CN118339024A - Polyimide film having multilayer structure and method for producing same - Google Patents

Polyimide film having multilayer structure and method for producing same Download PDF

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Publication number
CN118339024A
CN118339024A CN202280078706.2A CN202280078706A CN118339024A CN 118339024 A CN118339024 A CN 118339024A CN 202280078706 A CN202280078706 A CN 202280078706A CN 118339024 A CN118339024 A CN 118339024A
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mol
polyimide film
dianhydride
content
multilayer polyimide
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Inventor
柳大建
金烔暎
元东荣
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Polyimide Advanced Materials Co ltd
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Polyimide Advanced Materials Co ltd
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Priority claimed from KR1020210166834A external-priority patent/KR102682573B1/en
Application filed by Polyimide Advanced Materials Co ltd filed Critical Polyimide Advanced Materials Co ltd
Publication of CN118339024A publication Critical patent/CN118339024A/en
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    • 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
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The present invention provides a multilayer polyimide film which comprises a first skin layer and a second skin layer formed on one outer surface of a core layer and on the opposite surface of the outer surface, respectively, and has an adhesion force with a copper foil of 0.8kgf/cm or more, and a method for producing the same.

Description

Polyimide film having multilayer structure and method for producing same
Technical Field
The present invention relates to a multilayer polyimide film having excellent dimensional stability and excellent adhesion, and more particularly, to a multilayer polyimide film having high thermal dimensional stability and moisture dimensional stability and excellent adhesion, and a method for producing 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 having a rigid aromatic main chain and excellent chemical stability.
Polyimide films have been attracting attention as materials for various electronic devices requiring the above characteristics.
As an example of a microelectronic device to which a polyimide film is applied, a thin circuit board having high and gentle circuit integration in order to cope with weight reduction and miniaturization of electronic products is given, and polyimide films are particularly widely used as insulating films of thin circuit boards.
The thin circuit board is generally configured such that a circuit including a metal foil is formed on an insulating film, and such a thin circuit board is broadly referred to as a Flexible metal foil laminate (Flexible Metal Foil CLAD LAMINATE), and when a thin Copper plate is used as a metal foil, it is also referred to as a Flexible Copper foil laminate (FCCL) in a narrow sense.
As a method for producing the flexible metal foil laminate, for example, there can be mentioned: (i) A casting method of performing imidization after casting (casting) or coating polyamic acid as a precursor of polyimide on a metal foil; (ii) A metallization method in which a metal layer is directly provided on a polyimide film by Sputtering (Sputtering); and (iii) a lamination method of bonding a polyimide film to a metal foil by thermoplastic polyimide and using heat and pressure.
In particular, the metallization method is a method of producing a flexible metal foil laminate by sputtering a metal such as copper on a polyimide film having a thickness of 20 to 38 μm and sequentially vapor depositing a bonding (Tie) layer and a Seed (Seed) layer, and is useful for forming an ultrafine circuit having a pitch (pitch) of 35 μm or less, and is widely used for producing a flexible metal foil laminate for Chip On Film (COF).
Polyimide films used in flexible metal foil laminates using metallization must have high dimensional stability. In general, dimensional stability is measured by thermal dimensional stability expressed by a coefficient of thermal expansion, but moisture dimensional stability expressed by a coefficient of hygroscopic expansion is becoming more and more important as thermal dimensional stability.
That is, although there is an increasing demand for polyimide films having excellent thermal dimensional stability and moisture dimensional stability, when polyimide films having a structure having a low thermal expansion coefficient and high thermal dimensional stability are actually designed, there is a problem that the moisture dimensional stability is lowered.
In addition, polyimide films having high dimensional stability generally have a problem of reduced adhesion to sputtered metal plating.
Therefore, there is an urgent need for a polyimide film having not only high thermal dimensional stability and high moisture dimensional stability but also excellent adhesion.
The matters described in the foregoing background art are for aiding in the understanding of the background of the invention and may include matters not prior art known to those of ordinary skill in the art.
Prior art literature
Patent literature
Patent document 1: korean laid-open patent publication No. 10-2012-0136807
Disclosure of Invention
Technical problem
The present invention provides a polyimide multilayer film having both high thermal dimensional stability and high moisture dimensional stability, and excellent adhesion.
