CN118043383A - Polyimide film containing graphene nanoplatelets and method for producing same - Google Patents

Polyimide film containing graphene nanoplatelets and method for producing same Download PDF

Info

Publication number
CN118043383A
CN118043383A CN202280063233.9A CN202280063233A CN118043383A CN 118043383 A CN118043383 A CN 118043383A CN 202280063233 A CN202280063233 A CN 202280063233A CN 118043383 A CN118043383 A CN 118043383A
Authority
CN
China
Prior art keywords
mol
polyimide film
content
dianhydride
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202280063233.9A
Other languages
Chinese (zh)
Inventor
田珍硕
吕文真
白承烈
李吉男
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polyimide Advanced Materials Co ltd
Original Assignee
Polyimide Advanced Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polyimide Advanced Materials Co ltd filed Critical Polyimide Advanced Materials Co ltd
Publication of CN118043383A publication Critical patent/CN118043383A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Disclosed is a polyimide film which is obtained by imidizing a polyamic acid solution containing an acid dianhydride component including benzophenone tetracarboxylic acid dianhydride (BTDA), biphenyl tetracarboxylic acid dianhydride (BPDA), and pyromellitic acid dianhydride (PMDA), and a diamine component including m-tolidine (m-tolidine) and p-phenylenediamine (PPD), wherein the polyimide film contains 0.5-2.5 wt% of graphene nanoplatelets (graphene nanoplatelets).

