KR102652586B1 - Polyimide film with improved mechanical strength and thermal resistance and manufacturing method thereof - Google Patents

Abstract

The present invention relates to dianhydride components including biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and benzophenone tetracarboxylic dianhydride (BTDA); and a polyimide film prepared by imidizing a polyamic acid solution containing diamine components including oxydianiline (ODA), paraphenylene diamine (PPD), and 4,4'-diaminobenzanilide (DABA), and It relates to its manufacturing method

Description

Polyimide film with improved mechanical strength and thermal resistance and manufacturing method thereof {Polyimide film with improved mechanical strength and thermal resistance and manufacturing method thereof}

The present invention relates to a polyimide film having excellent mechanical strength and heat resistance and a method of manufacturing the same.

Polyimide (PI) is a polymer material that has the highest level of chemical resistance, electrical insulation, chemical resistance, and weather resistance among organic materials, based on an imide ring with a rigid aromatic main chain and excellent chemical stability.

In particular, it is attracting attention as a highly functional polymer material in the electrical, electronic, and optical fields due to its excellent electrical properties such as excellent insulating properties and low dielectric constant.

Recently, as electronic products become lighter and smaller, thin circuit boards with high integration and flexibility are being actively developed.

These thin circuit boards tend to have a structure in which a circuit including metal foil is formed on a polyimide film that has excellent heat resistance, low temperature resistance, and insulation characteristics and is easy to bend.

Flexible metal clad laminates are mainly used as such thin circuit boards, and an example includes Flexible Copper Clad Laminate (FCCL), which uses a thin copper plate as a metal foil. In addition, polyimide is also used as a protective film and insulating film for thin circuit boards.

In particular, as various functions have recently become embedded in electronic devices, fast calculation and communication speeds are required for the electronic devices, and to meet these requirements, thin circuit boards capable of high-speed communication at high frequencies are being developed.

However, the conventional polyimide film has the disadvantage of having relatively low heat resistance for use in the latest circuit boards, and various prior studies have been conducted to improve heat resistance. However, the improvement in heat resistance is dependent on thermal properties such as mechanical strength and glass transition temperature. accompanied by a decline.

Therefore, there is still a need to develop polyimide films that improve heat resistance while maintaining thermal properties such as polyimide's original mechanical strength and glass transition temperature.

Korean Patent No. 10-1004429

The purpose of the present invention is to provide a polyimide film with excellent high heat resistance and mechanical properties and a method for manufacturing the same.

In particular, the purpose of the present invention is to provide a polyimide film with high high temperature stability and excellent elastic modulus, tensile strength, and elongation characteristics, and a method for manufacturing the same.

Accordingly, the practical purpose of the present invention is to provide specific examples thereof.

One embodiment of the present invention for achieving the above object is biphenyltetracarboxylic dianhydride (3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (Pyromellitic dianhydride). dianhydride, PMDA) and dianhydride components including benzophenonetetracarboxylic dianhydride (3,3',4,4'-Benzophenonetetracarboxylic dianhydride, BTDA); and

Diamines including 4,4'-Oxydianiline (ODA), p-Phenylenediamine (PPD), and 4,4'-Diaminobenzanilide (DABA) Provided is a polyimide film manufactured by imidizing a polyamic acid solution containing a component.

In one embodiment, based on a total content of 100 mol% of the diamine component, the content of the oxydianiline is 23 mol% to 43 mol%, and the content of the paraphenylene diamine is 50 mol% to 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 the total content of the dianhydride component of 100 mol%, the content of the biphenyltetracarboxylic dianhydride is 15 mol% to 30 mol%, and the content of the pyromellitic dianhydride is 50 mol%. % or more and 65 mol% or less, and the content of the benzophenone tetracarboxylic dianhydride may be 10 mol% or more and 35 mol% or less.

Meanwhile, the polyimide film may include a block copolymer composed of 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 includes (a) biphenyl tetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and benzophenone tetracarboxylic dianhydride (BTDA). Preparing polyamic acid by polymerizing a dianhydride component and a diamine component consisting of oxydianiline (ODA), paraphenylene diamine (PPD), and 4,4'-diaminobenzanilide (DABA) in an organic solvent; and

(b) imidizing the polyamic acid; including,

A method for manufacturing a polyimide film is provided.