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.
Means for solving the problems
In order to achieve the above object, an aspect of the present invention provides a multi-layered polyimide film comprising a first skin layer and a second skin layer formed on one outer surface of a core layer and opposite surfaces of the outer surface,
The adhesion to the copper foil is 0.8kgf/cm or more.
Another aspect of the present invention provides a flexible metal foil laminate comprising the above multilayer polyimide film and a conductive metal foil.
Still another aspect of the present invention provides an electronic component comprising the flexible metal foil laminate described above.
Effects of the invention
The present invention provides a polyimide film having excellent thermal dimensional stability, moisture dimensional stability and adhesion by providing a polyimide film having a composition ratio, a reaction ratio and the like of acid dianhydride and diamine components adjusted.
Such polyimide films can be applied to various fields requiring polyimide films having excellent dimensional stability and adhesion, for example, flexible metal foil laminates manufactured by a metallization method or electronic parts including such flexible metal foil laminates.
Detailed Description
The terms or words used in the present specification and claims should not be construed as being limited to meanings in general or dictionary, but should be construed in terms of meanings and concepts conforming to the technical ideas of the present invention only on the basis that the inventors can properly define concepts of terms to explain the principles of 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 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, 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.
The multilayered polyimide film according to an embodiment of the present invention may include a first skin layer and a second skin layer formed on one outer surface of the core layer and an opposite surface of the outer surface, respectively, and may have an adhesion force with a copper foil of 0.8kgf/cm or more.
That is, the multilayer polyimide film may have a three-layer structure in which a first skin layer and a second skin layer are formed on one outer surface of a core layer and an opposite surface of the outer surface, respectively, with the core layer as a center.
In another aspect, the composition and composition ratio of the first skin layer and the second skin layer may be the same or different.
In addition, the thicknesses of the first skin layer and the second skin layer may be the same or different.
The copper foil may be formed on one or more surfaces of the multilayer polyimide film of the present application by sputtering (dispenser) -plating.
In one embodiment, the multilayer polyimide film may have a coefficient of thermal expansion in the width direction (Traverse direction, TD) of 2.0 ppm/DEG C or more and 6.0 ppm/DEG C or less, and a coefficient of hygroscopic expansion in the width direction (Traverse direction, TD) of 3.0ppm/RH% or more and 6.0ppm/RH% or less.
The coefficient of thermal expansion in the width direction (Traverse direction, TD) may be, for example, 2.5 ppm/DEG C or more and 6.0 ppm/DEG C or less.
The coefficient of hygroscopic expansion in the widthwise direction (Traverse direction, TD) may be, for example, 4.5ppm/RH% or more and 6.0ppm/RH% or less.
In one embodiment, the core layer of the multilayer polyimide film may be obtained by imidizing a polyamic acid solution containing an acid dianhydride component including diphenyl tetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) and a diamine component including p-phenylene diamine (PPD) and m-tolidine (m-tolidine).
On the other hand, any one or more of the first skin layer and the second skin layer may be obtained by imidizing a polyamic acid solution containing an acid dianhydride component and a diamine component, wherein the acid dianhydride component contains two or more of the group consisting of biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, oxydiphthalic anhydride (ODPA) and Benzophenone Tetracarboxylic Dianhydride (BTDA), and the diamine component contains any one or more of the group consisting of diaminodiphenyl ether (ODA) and 1, 3-diaminophenoxybenzene (TPE-R).
For example, any one or more of the first skin layer and the second skin layer may use biphenyl tetracarboxylic dianhydride and pyromellitic dianhydride simultaneously, or use biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride and oxydiphthalic anhydride simultaneously, or use biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride simultaneously as acid dianhydride components.
In addition, for example, any one or more of the first skin layer and the second skin layer may use only diaminodiphenyl ether, or may use diaminodiphenyl ether and 1, 3-diaminophenoxy benzene simultaneously as diamine components.
In one embodiment, in the core layer, the content of the biphenyltetracarboxylic acid dianhydride may be 40 to 60 mol% based on 100 mol% of the total content of the acid dianhydride component, the content of the pyromellitic acid dianhydride may be 40 to 60 mol% based on 100 mol% of the total content of the diamine component, the content of the p-phenylenediamine may be 50 to 70 mol% based on 100 mol% of the total content of the diamine component, and the content of the m-toluidine may be 30 to 50 mol% based on 100 mol% of the total content of the diamine component.