Description

Polyimide film containing graphene nanoplatelets and method for producing same
Technical Field
The present invention relates to a polyimide film having excellent dielectric characteristics including graphene nanoplatelets, and a method for manufacturing the same.
Background
Polyimide (PI) is a polymer material having the highest level of heat resistance, chemical resistance, electrical insulation, chemical resistance, and weather resistance among organic materials based on an imide ring and a rigid aromatic main chain, which are excellent in chemical stability.
In particular, since excellent insulating properties, i.e., excellent electrical properties such as low dielectric constant, are attracting attention as high-functional polymer materials in the fields of electric, electronic, optical, and the like.
In recent years, with the progress of weight reduction and miniaturization of electronic products, thin circuit boards having high integration and flexibility have been actively developed.
Many of such thin circuit boards have a structure in which a circuit including a metal foil is formed on a polyimide film having excellent heat resistance, low temperature resistance, and insulating properties and being easily bent.
As such a thin circuit board, a Flexible metal foil laminate is mainly used, and for example, a Flexible Copper foil laminate (Flexible Copper CLAD LAMINATE, FCCL) using a thin Copper plate as a metal foil is included. In addition, polyimide is also used as a protective film, an insulating film, or the like of a thin circuit board.
On the other hand, in recent years, various functions have been incorporated in electronic devices, and thus the electronic devices are required to have a fast operation speed and a fast communication speed, and in order to meet such a demand, thin circuit boards capable of high-speed communication at high frequencies have been developed.
In order to realize high-frequency and high-speed communication, an insulator having high impedance (impedance) capable of maintaining electrical insulation even at high frequencies is required. The impedance is inversely proportional to the frequency and dielectric constant (DIELECTRIC CONSTANT; dk) formed by the insulator, so that the dielectric constant should be as low as possible in order to maintain insulation also at high frequencies.
However, in the case of a general polyimide, it is a practical case that the dielectric characteristics have not yet reached an excellent level sufficient to maintain sufficient insulation in high frequency communication.
In addition, it is known that the lower the dielectric characteristics of the insulator, the less unwanted parasitic capacitance (STRAY CAPACITANCE) and noise are generated in the thin circuit board, and the problem of communication delay can be solved to a large extent.
Therefore, in practice, polyimide with low dielectric characteristics is considered to be the most important factor affecting the performance of a thin circuit substrate.
In particular, in the case of high-frequency communication, dielectric loss (DIELECTRIC DISSIPATION) is inevitably generated by polyimide, and dielectric loss tangent (DIELECTRIC DISSIPATION FACTOR; df) is a degree of waste of electric energy of a thin circuit board and is closely related to signal transmission delay determining communication speed, so that it is considered as an important factor affecting performance of the thin circuit board to keep dielectric loss tangent of polyimide as low as possible.
In addition, the more moisture the polyimide film contains, the greater the dielectric constant and the greater the dielectric loss tangent. Polyimide films are suitable as materials for thin circuit boards because of their excellent inherent properties, but they are relatively vulnerable to moisture due to polar imide groups, and thus may have reduced insulating properties.
Therefore, in practice, it is necessary to develop a polyimide film having dielectric properties which maintain the mechanical properties peculiar to polyimide at a certain level.
In addition, recently, as the transmission speed increases, a terminator (terminator) is attached to a circuit end portion to absorb energy in order to solve the problem that the reflected signal disturbs the rising time (RISING TIME) and hinders the operation of a semiconductor. For this absorption mode application, the impedance of the termination must be the same as the impedance of the transmission circuit.
At this time, since the impedance value of the terminator resistor (terminator Resistor) is fixed, it is necessary to adjust the circuit impedance of the printed circuit substrate (PCB).
That is, since the impedance decreases with the decrease in insulation thickness due to the miniaturization of electronic devices, the dielectric constant must be higher than that of the conventional polyimide film (Dk: 3.5) in order to satisfy the impedance value of the fixed terminator resistance.
[ Prior Art literature ]
[ Patent literature ]
(Patent document 1) Korean laid-open patent publication No. 10-2015-0069318
Disclosure of Invention
Technical problem
Accordingly, in order to solve the above-described problems, an object is to provide a polyimide film having excellent dielectric characteristics and a method for producing the same.
For this purpose, a practical object of the invention is to provide specific embodiments thereof.
Means for solving the problems
In order to achieve the above object, one embodiment of the present invention provides a polyimide film obtained by imidizing a polyamic acid solution containing an acid dianhydride component including Benzophenone Tetracarboxylic Dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA), and pyromellitic dianhydride (PMDA) and a diamine component including m-toluidine (m-tolidine) and p-phenylene diamine (PPD), and containing 0.5 to 2.5 wt% of graphene nanoplatelets (graphene nanoplatelets).
The content of m-toluidine may be 20 to 40 mol% based on 100 mol% of the total diamine component, and the content of p-phenylenediamine may be 60 to 80 mol%.
The content of benzophenone tetracarboxylic acid dianhydride may be 20 to 45 mol% based on 100 mol% of the total content of the acid dianhydride component, the content of biphenyl tetracarboxylic acid dianhydride may be 20 to 45 mol%, and the content of pyromellitic acid dianhydride may be 20 to 45 mol%.