Another embodiment of the present invention provides a multilayer film including the polyimide film or a multilayer film including the polyimide film and a thermoplastic resin layer.

Another embodiment of the present invention provides a flexible metal clad laminate including the polyimide film and an electrically conductive metal foil, and an electronic component including the flexible metal clad laminate.

The polyimide film according to an embodiment of the present invention can have excellent high heat resistance properties and mechanical properties at the same time by using a specific dianhydride component and a specific diamine component in combination at a specific molar ratio. Additionally, adhesion can be improved.

Meanwhile, the present invention can be usefully applied to electronic components such as flexible metal clad laminates, including polyimide films as described above.

Hereinafter, embodiments of the 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 or words used in this specification and claims should not be construed as limited to their usual or dictionary meanings, and the inventor should appropriately define the concept of terms in order to explain his or her invention in the best way. It must be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle of definability.

Therefore, the configuration of the embodiments described in this specification is only one of the most preferred embodiments of the present invention and does not represent the entire technical idea of the present invention, so various equivalents and modifications that can replace them at the time of filing the present application It should be understood that examples may exist.

In this specification, singular expressions include plural expressions, unless the context clearly dictates otherwise. In this specification, terms such as “comprise,” “comprise,” or “have” are intended to designate the presence of implemented features, numbers, steps, components, or combinations thereof, and are intended to indicate the presence of one or more other features or It should be understood that this does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.

When amounts, concentrations, or other values or parameters are given herein as ranges, preferred ranges, or enumerations of upper preferred values and lower preferred values, any pair of upper range limits or It is to be understood that the preferred values and any lower range limits or all ranges formed from the preferred values are specifically disclosed.

When a range of numerical values is stated herein, unless otherwise stated, the range is intended to include the endpoints and all integers and fractions within the range. The scope of the invention is not intended to be limited to the specific values recited when defining the scope.

As used herein, “dianhydride acid” is intended to include precursors or derivatives thereof, which may not technically be dianhydride acids, but which will nonetheless react with diamines to form polyamic acids, which in turn will form polyamic acids. It can be converted to mead.

As used herein, “diamine” is intended to include precursors or derivatives thereof, which may not technically be diamines, but which will nonetheless react with dianhydride to form polyamic acids, which in turn will form polyamic acids. It can be converted to mead.

The polyimide film according to the present invention includes biphenyltetracarboxylic dianhydride (3,3′,4,4′-Biphenyltetracarboxylic dianhydride, BPDA), pyromellitic dianhydride (PMDA), and benzophenone tetrahydride. Dianhydride components including carboxylic dianhydride (3,3',4,4'-Benzophenenetetracarboxylic dianhydride, BTDA); and oxydianiline (4,4'-Oxydianiline, ODA), p-Phenylenediamine (PPD), and 4,4'-diaminobenzanilide (DABA). It is manufactured by imidizing a polyamic acid solution containing a diamine component.

In one embodiment, based on a total content of 100 mol% of the diamine component, the content of the oxydianiline is 23 mol% or more and 43 mol% or less, and the content of the paraphenylene diamine is 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.

Since the 4,4'-diaminobenzanilide contains an amide group, it greatly contributes to the excellent heat resistance and improvement of mechanical properties of the polyimide film of the present application within the content range of the present application.

In one embodiment, the content of the biphenyltetracarboxylic dianhydride is 15 mol% or more and 30 mol% or less based on the total content of the dianhydride component of 100 mol%, and the content of the pyromellitic dianhydride is The content is 50 mol% or more and 65 mol% or less, and the content of the benzophenone tetracarboxylic 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), that is, the electron donor and electron acceptor are close to each other. It has a regular straight structure and intermolecular interaction is strengthened.

In addition, benzophenone tetracarboxylic dianhydride, which has a carbonyl group, contributes to the expression of CTC like biphenyl tetracarboxylic dianhydride.

In particular, the dianhydride component may additionally include pyromellitic dianhydride. Pyromellitic dianhydride is a dianhydride component with a relatively rigid structure and is preferred because it can provide appropriate elasticity to the polyimide film.

In addition, biphenyltetracarboxylicdianhydride and benzophenonetetracarboxylicdianhydride contain two benzene rings corresponding to the aromatic portion, while pyromellitic dianhydride contains a benzene ring corresponding to the aromatic portion. Includes 1.