In one embodiment, in any one or more of the first skin layer and the second skin layer, the content of the biphenyl tetracarboxylic dianhydride may be 15 mol% or more and 85 mol% or less, the content of the pyromellitic dianhydride may be 15 mol% or more and 60 mol% or less, the content of the oxydiphthalic anhydride may be 35 mol% or less, the content of the benzophenone tetracarboxylic dianhydride may be 35 mol% or less, the content of the diaminodiphenyl ether may be 20 mol% or more and 100 mol% or less, and the content of the 1, 3-diaminophenoxy benzene may be 80 mol% or less, based on 100 mol% of the total content of the diamine component.
The p-phenylenediamine is a rigid monomer, and the synthesized polyimide has a more linear structure along with the increase of the content of the p-phenylenediamine, so that the mechanical properties of the polyimide are improved.
In addition, m-toluidine contributes to low moisture absorption characteristics of polyimide films related to moisture dimensional stability, particularly because it has a methyl group that is hydrophobic.
The polyimide chain derived from biphenyl tetracarboxylic dianhydride of the present invention has 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 adjacent to each other, and intermolecular interactions (intermolecular interaction) are enhanced.
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 hygroscopicity of the polyimide film that affects the dimensional stability of moisture.
In addition, pyromellitic dianhydride is an acid dianhydride component having a relatively rigid structure, and is preferable in that it can impart moderate elasticity to the polyimide film.
The content ratio of the acid dianhydride is important for providing the polyimide film with excellent dimensional stability. For example, as the content ratio of biphenyltetracarboxylic dianhydride decreases, it is difficult to expect a low moisture absorption rate due to the CTC structure, and the dimensional stability of moisture also decreases.
In addition, the biphenyl tetracarboxylic dianhydride contains 2 benzene rings corresponding to the aromatic moiety, and the pyromellitic dianhydride contains 1 benzene ring corresponding to the aromatic moiety.
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.
That is, an increase in the content of pyromellitic dianhydride is considered to be a relative increase in the imide groups of the polyimide film as a whole, and therefore, it is difficult to expect high moisture dimensional stability due to a low moisture absorption rate.
In contrast, if the content ratio of pyromellitic dianhydride is reduced, the composition of the rigid structure is relatively reduced, and the elasticity of the polyimide film can be reduced below a desired level.
For this reason, when the content of the biphenyl tetracarboxylic dianhydride is higher than the above range or the content of the pyromellitic dianhydride is lower than the above range, the dimensional stability of the polyimide film is lowered.
In contrast, when the content of the biphenyl tetracarboxylic dianhydride is lower than the above range or when the content of the pyromellitic dianhydride is higher than the above range, the dimensional stability of the polyimide film is adversely affected.
In the present invention, the polyamic acid can be produced by, for example, 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 comprising adding the entire acid dianhydride component to a solvent, and then adding a diamine component 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 the diamine component and the acid dianhydride component are polymerized so as to be substantially equimolar;
(4) A method in which a part of the diamine compound is mixed at a ratio of about 95 to 105 mol% with respect to the reaction component 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 the diamine component and the acid dianhydride component are polymerized so as to be 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 the whole diamine component used in their reactions is polymerized so as to be in substantially equimolar relation to the acid dianhydride component; etc.
In the present invention, the polymerization method of the polyamic acid as described above can be defined by a random (random) polymerization method, and a polyimide film produced from the polyamic acid of the present invention produced by the process as described above can be preferably used in terms of maximizing the effect of the present invention of improving dimensional stability and chemical resistance.
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. Accordingly, 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 organic 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 may be used alone or in combination as needed.
In one example, the above organic 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, but 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 to be 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 not easily 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 according to the film properties to be modified, the filler particle diameter, 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 the filler is less than the above range, the modifying effect by the filler is not easily exhibited, and if it exceeds 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 or an infrared dryer, excluding a chemical catalyst.