The average thickness of the graphene nano-sheets can be 6-8 nm, the average particle size can be 5-25 mu m, and the specific surface area can be 120-150 m 2/g.
On the other hand, the dielectric constant of the polyimide film may be 4.0 to 7.0, and the dielectric loss tangent may be 0.01.
Another embodiment of the present invention provides a method for producing a polyimide film, including: (a) A step of polymerizing an acid dianhydride component including Benzophenone Tetracarboxylic Dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) with a diamine component composed of m-tolidine m-toluidine (m-tolidine) and p-phenylenediamine (PPD) in an organic solvent to produce a polyamic acid; (b) Adding graphene nanoplatelets into the polyamide acid and mixing; and (c) imidizing the polyamic acid including the graphene nanoplatelets.
Still another embodiment of the present invention provides a multilayer film including the polyimide film, a flexible metal foil laminate including the polyimide film and a conductive metal foil, and an electronic component including the flexible metal foil laminate.
Effects of the invention
As described above, the present invention provides a polyimide film having excellent dielectric characteristics by a polyimide film composed of a specific component and a specific composition ratio, and a method for producing the same, and can be effectively applied to various fields requiring such characteristics, in particular, electronic components such as flexible metal foil laminated boards.
Detailed Description
Hereinafter, 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.
Before this, the terms or words used in the present specification and claims should not be interpreted as meaning in general or dictionary, but should be interpreted in accordance with the meaning and concept conforming to the technical idea of the present invention on the basis of the principle that the inventor can properly define the concept of terms to explain the invention in an optimal way.
Therefore, the configuration of the embodiment described in the present specification is only one embodiment which is the most preferable of the present application, and does not represent all the technical ideas of the present application, and therefore it should be understood that there may be various equivalents and modifications that can replace these embodiments when the present application is proposed.
In this specification, the expression in the singular includes the expression in the plural unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprises," "comprising," "includes," or "having," etc., are intended to specify the presence of stated features, integers, steps, components, or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components, or groups thereof.
In the present specification, where amounts, concentrations or other values or parameters are given as a list of ranges, preferred ranges or upper values and preferred lower values, it is to be understood that any pair of any upper range limit or preferred value and any lower range limit or preferred value is specifically disclosed whether or not the ranges are individually disclosed.
Where a range of values is recited in the specification, 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 particular values recited when defining the range.
In this specification, "acid dianhydride" is intended to include precursors or derivatives thereof which, although they may not be technically acid dianhydrides, still react with diamines to form polyamic acids which can be reconverted to polyimides.
In this specification, "diamine" is intended to include precursors or derivatives thereof which, although they may not be technically diamines, still react with dianhydrides to form polyamic acids which can be reconverted to polyimides.
In the present specification, "a to b" and "to" representing the numerical ranges of "a to b" are defined as ≡a and ≡b.
The polyimide film of the present invention is obtained by imidizing a polyamic acid solution containing an acid dianhydride component including benzophenone tetracarboxylic acid dianhydride (BTDA), biphenyl tetracarboxylic acid dianhydride (BPDA), and pyromellitic acid dianhydride (PMDA) and a diamine component including m-tolidine (m-tolidine) and p-phenylenediamine (PPD), and containing 0.5 to 2.5 wt% of graphene nanoplatelets (graphene nanoplatelets).
The content of m-toluidine may be 20 to 40 mol% based on 100 mol% of the total diamine component, and the content of p-phenylenediamine may be 60 to 80 mol%.
In particular, m-toluidine contributes to low moisture absorption characteristics of polyimide films because it has methyl groups exhibiting hydrophobicity, in particular.
The content of benzophenone tetracarboxylic dianhydride may be 20 mol% to 45 mol% based on 100 mol% of the total content of the acid dianhydride component, the content of biphenyl tetracarboxylic dianhydride may be 20 mol% to 45 mol% based on the total content of the acid dianhydride component, and the content of pyromellitic dianhydride may be 20 mol% to 45 mol% based on the total content of the acid dianhydride component.
Polyimide chains derived from the biphenyltetracarboxylic dianhydride of the present invention have a structure called a charge transfer complex (CTC: CHARGE TRANSFER complex), i.e., a regular linear structure in which an electron donor (electron donnor) and an electron acceptor (electron acceptor) are close to each other, and thus intermolecular interactions (intermolecular interaction) are enhanced.
In addition, the benzophenone tetracarboxylic dianhydride having a carbonyl group contributes to expression of CTCs, similarly to the biphenyl tetracarboxylic dianhydride.
Such a structure has an effect of preventing hydrogen bonding with moisture, and thus can exert an influence on reducing the moisture absorption rate, thereby maximizing the effect of reducing the moisture absorption of the polyimide film.
In one embodiment, the acid dianhydride component may further contain pyromellitic dianhydride. The pyromellitic dianhydride is an acid dianhydride component having a relatively rigid structure, and is preferable in that it imparts moderate elasticity to the polyimide film.
