenone tetracarboxylic dianhydride is 10 mol% or more and 35 mol% or less.
The polyimide film according to claim 1 . Including block copolymers consisting of two or more blocks,
The polyimide film according to claim 1 . The elastic modulus is 5 GPa or more and the strength is 340 MPa or more.
The polyimide film according to claim 1 . The glass transition temperature (Tg) is 360° C. or higher and the elongation is 60% or higher.
The polyimide film according to claim 1 . (a) preparing a polyamic acid by polymerizing a dianhydride component including biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA) and benzophenonetetracarboxylic dianhydride (BTDA) and a diamine component including oxydianiline (ODA), paraphenylenediamine (PPD) and 4,4′-diaminobenzanilide (DABA) in an organic solvent;
(b) imidizing the polyamic acid.
A method for producing a polyimide film. the content of the oxydianiline is from 23 mol % to 43 mol %, the content of the paraphenylenediamine is from 50 mol % to 60 mol %, and the content of the 4,4'-diaminobenzanilide is from 10 mol % to 30 mol %, based on 100 mol % of the total content of the diamine components;
With respect to 100 mol% of the total content of the dianhydride acid components, the content of the biphenyl tetracarboxylic dianhydride is 15 mol% or more and 30 mol% or less, the content of the pyromellitic dianhydride is 50 mol% or more and 65 mol% or less, and the content of the benzophenone tetracarboxylic dianhydride is 10 mol% or more and 35 mol% or less.
The method for producing a polyimide film according to claim 7 . The elastic modulus of the polyimide film is 5 GPa or more,
The strength is 340 MPa or more,
The glass transition temperature (Tg) is 360° C. or higher,
The elongation is 60% or more.
The method for producing a polyimide film according to claim 7 . The polyimide film according to any one of claims 1 to 6,
Multilayer film. The polyimide film according to any one of claims 1 to 6,
A thermoplastic resin layer,
Multilayer film. The polyimide film according to any one of claims 1 to 6,
an electrically conductive metal foil;
Flexible metal foil laminate. Comprising the flexible metal foil laminate of claim 12.
Electronic components.