In the thermal imidization method, the gel film may be heat-treated at a variable temperature ranging from 100 to 600 ℃ to imidize the amide groups present in the gel film, and in detail, may be heat-treated at 200 to 500 ℃, and in more detail, may be heat-treated at 300 to 500 ℃ to imidize the amide groups present in the gel film.
However, some of the amic acid (about 0.1 mole% to 10 mole%) may also undergo imidization during the formation of the gel film, and for this purpose, 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 process 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.
On the other hand, the multilayer polyimide film of the present invention described so far can be produced by any one or more of coextrusion and coating.
The coextrusion method is a method in which a polyimide film having a multilayer structure is produced by filling a tank with a polyamic acid solution or a polyimide resin produced by imidizing the polyamic acid solution, then subjecting the resulting product to multilayer extrusion on a casting belt using a coextrusion die, and then curing the resulting product.
For example, the method for producing a multilayer polyimide film of the present invention can be carried out by comprising the steps of: a first filling step of filling a first tank with a first polyamic acid solution or a first polyimide resin produced by imidizing the first polyamic acid solution, that is, a first solution; a second filling step of filling a second tank with a second polyamic acid solution or a second polyimide resin produced by imidizing the second polyamic acid solution, that is, a second solution; a coextrusion step of coextruding the first solution and the second solution through a coextrusion die formed inside each of a first flow path connected to the first reservoir, a second flow path connected to the second reservoir, and a third flow path; and a curing step of curing the first solution and the second solution obtained by the coextrusion.
The first polyamic acid solution is intended to form a core layer, and is preferably produced by polymerizing an acid dianhydride component including diphenyl tetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) and a diamine component including p-phenylene diamine (PPD) and m-tolidine (m-tolidine).
The second polyamic acid solution is preferably produced by polymerizing an acid dianhydride component including two or more selected from the group consisting of diphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, oxydiphthalic anhydride (ODPA) and Benzophenone Tetracarboxylic Dianhydride (BTDA), and a diamine component including any one or more selected from the group consisting of diaminodiphenyl ether (ODA) and 1, 3-diaminophenoxybenzene (TPE-R), for forming the first skin layer and the second skin layer.
On the other hand, in the case of using the first polyamic acid solution as the first solution and using the second polyamic acid solution as the second solution, it is preferable that the method further comprises an imidization step of imidizing the first solution and the second solution which are co-extruded before the curing step.
The present invention provides a flexible metal foil laminate comprising the above-described multilayer polyimide film and a conductive metal foil.
The metal foil to be used is not particularly limited, but 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 have a structure in which a metal foil is laminated on at least one surface of the multilayered polyimide film.
Description of the embodiments
Hereinafter, the operation and effects of the present invention will be described in more detail by means of specific production examples and examples of the present invention. These examples and embodiments are provided only as illustrations of the invention and the scope of the invention is not limited thereto.
Manufacturing example: production of multilayer polyimide film
The first polyamic acid solution for manufacturing the core layer is manufactured by selecting and polymerizing acid dianhydride and diamine components among diphenyl tetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), oxydiphthalic anhydride (ODPA), benzophenone Tetracarboxylic Dianhydride (BTDA), p-phenylenediamine (PPD), m-tolidine, MTD), 1, 3-diaminophenoxybenzene (TPE-R), and diaminodiphenyl ether (ODA).
The acid dianhydride and diamine components are selected from biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, oxydiphthalic anhydride, benzophenone tetracarboxylic dianhydride, p-phenylenediamine, m-tolidine, 1, 3-diaminophenoxybenzene and diaminodiphenyl ether and subjected to polymerization, thereby producing a second polyamic acid solution for producing the first and second skin layers.
The first polyamic acid solution and the second polyamic acid solution produced as described above are co-extruded by a co-extrusion method, imidized, and then cured to produce a multilayer polyimide film having a first skin layer and a second skin layer formed around a core layer.
Wherein the core layer is produced by coextruding a first polyamic acid solution, and the first skin layer and the second skin layer are produced by coextruding a second polyamic acid solution.
In the production of the polyamic acid, the solvent is generally an amide-based solvent, and an aprotic polar solvent (Aprotic solvent), for example, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, or a combination thereof may be used.
The acid dianhydride and the diamine component may be added in the form of powder, block, or solution, and it is preferable to add the acid dianhydride and the diamine component in the form of powder at the initial stage of the reaction to perform the reaction, and then add the acid dianhydride and the diamine component in the form of solution to adjust the polymerization viscosity.