The content ratio of the acid dianhydride is particularly important in order to achieve a polyimide film that satisfies both moderate elasticity and moisture absorption. For example, the lower the content ratio of biphenyl tetracarboxylic dianhydride, the more difficult it is to expect the low moisture absorption rate due to the CTC structure.
In addition, biphenyl tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride contain 2 benzene rings corresponding to aromatic moieties, and pyromellitic dianhydride contains 1 benzene ring corresponding to aromatic moieties.
In the acid dianhydride component, an increase in the content of pyromellitic dianhydride based on the same molecular weight is understood to be an increase in the number of imide groups in the molecule, and this is understood to be a relative increase in the ratio of imide groups derived from pyromellitic dianhydride in the polyimide polymer chain as compared with imide groups derived from biphenyl tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.
That is, an increase in the content of pyromellitic dianhydride can be considered as a relative increase in the imide groups relative to the whole polyimide film, and therefore it is difficult to expect a low moisture absorption rate.
Conversely, if the content ratio of pyromellitic dianhydride is reduced, the composition of the rigid structure is relatively reduced, so that the elasticity of the polyimide film may be reduced below a desired level.
For this reason, when the content of the biphenyl tetracarboxylic dianhydride and the benzophenone tetracarboxylic dianhydride is higher than the above range or the content of the pyromellitic dianhydride is lower than the above range, the mechanical properties of the polyimide film are lowered, and the heat resistance at a level suitable for manufacturing a flexible metal foil laminate cannot be ensured.
In contrast, in the case where the content of the above-mentioned biphenyl tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride is lower than the above-mentioned range or the content of pyromellitic dianhydride is higher than the above-mentioned range, it is difficult to achieve a proper level of dielectric constant, dielectric loss tangent and moisture absorption rate, and thus it is not preferable.
On the other hand, the average thickness of the graphene nanoplatelets may be 6 to 8nm, the average particle size may be 5 to 25 μm, and the specific surface area may be 120 to 150m 2/g.
The graphene nanoplatelets have relatively excellent dispersibility compared to other carbon nanomaterials, and can minimize a decrease in dielectric loss tangent of a polyimide film when added to the polyimide film.
In one embodiment, the polyimide film may have a dielectric constant of 4.0 to 7.0, and a dielectric loss tangent of 0.01.
The dielectric constant may be preferably 4.5 or more, and more preferably 5.0 or more.
In this regard, in the case of a polyimide film in which all of the dielectric constant (Dk) and dielectric dissipation factor (Df) are satisfied, the polyimide film can be used as an insulating film for a flexible metal foil laminate, and even if the manufactured flexible metal foil laminate is used for an electric signal transmission circuit that transmits a signal at a high frequency of 10GHz or more, the insulation stability thereof can be ensured, and the signal transmission delay can be minimized.
In the present invention, the polyamic acid can be produced by the following method:
(1) A method in which the entire diamine component is added to a solvent, and then an acid dianhydride component is added in a substantially equimolar manner to the diamine component to polymerize the diamine component;
(2) A method in which the entire acid dianhydride component is added to a solvent, and then a diamine component is added in a substantially equimolar manner to the acid dianhydride component to polymerize the acid dianhydride component;
(3) A method in which a part of the diamine component is added to a solvent, and then a part of the acid dianhydride component is mixed at a ratio of about 95 to 105 mol% with respect to the reaction component, and then the remaining diamine component is added, and then the remaining acid dianhydride component is added, whereby polymerization is performed so that the diamine component and the acid dianhydride component are substantially equimolar;
(4) A method in which a part of the components in the diamine compound is mixed at a ratio of about 95 to 105 mol% with respect to the reaction components after adding the acid dianhydride component to the solvent, then the other acid dianhydride component is added, and then the remaining diamine component is added, whereby polymerization is performed so that the diamine component and the acid dianhydride component are substantially equimolar;
(5) A method in which a part of the diamine component and a part of the acid dianhydride component are reacted in a solvent so as to be in excess of either one to form a first composition, and a part of the diamine component and a part of the acid dianhydride component are reacted in another solvent so as to be in excess of either one to form a second composition, and then the first and second compositions are mixed and polymerized, wherein when the first composition is formed, if the diamine component is in excess, the acid dianhydride component is in excess in the second composition, and if the acid dianhydride component is in excess in the first composition, the diamine component is in excess in the second composition, whereby the first and second compositions are mixed and polymerized so that the entire diamine component used in the reaction thereof and the acid dianhydride component are substantially equimolar; etc.
However, the polymerization method is not limited to the above examples, and any known method can be used for producing the polyamic acid.
In one specific example, the method for producing a polyimide film of the present invention may comprise:
(a) A step of producing a polyamic acid by performing an acid dianhydride component comprising Benzophenone Tetracarboxylic Dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA), and pyromellitic dianhydride (PMDA) and a diamine component comprising m-tolidine and p-phenylenediamine (PPD) in an organic solvent;