The increase in the pyromellitic dianhydride content in the dianhydride component can be understood as an increase in the imide group within the molecule based on the same molecular weight, which means that the imide group derived from the pyromellitic dianhydride is added to the polyimide polymer chain. It can be understood that the ratio of groups increases relative to the imide group derived from biphenyl tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.

If the content ratio of pyromellitic dianhydride is reduced too much, the component having a relatively rigid structure is reduced, and the mechanical properties of the polyimide film may be lowered below a desired level.

For this reason, when the content of biphenyltetracarboxylicdianhydride and benzophenonetetracarboxylicdianhydride exceeds the above range, the mechanical properties of the polyimide film deteriorate.

In one embodiment, the polyimide film may include a block copolymer composed of two or more blocks.

At least one block of the block copolymer may include a bond of pyromellitic dianhydride and 4,4'-diaminobenzanilide.

By adjusting the blocks of this block copolymer, the glass transition temperature of the polyimide film can be increased, thereby ensuring 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.

Additionally, 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 may generally be difficult to coexist with strength at a desirable level, but the composition and composition ratio including 4,4'-diaminobenzanilide containing an amide group of the present invention exhibits a desirable level of strength. At the same time, it can play a major role in suppressing the decrease in elongation.

In the present invention, the production of polyamic acid is, for example,

(1) A method of polymerizing the entire amount of the diamine component in a solvent and then adding the dianhydride component in substantially equimolar amounts to the diamine component;

(2) A method of polymerizing the entire amount of the dianhydride component in a solvent, and then adding the diamine component in substantially equimolar amounts to the dianhydride component;

(3) After adding some of the diamine components into the solvent, mixing some of the dianhydride components in a ratio of about 95 to 105 mol% with respect to the reaction components, adding the remaining diamine components, and then adding the remaining dianhydride components continuously. A method of polymerizing by adding components such that the diamine component and the dianhydride component are substantially equimolar;

(4) After adding the dianhydride component into the solvent, mixing some components of the diamine compound in a ratio of 95 to 105 mol% with respect to the reaction component, adding another dianhydride component, and then adding the remaining diamine component, A method of polymerizing the diamine component and the dianhydride component in substantially equimolar amounts;

(5) reacting some diamine components and some dianhydride components in a solvent so that either one is in excess to form a first composition, and reacting some diamine components with some dianhydride components in another solvent so that any one is in excess to form a first composition. 2 After forming the composition, the first and second compositions are mixed and polymerization is completed. In this case, if the diamine component is excessive when forming the first composition, the dianhydride component is added in excess in the second composition. When the dianhydride component is excessive in the first composition, the diamine component is excessive in the second composition, and the first and second compositions are mixed so that the total diamine component and dianhydride component used in these reactions are substantially equal. A method of polymerizing the molar mass may be included.

However, the polymerization method is not limited to the above examples, and of course, any known method can be used to produce polyamic acid.

In one specific example, the method for producing a polyimide film according to the present invention includes,

(a) dianhydride components including biphenyl tetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and benzophenone tetracarboxylic dianhydride (BTDA), and oxydianiline ( Preparing polyamic acid by polymerizing a diamine component consisting of ODA), paraphenylene diamine (PPD), and 4,4'-diaminobenzanilide (DABA) in an organic solvent; and (b) imidizing the polyamic acid.

In one embodiment, based on a total content of 100 mol% of the diamine component, the content of the oxydianiline is 23 mol% to 43 mol%, and the content of the paraphenylene diamine is 50 mol% to 60 mol%. Below, the content of the 4,4'-diaminobenzanilide is 10 mol% or more and 30 mol% or less, and the biphenyltetracarboxylic dianhydride is based on 100 mol% of the total content of the dianhydride component. The content of the pyromellitic 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 benzophenonetetracarboxylic dianhydride is 10 mol% or more. It may be 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 the polyimide film manufactured from the polyamic acid of the present invention manufactured through the above process has improved mechanical properties and heat resistance. It can be preferably applied to the effect of the present invention.

On the other hand, the solvent for synthesizing polyamic acid is not particularly limited, and any solvent can be used as long as it dissolves polyamic acid, but it is preferable that it is an amide-based solvent.