The polyamic acid solution obtained may be mixed with an imidization catalyst and a dehydrating agent and applied to a support.
Examples of the catalyst to be used include tertiary amines (e.g., isoquinoline, β -picoline, pyridine, etc.), and examples of the dehydrating agent include acid anhydrides, but are not limited thereto.
Examples and comparative examples
As shown in table 1 below (composition and composition ratio of core layer) and table 2 below (composition and composition ratio of skin layer), the contents of the acid dianhydride component and the above diamine component of the core layer and the skin layer in examples 1 to 6 and comparative examples 1 to 9 were adjusted, and a multilayer polyimide film was produced according to the production example.
The first skin layer and the second skin layer of examples 1 to 6 and comparative example 9 were made to have the same composition and composition ratio, and the thicknesses were also made to be the same.
However, comparative examples 1 to 8 were single-layer polyimide films, and only core layers were produced.
TABLE 1
TABLE 2
The coefficient of thermal expansion (coefficient of thermal expansion, CTE) in the width direction, the coefficient of hygroscopic expansion (coefficient of hydroscopic expansion, CHE) in the width direction, and the adhesion of the polyimide film produced were measured and are shown in table 3 below.
TABLE 3
(1) Measurement of thermal expansion coefficient
The Coefficient of Thermal Expansion (CTE) is determined as follows: the multilayer polyimide film thus produced was cut into a sheet having a width of 4mm and a length of 20mm using a thermo-mechanical analyzer (thermomechanical analyzer) model Q400 from TA company, and then heated from 30℃to 400℃at a rate of 10℃per minute while applying a tension of 0.05N under a nitrogen atmosphere, and then cooled again at a rate of 10℃per minute, and then the slope in the range of 50℃to 200℃was measured.
(2) Determination of the coefficient of hygroscopic expansion
The Coefficient of Hygroscopic Expansion (CHE) was determined as follows: the dimensional change rate was measured by adjusting the humidity to 3% RH at 25℃until the film was completely saturated and measuring the dimensions, adjusting the humidity to 90% RH, and similarly, measuring the dimensions after saturated and hygroscopic, with the minimum load applied to the produced multilayer polyimide film (about 1g for a 25 mm. Times.150 mm sample) so as not to loosen.
(3) Adhesive force measurement
A flexible metal foil laminate for COF was produced by vapor-depositing a copper thin film layer having a thickness of about 80 to 300nm as a copper seed layer for a plating electrode on the produced multilayer polyimide film by sputtering, and then forming a copper conductive layer having a thickness of about 8 to 9 μm by electroplating.
The flexible metal foil laminate was etched into a bar shape having a width of 2mm by a wet etching method, and then subjected to a 90 ° peel test by a Universal tester (Universal TESTING MACHINE), and stretched at a speed of 20mm/min to measure the adhesion.
The measurement results showed the following characteristics: the multilayer polyimide films of examples 1 to 6 have a coefficient of thermal expansion in the width direction of 2.0 ppm/DEG C or more and 6.0 ppm/DEG C or less, a coefficient of hygroscopic expansion in the width direction of 3.0ppm/RH% or more and 6.0ppm/RH% or less, and an adhesion to a copper foil of 0.8kgf/cm or more.
In contrast, any one or more of the characteristics of the thermal expansion coefficient, the hygroscopic expansion coefficient, and the adhesion to copper foil of the polyimide films of comparative examples 1 to 8, which are different in composition and/or layer-by-layer ratio from the examples and are composed of only 1 layer, and the multilayered polyimide film of comparative example 9, cannot satisfy the characteristics required for the multilayered polyimide film of the present application.
Therefore, it was confirmed that the multilayer polyimide films of examples 1 to 6 produced within the appropriate range of the present application were excellent in thermal dimensional stability, moisture dimensional stability and adhesion to copper foil, but the thermal dimensional stability, moisture dimensional stability and adhesion to copper foil of the multilayer polyimide films of the present application could not all be satisfied when they were out of the appropriate range of the present application.