(b) Adding graphene nanoplatelets into the polyamide acid and mixing; and
(C) Imidizing the polyamic acid containing the graphene nanoplatelets.
The content of m-toluidine may be 20 to 40 mol% based on 100 mol% of the total diamine component, the content of p-phenylenediamine may be 60 to 80 mol% based on 100 mol% of the total acid dianhydride component, the content of benzophenone tetracarboxylic dianhydride may be 20 to 45 mol% based on 100 mol% of the total acid dianhydride component, the content of biphenyl tetracarboxylic dianhydride may be 20 to 45 mol% based on 20 mol% of the total acid dianhydride component, and the content of pyromellitic dianhydride may be 20 to 45 mol% based on 20 mol% of the total acid dianhydride component.
In the present invention, the polymerization method of the polyamic acid as described above can be defined by a random (random) polymerization method, and from the viewpoint of maximizing the effect of the present invention with excellent dielectric characteristics, a polyimide film produced from the polyamic acid of the present invention produced by the process as described above can be preferably used.
However, the polymerization method described above may have a limitation in that the length of the repeating unit in the polymer chain described above is made short, and therefore, the polyimide chain derived from the acid dianhydride component may exhibit various excellent properties. Therefore, the polymerization method of the polyamic acid that can be particularly preferably used in the present invention may be a block polymerization method.
On the other hand, the solvent used for synthesizing the polyamic acid is not particularly limited, and any solvent may be used as long as it is a solvent that dissolves the polyamic acid, and an amide-based solvent is preferable.
Specifically, the solvent may be an organic polar solvent, specifically, an aprotic polar solvent (aprotic polar solvent), for example, one or more selected from the group consisting of N, N-Dimethylformamide (DMF), N-dimethylacetamide, N-methyl-pyrrolidone (NMP), γ -butyrolactone (GBL), and diglyme (Diglyme), but not limited thereto, and two or more may be used alone or in combination as needed.
In one example, the above solvent may particularly preferably be used N, N-dimethylformamide and N, N-dimethylacetamide.
In addition, fillers may be added in the polyamic acid production process to improve various properties of the film such as slidability, thermal conductivity, corona resistance, knoop hardness, and the like. The filler to be added is not particularly limited, and preferable examples thereof include silica, titanium oxide, aluminum oxide, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and the like.
The particle diameter of the filler is not particularly limited as long as it is determined according to the film characteristics to be modified and the kind of filler added. In general, the average particle diameter is from 0.05 to 100. Mu.m, preferably from 0.1 to 75. Mu.m, more preferably from 0.1 to 50. Mu.m, particularly preferably from 0.1 to 25. Mu.m.
If the particle diameter is less than the above range, the modifying effect is hardly exhibited, and if it is more than the above range, the surface properties may be greatly impaired or the mechanical properties may be greatly lowered.
The amount of 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, and the like. In general, the filler is added in an amount of 0.01 to 100 parts by weight, preferably 0.01 to 90 parts by weight, more preferably 0.02 to 80 parts by weight, relative to 100 parts by weight of the polyimide.
If the amount of filler is less than the above range, the modifying effect by the filler is hardly exhibited, and if it is more than the above range, the mechanical properties of the film may be greatly impaired. 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 a thermal imidization method and a chemical imidization method.
Further, the polyimide resin can be produced by a composite imidization method using a thermal imidization method and a chemical imidization method in combination.
The thermal imidization method is a method of inducing imidization reaction by using a heat source such as a hot air dryer or an infrared dryer while excluding a chemical catalyst.
In the thermal imidization method, the gel film may be heat-treated at a variable temperature in the range of 100 to 600 ℃ to imidize the amidic acid groups present in the gel film, specifically, at 200 to 500 ℃, and more specifically, at 300 to 500 ℃.
However, imidization may also occur in a part (about 0.1 to 10 mol%) of the amic acid during the formation of the gel film, and for this reason, the polyamic acid composition may be dried at a variable temperature in the range of 50 to 200 ℃, which also falls within the scope of the thermal imidization method described above.
In the case of the chemical imidization method, a polyimide film may be manufactured using a dehydrating agent and an imidizing agent according to a method well known in the art.
As an example of the composite imidization method, a polyimide film may be produced by adding a dehydrating agent and an imidizing agent to a polyamic acid solution, heating at 80 to 200 ℃, preferably 100 to 180 ℃ to perform partial curing and drying, and then heating at 200 to 400 ℃ for 5 to 400 seconds.
The polyimide film of the present invention produced by the production method as described above may have a dielectric constant of 4.0 to 7.0, and a dielectric loss tangent of 0.01.
The present invention provides a multilayer film comprising the polyimide film and a flexible metal foil laminate comprising the polyimide film and a conductive metal foil.
The above-mentioned multilayer film may contain a thermoplastic resin layer, in particular, a thermoplastic polyimide resin layer.
The metal foil to be used is not particularly limited, and in the case of using the flexible metal foil laminate of the present invention in electronic equipment or electrical equipment applications, for example, a metal foil containing copper or copper alloy, stainless steel or an alloy thereof, nickel or nickel alloy (including 42 alloy), aluminum or aluminum alloy may be used.