Specifically, the solvent may be an organic polar solvent, and in particular, may be an aprotic polar solvent, for example, N,N-dimethylformamide (DMF), N,N- Dimethylacetamide (DMAc), N-methyl-pyrrolidone (NMP), p-chlorophenol, o-chlorophenol, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), digrim ( Diglyme) may be one or more selected from the group consisting of, but is not limited to, and may be used alone or in combination of two or more types as needed.

In one example, N,N-dimethylformamide and N,N-dimethylacetamide may be particularly preferably used as the solvent.

Additionally, in the polyamic acid manufacturing process, fillers other than nano silica may be added to improve various properties of the film such as sliding properties, thermal conductivity, corona resistance, and loop hardness. The added filler is not particularly limited, but preferred examples include titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.

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. Generally, the average particle diameter 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, it becomes difficult to achieve a reforming effect, and if the particle size is above this range, the surface properties may be greatly damaged or the mechanical properties may be greatly reduced.

Additionally, the amount of filler added is not particularly limited and may be determined based on the film properties to be modified, the particle size of the filler, etc. Generally, the amount of filler 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 filler added is less than this range, it is difficult to achieve a reforming effect due to the filler, and if it is more than 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 can be produced by thermal imidization and chemical imidization.

In addition, it may be manufactured by a complex imidization method in which thermal imidization and chemical imidization are combined.

The thermal imidization method is a method of inducing an imidization reaction using a heat source such as hot air or an infrared dryer, excluding chemical catalysts.

The thermal imidization method can imidize the amic acid group present in the gel film by heat treating the gel film at a variable temperature in the range of 100 to 600 ℃, specifically 200 to 500 ℃, more specifically, The amic acid group present in the gel film can be imidized by heat treatment at 300 to 500°C.

However, even in the process of forming a gel film, some of the amic acid (about 0.1 mol% to 10 mol%) may be imidized, and for this purpose, the polyamic acid composition is dried at a variable temperature in the range of 50 ℃ to 200 ℃. It can also be included in the scope of the thermal imidization method.

In the case of chemical imidization, a polyimide film can be produced using a dehydrating agent and an imidizing agent according to methods known in the art. Here, “dehydrating agent” refers to a substance that promotes ring closure reaction through a dehydrating effect on polyamic acid, and non-limiting examples thereof include aliphatic acid anhydride, aromatic acid anhydride, N, N' -Dialkyl carbodiimide, halogenated lower aliphatic, halogenated lower fatty acid anhydride, aryl phosphonic dihalide, and thionyl halide. Among these, aliphatic acid anhydride may be preferable in terms of ease of acquisition and cost, and non-limiting examples thereof include acetic anhydride (or acetic anhydride, AA), propionic acid anhydride, and lactic acid anhydride. Examples include acid anhydride, and these can be used alone or in combination of two or more types.

In addition, “imidizing agent” refers to a substance that has the effect of promoting the ring closure reaction for polyamic acid, and may include, for example, imine-based components such as aliphatic tertiary amines, aromatic tertiary amines, and heterocyclic tertiary amines. You can. Among these, heterocyclic tertiary amines may be preferable from the viewpoint of reactivity as a catalyst. Non-limiting examples of heterocyclic tertiary amines include quinoline, isoquinoline, β-picoline (BP), pyridine, etc., and these can be used alone or in a mixture of two or more.

The amount of the dehydrating agent added is preferably in the range of 0.5 to 5 mole, and particularly preferably in the range of 1.0 mole to 4 mole, per 1 mole of amic acid groups in the polyamic acid. In addition, the amount of imidizing agent added is preferably in the range of 0.05 mole to 2 mole, and particularly preferably in the range of 0.2 mole to 1 mole, per 1 mole of amic acid groups in the polyamic acid.

If the dehydrating agent and imidizing agent are below the above range, chemical imidization may be insufficient, cracks may be formed in the produced polyimide film, and the mechanical strength of the film may also decrease. In addition, if these addition amounts exceed the above range, imidization may proceed excessively quickly, and in this case, it may be difficult to cast into a film form or the produced polyimide film may exhibit brittle characteristics, which is not desirable. not.

An example of the complex imidization method is to add a dehydrating agent and an imidizing agent to a polyamic acid solution, heat it at 80 to 200°C, preferably 100 to 180°C, partially cure and dry, and then heat it at 5 to 400°C at 200 to 400°C. A polyimide film can be produced by heating for a few seconds.

The present invention provides a multilayer film including the above-described polyimide film and a thermoplastic resin layer, and a flexible metal-clad laminate including the above-described polyimide film and an electrically conductive metal foil.

As the thermoplastic resin layer, for example, a thermoplastic polyimide resin layer may be applied.

There is no particular limitation on the metal foil to be used, but when using the flexible metal clad laminate of the present invention for electronic or electrical equipment, for example, copper or copper alloy, stainless steel or its alloy, nickel or nickel alloy (42 alloy) Also included), may be a metal foil containing aluminum or aluminum alloy.

In general flexible metal clad laminates, copper foils such as rolled copper foil and electrolytic copper foil are widely used, and can also be preferably used in the present invention. Additionally, a rust-prevention layer, a heat-resistant layer, or an adhesive layer may be applied to the surface of these metal foils.

In the present invention, the thickness of the metal foil is not particularly limited, and may be sufficient to provide sufficient function depending on the intended use.

The flexible metal clad laminate according to the present invention has metal foil laminated on one side of the polyimide film, or an adhesive layer containing thermoplastic polyimide is added to one side of the polyimide film, and the metal foil is attached to the adhesive layer. It may be a laminated structure.

The present invention also provides an electronic component including the flexible metal clad laminate as an electrical signal transmission circuit.

Hereinafter, the operation and effects of the invention will be described in more detail through specific examples of the invention. However, these examples are merely presented as examples of the invention and do not determine the scope of the invention.

<Manufacturing example>

DMF was added while nitrogen was injected into a 500 ml reactor equipped with a stirrer and nitrogen injection/discharge pipes, the temperature of the reactor was set to 30°C, and oxydianiline (ODA), paraphenylene diamine (PPD) and 4 were added as diamine components. , 4'-diaminobenzanilide (DABA), and biphenyl tetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and benzophenone tetracarboxylic dianhydride as dianhydride components. Add (BTDA) and check that it is completely dissolved.

Afterwards, the temperature of the reactor was raised to 40°C under a nitrogen atmosphere and stirring was continued for 120 minutes while heating to prepare polyamic acid.

A catalyst and a dehydrating agent were added to the polyamic acid prepared in this way, bubbles were removed through high-speed rotation of over 1,500 rpm, and then it was applied to a glass substrate using a spin coater.

Afterwards, a gel film was prepared by drying at a temperature of 120°C for 30 minutes under a nitrogen atmosphere, which was heated to 450°C at a rate of 2°C/min, heat treated at 450°C for 60 minutes, and then heated to 30°C for 2 minutes. By cooling again at a rate of ℃/min, the final polyimide film was obtained, and it was peeled from the glass substrate by dipping in distilled water.

The thickness of the prepared polyimide film was 15 ㎛. The thickness of the manufactured polyimide film was measured using an electric film thickness tester from Anritsu.

<Examples 1 to 4 and Comparative Examples 1 to 3>

It was prepared according to the preparation example described above, but the contents of diamine monomer and dianhydride monomer were adjusted as shown in Table 1.

diamine monomer
(mole%) dianhydride monomer
(mole%) PPD O.D.A. 4,4-DABA PMDA BTDA BPDA Example 1 55 25 20 55 27 18 Example 2 55 30 15 55 27 18 Example 3 55 35 10 55 27 18 Example 4 55 35 10 63 10 27 Comparative Example 1 55 45 0 63 10 27 Comparative Example 2 55 45 0 58 20 22 Comparative Example 3 67.5 22.5 10 40 35 25

<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 shown in Table 2.

(1) Elastic modulus, strength and elongation

The elastic modulus, strength, and elongation were measured using Instron 3365SER equipment according to the ASTM D 882 measurement method.

(2) Glass transition temperature measurement

For the glass transition temperature (T _g ), the loss modulus and storage modulus of each film were obtained using DMA, and the inflection point in their tangent graph was measured as the glass transition temperature.

modulus of elasticity
(GPa) robbery
(MPa) believer
(%) Tg
(℃) Example 1 5.1 370 85 364 Example 2 5.4 370 80 377 Example 3 5.7 375 77 369 Example 4 5.3 350 65 369 Comparative Example 1 6.2 330 40 371 Comparative Example 2 6.0 325 45 346 Comparative Example 3 6.1 330 56 357

As confirmed in Table 2, the polyimide film manufactured according to the examples of the present invention not only has an elastic modulus of 5GPa or more and a strength of 340MPa or more, which is excellent in mechanical strength, but also has a glass transition temperature (Tg) of 360°C or more. Accordingly, thermal stability was excellent.