That is, it can be confirmed that a multilayer polyimide film which fully satisfies various conditions applicable to the application field while having excellent dimensional stability and adhesion to copper foil is a multilayer polyimide film manufactured within an appropriate range of the present application.
The embodiments of the multilayer polyimide film and the method for producing a multilayer polyimide film of the present invention are merely preferred embodiments that enable a person skilled in the art to which the present invention pertains to easily practice the present invention, and are not limited to the above embodiments, and therefore do not limit the scope of the claims of the present invention. Therefore, the true technical scope of the present invention is defined by the technical ideas of the scope of the appended claims. It will be apparent to those skilled in the art that various substitutions, modifications and changes can be made without departing from the technical spirit of the present invention, and it is needless to say that the portions that can be easily changed by those skilled in the art are also within the scope of the claims of the present invention.
Industrial applicability
The present invention provides a polyimide film having excellent thermal dimensional stability, moisture dimensional stability and adhesion by providing a polyimide film having a composition ratio, a reaction ratio and the like of acid dianhydride and diamine components adjusted.
Such polyimide films can be applied to various fields requiring polyimide films having excellent dimensional stability and adhesion, for example, flexible metal foil laminates manufactured by a metallization method or electronic parts including such flexible metal foil laminates.

Claims (9)

1. A multilayer polyimide film comprising a first skin layer and a second skin layer formed on one outer surface of a core layer and on opposite surfaces of the outer surface, respectively,
The adhesion force between the multilayer polyimide film and the copper foil is more than 0.8 kgf/cm.
2. The multilayer polyimide film according to claim 1, which has a coefficient of thermal expansion in the widthwise direction TD of 2.0 ppm/DEG C or more and 6.0 ppm/DEG C or less,
The coefficient of hygroscopic expansion in the widthwise direction TD is 3.0ppm/RH% or more and 6.0ppm/RH% or less.
3. The multilayer polyimide film according to claim 1, wherein the core layer is obtained by imidizing a polyamic acid solution comprising an acid dianhydride component and a diamine component,
Wherein the acid dianhydride component comprises diphenyl tetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA), and the diamine component comprises p-phenylenediamine (PPD) and m-toluidine.
4. The multilayer polyimide film according to claim 1, wherein any one or more selected from the group consisting of the first skin layer and the second skin layer is obtained by imidizing a polyamic acid solution comprising an acid dianhydride component and a diamine component,
Wherein the acid dianhydride component comprises two or more selected from the group consisting of diphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, oxydiphthalic anhydride ODPA and benzophenone tetracarboxylic dianhydride BTDA, and the diamine component comprises any one or more selected from the group consisting of diaminodiphenyl ether ODA and 1, 3-diaminophenoxy benzene TPE-R.
5. The multilayer polyimide film according to claim 3, wherein the content of biphenyl tetracarboxylic dianhydride is 40 mol% or more and 60 mol% or less, the content of pyromellitic dianhydride is 40 mol% or more and 60 mol% or less, based on 100 mol% of the total content of the acid dianhydride component,
The content of p-phenylenediamine is 50 to 70 mol% and the content of m-toluidine is 30 to 50 mol%, based on 100 mol% of the total diamine component.
6. The multilayer polyimide film according to claim 4, wherein the content of biphenyl tetracarboxylic dianhydride is 15 mol% or more and 85 mol% or less, the content of pyromellitic dianhydride is 15 mol% or more and 60 mol% or less, the content of oxydiphthalic anhydride is 35 mol% or less, the content of benzophenone tetracarboxylic dianhydride is 35 mol% or less, based on 100 mol% of the total content of the acid dianhydride components,
The diaminodiphenyl ether is contained in an amount of 20 to 100 mol% and the 1, 3-diaminophenoxy benzene is contained in an amount of 80 mol% inclusive, based on 100 mol% of the total diamine component.
7. The multilayer polyimide film according to any one of claims 1 to 6, which is manufactured by any one or more selected from the group consisting of coextrusion and coating.
8. A flexible metal foil laminate comprising the multilayer polyimide film of any one of claims 1 to 6 and a conductive metal foil.
9. An electronic component comprising the flexible metal foil laminate of claim 8.
CN202280078706.2A 2021-11-29 2022-11-28 Polyimide film having multilayer structure and method for producing same Pending CN118339024A (en)

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