In general, a copper foil such as a rolled copper foil or an electrolytic copper foil is often used for a flexible metal foil laminate, and the present invention can be preferably used. The surface of the metal foil may be coated with a rust preventive layer, a heat resistant layer, or an adhesive layer.
In the present invention, the thickness of the metal foil is not particularly limited as long as it can exert a sufficient function according to the application.
The flexible metal foil laminate of the present invention may be a structure in which a metal foil is laminated on one surface of the polyimide film, or a structure in which an adhesive layer containing thermoplastic polyimide is attached to one surface of the polyimide film and the metal foil is laminated in a state in which the metal foil is attached to the adhesive layer.
The invention also provides an electronic component comprising the flexible metal foil laminate as an electrical signal transmission circuit. The above-mentioned electric signal transmission circuit may be an electronic component that performs signal transmission at a high frequency of at least 2GHz, specifically at a high frequency of at least 5GHz, more specifically at a high frequency of at least 10 GHz.
The electronic component may be, for example, a communication circuit for a portable terminal, a communication circuit for a computer, or a communication circuit for a spacecraft, but is not limited thereto.
Description of the embodiments
Hereinafter, the operation and effects of the invention will be described in more detail by means of specific examples of the invention. These examples are provided only as illustrations of the invention and the scope of the claims of the invention is not limited thereto.
< Production example >
In a 500ml reactor equipped with a stirrer and a nitrogen gas injection/discharge tube, DMF was charged while nitrogen gas was injected, and after the temperature of the reactor was set to 30 ℃, m-tolidine and p-phenylenediamine as diamine components and benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and pyromellitic dianhydride as acid dianhydride components were charged, and complete dissolution was confirmed.
The content of m-tolidine was 34 mol% based on 100 mol% of the total diamine component, the content of p-phenylenediamine was 66 mol%, the content of benzophenone tetracarboxylic dianhydride was 33 mol% based on 100 mol% of the total acid dianhydride component, the content of biphenyl tetracarboxylic dianhydride was 32 mol%, and the content of pyromellitic dianhydride was 35 mol%.
Thereafter, the temperature of the reactor was heated to 40 ℃ under a nitrogen atmosphere while stirring was continued for 120 minutes to produce polyamic acid.
The graphene nanoplatelets were added to the polyamic acid thus produced, followed by stirring.
The final polyamic acid thus produced was coated on a glass substrate by a spin coater after removing bubbles by a high-speed rotation of 1,500rpm or more by adding a catalyst and a dehydrating agent.
Then, a gel film was manufactured by drying at a temperature of 120 ℃ for 30 minutes under a nitrogen atmosphere, heating to 450 ℃ at a rate of 2 ℃/min, and after heat treatment at 450 ℃ for 60 minutes, cooling again to 30 ℃ at a rate of 2 ℃/min, thereby obtaining a final polyimide film, which was then immersed (dipping) in distilled water to peel it from a glass substrate.
The thickness of the polyimide film produced was 15. Mu.m. The thickness of the polyimide film produced was measured using a film thickness measuring instrument (ELECTRIC FILM THICKNESS TESTER) from Anritsu (Anritsu).
< Examples 1 and 2 and comparative examples 1 to 5>
When the graphene nanoplatelets were produced by the production examples described above, the content of the graphene nanoplatelets was adjusted as shown in table 1.
TABLE 1
Experimental example permittivity and dielectric loss factor evaluation
As shown in table 1 above, dielectric constants and dielectric loss factors were measured for the polyimide films manufactured in examples 1 and 2 and comparative examples 1 to 5, respectively.
(1) Dielectric constant measurement
The dielectric constant (Dk) is a dielectric constant at 10GHz measured using SPDR measuring instrument from De technology (Keysight).
(2) Dielectric loss factor measurement
Dielectric loss factor (Df) was measured using an impedance meter Agilent 4294A and leaving the flexible metal foil laminate for 72 hours.
As shown in table 1, the polyimide film manufactured according to the examples of the present invention satisfies all conditions that the dielectric constant is 4.0 to 7.0, and the dielectric loss tangent is 0.01.
The dielectric constant of the polyimide films of comparative examples 1 and 2 containing no graphene nanoplatelets or a small amount (0.1 wt%) thereof was less than 4.0.
In addition, the dielectric constants of comparative examples 3 to 5 including graphene nanoplatelets in excess (3 wt% or more) were more than 7.0, and in particular, the dielectric loss factors of comparative examples 4 and 5 were also more than 0.01.
Therefore, it was confirmed that the dielectric constant and the dielectric loss tangent were at desired levels only within the content range of the graphene nanoplatelets of the examples.
The results are achieved by the specific components and composition ratios in the present application, and it is understood that the content of each component plays a decisive role.
On the other hand, it is expected that the polyimide films of comparative examples 1 and 2 having different compositions from the examples are difficult to be used for electronic parts for signal transmission at high frequencies of giga units due to any one or more of the dielectric constant and the dielectric loss tangent, as compared with the polyimide films of the examples.
While the present invention has been described with reference to the embodiments thereof, those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above description.
Industrial applicability
As described above, the polyimide film having excellent dielectric characteristics is provided by the polyimide film formed with a specific composition and a specific composition ratio and the method for producing the same, and thus the present invention can be effectively applied to various fields requiring these characteristics, in particular, electronic components such as flexible metal foil laminated boards.