In addition, the elongation was over 60%, making it possible to achieve both excellent mechanical strength and excellent elongation.

These results are achieved by the components and composition ratio specified herein, and it can be seen that the content of each component plays a decisive role.

On the other hand, the polyimide films of Comparative Examples 1 to 3 were measured to have higher elastic modulus compared to the polyimide films of Examples 1 to 4.

However, 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 were lower than those of the polyimide films of Examples 1 to 4. The glass transition temperature was also confirmed to be low.

From this, it could be expected that the polyimide films of the comparative example would have difficulty actually being applied to electronic components.

Although the present invention has been described with reference to embodiments of the present invention, those skilled in the art will be able to make various applications and modifications based on the above contents within the scope of the present invention.

Claims (13)

A dianhydride component consisting of biphenyl tetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and benzophenone tetracarboxylic dianhydride (BTDA); and
It is prepared by imidizing a polyamic acid solution containing a diamine component including oxydianiline (ODA), paraphenylene diamine (PPD), and 4,4'-diaminobenzanilide (DABA),
It is a block copolymer composed of two or more blocks,
At least one of the blocks includes a bond of pyromellitic dianhydride and 4,4'-diaminobenzanilide,
The glass transition temperature (Tg) is 360 ℃ or higher,
With more than 60% believers,
Polyimide film. According to paragraph 1,
Based on the total content of the diamine component of 100 mol%, the content of the oxydianiline is 23 mol% to 43 mol%, the content of the paraphenylene diamine is 50 mol% to 60 mol%, and the above 4 , the content of 4'-diaminobenzanilide is 10 mol% or more and 30 mol% or less,
Polyimide film. According to paragraph 1,
Based on the total content of the dianhydride component of 100 mol%, the content of the biphenyltetracarboxylic dianhydride is 15 mol% or more and 30 mol% or less, and the content of the pyromellitic dianhydride is 50 mol% or more. 65 mol% or less, and the content of the benzophenone tetracarboxylic dianhydride is 10 mol% or more and 35 mol% or less,
Polyimide film. delete According to paragraph 1,
The elastic modulus is 5GPa or more and the strength is 340MPa or more,
Polyimide film. delete (a) a dianhydride component consisting of biphenyl tetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and benzophenone tetracarboxylic dianhydride (BTDA), and oxydianiline (ODA) ), preparing polyamic acid by polymerizing a diamine component composed of paraphenylene diamine (PPD) and 4,4'-diaminobenzanilide (DABA) in an organic solvent; and
(b) imidizing the polyamic acid; including,
The polyimide film produced is a block copolymer composed of two or more blocks,
At least one of the blocks includes a combination of pyromellitic dianhydride and 4,4'-diaminobenzanilide,
The polyimide film produced has a glass transition temperature (Tg) of 360 ℃ or more and an elongation of 60% or more,
Method for producing polyimide film. In clause 7,
Based on a total content of 100 mol% of the diamine component, the content of the oxydianiline is 23 mol% to 43 mol%, the content of the paraphenylene diamine is 50 mol% to 60 mol%, and 4, The content of 4'-diaminobenzanilide is 10 mol% or more and 30 mol% or less,
Based on the total content of the dianhydride component of 100 mol%, the content of the biphenyltetracarboxylic dianhydride is 15 mol% or more and 30 mol% or less, and the content of the pyromellitic dianhydride is 50 mol% or more. 65 mol% or less, and the content of the benzophenone tetracarboxylic dianhydride is 10 mol% or more and 35 mol% or less,
Method for producing polyimide film. In clause 7,
The elastic modulus of the polyimide film is 5GPa or more,
With a strength of more than 340 MPa,
Method for producing polyimide film. Comprising the polyimide film of any one of claims 1 to 3 and 5,
Multilayer film. The polyimide film of any one of claims 1 to 3 and 5; and
Containing a thermoplastic resin layer;
Multilayer film. The polyimide film of any one of claims 1 to 3 and 5; and
Containing: electrically conductive metal foil;
Flexible metal foil laminate. Containing a flexible metal clad laminate according to paragraph 12,
Electronic parts.