Claims (11)

1. A polyimide film obtained by imidizing a polyamic acid solution containing an acid dianhydride component and a diamine component, and containing 0.5 to 2.5 wt% of graphene nanoplatelets,
The acid dianhydride component comprises diphenyl ketone tetracarboxylic dianhydride BTDA, diphenyl ketone tetracarboxylic dianhydride BPDA and pyromellitic dianhydride PMDA, and the diamine component comprises m-toluidine and p-phenylenediamine PPD.
2. The polyimide film according to claim 1, wherein the content of m-toluidine is 20 to 40 mol% and the content of p-phenylenediamine is 60 to 80 mol% based on 100 mol% of the total diamine component.
3. The polyimide film according to claim 1, wherein the content of benzophenone tetracarboxylic dianhydride is 20 to 45 mol% based on 100 mol% of the total content of the acid dianhydride component, the content of biphenyl tetracarboxylic dianhydride is 20 to 45 mol% based on 20 to 45 mol% of the total content of the acid dianhydride component, and the content of pyromellitic dianhydride is 20 to 45 mol% based on 20 mol% of the total content of the acid dianhydride component.
4. The polyimide film according to claim 1, wherein the graphene nanoplatelets have an average thickness of 6 to 8nm, an average particle size of 5 to 25 μm, and a specific surface area of 120 to 150m 2/g.
5. The polyimide film according to claim 1, which has a dielectric constant of 4.0 to 7.0, and a dielectric loss tangent of 0.01.
6. A method for producing a polyimide film, comprising:
(a) A step of polymerizing an acid dianhydride component including benzophenone tetracarboxylic dianhydride BTDA, biphenyl tetracarboxylic dianhydride BPDA, and pyromellitic dianhydride PMDA with a diamine component composed of m-tolidine and p-phenylenediamine PPD in an organic solvent to produce a polyamic acid;
(b) Adding graphene nanoplatelets into the polyamic acid and mixing; and
(C) And imidizing the polyamic acid including the graphene nanoplatelets.
7. The method for producing a polyimide film according to claim 6, wherein the content of m-toluidine is 20 to 40 mol% based on 100 mol% of the total diamine component, the content of p-phenylenediamine is 60 to 80 mol%,
The content of benzophenone tetracarboxylic dianhydride is 20 to 45 mol% inclusive, the content of biphenyl tetracarboxylic dianhydride is 20 to 45 mol% inclusive, and the content of pyromellitic dianhydride is 20 to 45 mol% inclusive, based on 100 mol% of the total content of the acid dianhydride components.
8. The method for producing a polyimide film according to claim 6, wherein the polyimide film has a dielectric constant of 4.0 to 7.0 and a dielectric loss tangent of 0.01.
9. A multilayer film comprising the polyimide film of any one of claims 1 to 5.
10. A flexible metal foil laminate comprising the polyimide film of any one of claims 1 to 5 and a conductive metal foil.
11. An electronic component comprising the flexible metal foil laminate of claim 10.
CN202280063233.9A 2021-09-30 2022-09-29 Polyimide film containing graphene nanoplatelets and method for producing same Pending CN118043383A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR10-2021-0129373 2021-09-30
KR1020210129373A KR102606060B1 (en) 2021-09-30 2021-09-30 Polyimide film comprising gpaphene platelets and manufacturing method thereof
PCT/KR2022/014667 WO2023055131A1 (en) 2021-09-30 2022-09-29 Polyimide film comprising graphene nanoplatelets and method for manufacturing same

Publications (1)

Publication Number Publication Date
CN118043383A true CN118043383A (en) 2024-05-14

Family

ID=85783252

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280063233.9A Pending CN118043383A (en) 2021-09-30 2022-09-29 Polyimide film containing graphene nanoplatelets and method for producing same

Country Status (3)

Country Link
KR (1) KR102606060B1 (en)
CN (1) CN118043383A (en)
WO (1) WO2023055131A1 (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101311458B1 (en) * 2011-06-21 2013-09-25 동의대학교 산학협력단 polyimide-graphene Composite material and method of producing the same
KR101271606B1 (en) * 2011-08-10 2013-06-11 동의대학교 산학협력단 Method of producing polyimide-graphene composite material
KR101769101B1 (en) 2013-12-13 2017-08-30 주식회사 엘지화학 Poly-imide resin with low dielectric constant and flexible metal laminate using the same
KR102239605B1 (en) * 2014-12-23 2021-04-12 주식회사 두산 Double-sided flexible metallic laminate and method thereof
KR101748612B1 (en) * 2015-09-15 2017-06-21 한국화학연구원 Dielectric composition and electronic device including the same
KR20190067600A (en) * 2017-12-07 2019-06-17 에스케이씨코오롱피아이 주식회사 Polyimide Film Having Low Dielectric Constant And High Thermal Conductivity
KR102284431B1 (en) * 2018-11-07 2021-08-03 피아이첨단소재 주식회사 Polyimide Composite Film with Superior Performance for Dielectric Property and Method for Preparing the Same
KR102347588B1 (en) * 2019-11-07 2022-01-10 피아이첨단소재 주식회사 High Heat Resistant and Low Dielectric Polyimide Film and Manufacturing Method Thereof

Also Published As

Publication number Publication date
WO2023055131A1 (en) 2023-04-06
KR20230046415A (en) 2023-04-06
KR102606060B1 (en) 2023-11-29

Similar Documents

Publication Publication Date Title
CN114651035B (en) Polyimide film with high heat resistance and low dielectric property and preparation method thereof
CN114616271B (en) Polyimide film with improved dielectric properties and preparation method thereof
CN114729136B (en) Low dielectric polyimide film and method for producing same
TWI823032B (en) Polyimide film, method of producing the same, and multilayer film, flexible metal foil laminate and electronic component containing the same
CN116194512A (en) Low dielectric polyimide film and method for producing same
CN118043383A (en) Polyimide film containing graphene nanoplatelets and method for producing same
TWI810713B (en) Polyimide film, method of producing the same, multilayer film, flexible metal foil clad laminate and electronic component containing the same
KR102475605B1 (en) Low dielectric polyamic acid comprising liquid crystal powders, polyimide film and manufacturing method thereof
KR102447652B1 (en) Polyimide film with improved dielectric properties and manufacturing method thereof
CN114729135B (en) High-adhesion low-dielectric polyimide film and method for producing same
CN117580897A (en) Semitransparent low dielectric polyimide film and method for producing same
KR20230075343A (en) POLYIMIDE PRECURSOR COMPOSITION AND Polyimide Film INCLUDING THE SAME
KR20230075240A (en) Polyamic acid, polyimide film and flexible metal clad laminate using the same
TW202330728A (en) Polyimide precursor composition, polyimide film, multilayer film, flexible metal clad laminate and electronic parts including the same
CN116490545A (en) Polyimide film having high dimensional stability and method for producing same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination