WO2019194386A1 - Film de polyimide permettant de préparer un stratifié plaqué d'une feuille métallique souple et stratifié plaqué d'une feuille métallique souple comprenant celui-ci - Google Patents

Film de polyimide permettant de préparer un stratifié plaqué d'une feuille métallique souple et stratifié plaqué d'une feuille métallique souple comprenant celui-ci Download PDF

Info

Publication number
WO2019194386A1
WO2019194386A1 PCT/KR2018/014616 KR2018014616W WO2019194386A1 WO 2019194386 A1 WO2019194386 A1 WO 2019194386A1 KR 2018014616 W KR2018014616 W KR 2018014616W WO 2019194386 A1 WO2019194386 A1 WO 2019194386A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyimide film
diamine
polyimide
metal foil
polyamic acid
Prior art date
Application number
PCT/KR2018/014616
Other languages
English (en)
Korean (ko)
Inventor
백승열
이길남
최정열
Original Assignee
에스케이씨코오롱피아이 주식회사
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 에스케이씨코오롱피아이 주식회사 filed Critical 에스케이씨코오롱피아이 주식회사
Priority to CN201880091990.0A priority Critical patent/CN111918907B/zh
Publication of WO2019194386A1 publication Critical patent/WO2019194386A1/fr

Links

Classifications

    • 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
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

Definitions

  • the present invention relates to a polyimide film for producing a flexible metal laminate and a flexible metal laminate comprising the same.
  • Polyimide (PI) is a polymer 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 high chemical stability with a rigid aromatic backbone. Material.
  • polyimide is in the spotlight as an insulating material for microelectronic components in which the above characteristics are strongly required.
  • microelectronic component examples include a thin circuit board having a high degree of circuit integration and a flexible circuit board to cope with light weight and miniaturization of electronic products.
  • the polyimide is widely used as an insulating film of a thin circuit board.
  • a thin circuit board generally has a structure in which a circuit including a metal foil is formed on a polyimide film, and such a thin circuit board is also referred to as a flexible metal foil clad laminate in a broad sense.
  • an insulator having a high impedance capable of maintaining electrical insulation even at high frequencies is required.
  • the dielectric constant should be as low as possible to maintain insulation at high frequencies.
  • the dielectric constant is not high enough to maintain sufficient insulation in the high frequency communication of about 3.4 to 3.6, and for example, the insulation is partially provided in the thin circuit board having the high frequency communication of 2 GHz or more. Or there is a possibility of total loss.
  • the dielectric constant of the insulator is lowered, it is possible to reduce undesirable stray capacitance and noise in the thin circuit board, and it is known that the cause of communication delay can be largely eliminated. As low as possible, the dielectric constant is considered to be the most important factor in the performance of thin circuit boards.
  • Dielectric dissipation factor (Df) refers to the degree of waste of electrical energy in thin circuit boards and is closely related to the signal propagation delays that determine the communication speed, so that the dielectric loss rate of polyimide is as low as possible. It is recognized as an important factor for the performance of the substrate.
  • a polyimide film prepared by combining a specific diamine monomer containing a nonpolar aliphatic moiety and a pyromellitic dianhydride, and imidizing the polyimide film is prepared in a polyimide polymer chain. Based on the special structure containing the nonpolar aliphatic moiety, it is possible to suppress moisture absorption which adversely affects the dielectric constant and the dielectric loss rate.
  • the flexible metal laminate comprising the polyimide film is a circuit capable of high-speed communication at a high frequency based on the relatively low dielectric constant and dielectric loss rate of the polyimide film while having a desired glass transition temperature It can be implemented as.
  • the present invention has a substantial object to provide a specific embodiment thereof.
  • a diamine monomer comprising a first diamine represented by the following formula (1) and a second diamine represented by the following formula (2);
  • polyimide film prepared by imidizing a polyamic acid derived from polymerization of pyromellitic dianhydride (PMDA), having a dielectric constant (Dk) of 3.4 or less and a dielectric loss factor (Df) of 0.005 or less. .
  • PMDA pyromellitic dianhydride
  • the dielectric loss ratio is also improved at the same time while having the desired glass transition temperature and dielectric constant, so that the insulation reliability is high even at a high frequency and signal transmission delay can be minimized.
  • a diamine monomer comprising a first diamine represented by the following formula (1) and a second diamine represented by the following formula (2);
  • It is prepared by imidating a polyamic acid derived from the polymerization of pyromellitic dianhydride (PMDA), and has a dielectric constant (Dk) of 3.4 or less and a dielectric loss ratio (Df) of 0.005 or less.
  • PMDA pyromellitic dianhydride
  • R 1 and R 2 are each independently a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group;
  • R 3 is —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, — (CH 2 ) n 1 —, or —O (CH 2 ) n 2 O—, wherein n 1 and n 2 Are each independently an integer of 1 to 10.
  • the dielectric loss factor (Df) is 0.005 or less
  • Glass transition temperature (Tg) is 320 degreeC or more.
  • the polyimide film that satisfies all the above four conditions, it can be used as an insulating film for the flexible metal laminate, and the manufactured flexible metal laminate is used as an electrical signal transmission circuit for transmitting signals at a high frequency of 2 GHz or more. Even if it is, its insulation stability can be ensured, and signal propagation delay can also be minimized.
  • the polyimide film having all four of these conditions is a novel polyimide film which has not been known so far, and the four conditions will be described in detail below.
  • Permittivity is an important characteristic value that represents the electrical properties of a dielectric (or insulator), that is, a non-conductor.
  • the permittivity is not directly representative of the electrical properties of a DC current, but is directly related to the characteristics of AC currents, especially AC electromagnetic waves. Known.
  • the + and-moment components which are normally scattered in a random direction in general, are aligned with an alternating current change of an electromagnetic field applied outside the insulator.
  • the moment components are changed in accordance with the change direction of the electromagnetic field, it is possible to enable the progress of electromagnetic waves inside even the non-conductor.
  • the degree of sensitivity and how sensitively the moment inside the material reacts can be expressed as permittivity.
  • the dielectric constant of liquid crystal polymers is known to be about 2.9 to 3.3, which is much better than an insulator compared to a conventional polyimide having most dielectric constants. can see.
  • the polyimide film according to the present invention may have a dielectric constant close to or lower than the dielectric constant of the liquid crystal polymer, specifically, a dielectric constant of 3.4 or less, specifically, 3.0 or less, and the lower limit thereof may be at least 2.8. have.
  • the capacitor has a property of lowering the impedance as the frequency of the current or voltage at both ends thereof, the value can be expressed as follows.
  • -C e * S / d; Where e is the dielectric constant, S is the area of the conductor, and d is the distance.
  • the polyimide film according to the present invention has a relatively low dielectric constant as described above, and thus is easy to maintain insulation even at a frequency in a giga (GIGA) unit, for example, communication equipment operating at a very high frequency of 10 GHz. There is an advantage.
  • GIGA giga
  • dielectric loss factor is meant the force dissipated by the dielectric (or insulator) when the friction of the molecules interferes with the molecular motion caused by the alternating electric field.
  • dielectric loss rate is commonly used as an index indicating the ease of dissipation (dielectric loss), and the higher the dielectric loss rate, the easier the charge is to be lost. Conversely, the lower the dielectric loss rate, the more difficult it is to be lost. have.
  • the dielectric loss rate is a measure of power loss. As the dielectric loss rate is lower, the signal transmission delay due to power loss is alleviated, and thus the communication speed can be maintained quickly.
  • polyimide films which are insulating films, in which the polyimide film according to the invention has a dielectric loss factor of 0.005 or less, in particular 0.004 or less, more specifically, 0.003 under a fairly high frequency of about 2 GHz. It may be:
  • a moisture absorption rate is a ratio which shows the moisture content which a material absorbs, and generally, it is known that dielectric constant and dielectric loss rate increase when moisture absorption rate is high.
  • the dielectric constant is at least 100, in the liquid state, it is about 80, and in the gaseous water vapor, it is known as 1.0059.
  • water present in the water vapor state other than the polyimide film does not substantially affect the dielectric constant and dielectric loss rate of the polyimide film.
  • the dielectric constant and dielectric loss rate of the polyimide film may change rapidly even with a small amount of moisture absorption.
  • the polyimide film according to the present invention may have a moisture absorption of 2.3% by weight or less, in detail, 2.0% by weight or less, and more specifically 1.7% by weight or less, based on the total weight of the polyimide film. It is due to the structural features of the polyimide film according to the invention.
  • non-polar part is included in the molecular structure of the polyimide film according to the present invention, and that the imide group close to hydrophilicity is occupied relatively low.
  • the glass transition temperature can be obtained from the storage modulus and loss modulus measured by the dynamic viscoelasticity measuring device (DMA), and in detail, the top peak of tan ⁇ which is the value of the calculated loss modulus divided by the storage modulus. ) Can be calculated as the glass transition temperature.
  • DMA dynamic viscoelasticity measuring device
  • the glass transition temperature is related to the heat resistance of the polyimide film, and may be higher when considering the use of the insulating film.
  • the highest level of glass transition temperature, dielectric constant, and wireline loss rate are difficult to achieve.
  • the reason is that the strong heat resistance of the polyimide film is due to the chemical stability of the imide group. It is expected to be due to a relatively weak point to moisture absorption.
  • the present invention provides a polyimide film in which both the glass transition temperature, the dielectric constant, and the streamline loss ratio are both at a desirable level.
  • the glass transition temperature of the polyimide film according to the present invention may be 320 ° C. or more.
  • the temperature may be 320 ° C or higher and 380 ° C or lower, and particularly preferably 350 ° C or higher and 370 ° C or lower.
  • the glass transition temperature is lower than the above range, when laminating, a large dimensional change may be accompanied because the viscosity of the polyimide film is relatively high. This is not preferable because it causes the appearance quality to be impaired.
  • the glass transition temperature is higher than the above range, the temperature required to soften the core layer to a level sufficient to alleviate the thermal distortion is too high, so that the existing laminate apparatus cannot sufficiently relieve thermal stress, and the dimensional change is worsened. There is a possibility.
  • the polyimide film according to the present invention can be utilized as an insulating film for a flexible metal laminate, as well as satisfying all four conditions described above, and also ensures insulation stability even at high frequencies, and delays signal transmission. Can also be minimized.
  • the dianhydride monomer, the diamine monomer and the blending ratio thereof are described in detail through the following non-limiting examples.
  • the diamine monomer may be 50 mol% or more and 80 mol% or less, and 20 mol% or more and 50 mol% or less of the first diamine, based on the total number of moles thereof. .
  • the molecular weight may be 400 g / mol to 600 g / mol, and for the first diamine, the molecular weight may be 200 g / mol to 250 g / mol.
  • the molecular weight of the polyimide polymer chain formed by imidating the polyamic acid may also increase.
  • the total molecular weight of one polyimide polymer chain increased with the content of the second diamine is such that the aromatic portion of the second diamine occupies most of the portion derived from the diamine monomer, while per second diamine molecule. Since only two amine groups are supplied, in the case of imide groups derived from the diamine, the proportion of the total molecular weight may be relatively reduced.
  • hydrophobicity improves also about the whole polyimide film, and lower moisture absorption can be expected.
  • the present invention emphasizes that it is not desirable for the second diamine to exceed 50 mol%, based on the total moles of the diamine monomer.
  • the moisture absorption rate is not preferable because it does not reach a desired level.
  • the molecular weight of the diamine monomer can be adjusted to an appropriate level, which is understood to control the proportion of the aromatic moiety in one polyimide polymer chain. Can be.
  • the first diamine may also serve as another source of amine groups for forming imide groups, for a desired level of heat resistance.
  • the polyimide polymer chain formed by imidating the polyamic acid may include an aliphatic moiety derived from R 1 and R 2 of the first diamine and R 3 of the second diamine.
  • Such aliphatic moieties may be appropriately selected to have non-polarity, and non-limiting examples of aliphatic moieties for understanding include -CH 3 , -CF 3 , and the like. As described above, since the aliphatic moieties derived from R1, R2, and R3 have nonpolarity, the hygroscopicity of the polyimide polymer chain can be reduced.
  • the proportion of amic acid groups that significantly affect the increase in hygroscopicity throughout the polyamic acid may be relatively low. Therefore, it can act positively to lower the hygroscopicity of the polyimide film containing such polyamic acid.
  • the aliphatic moieties derived from R1, R2, and R3 can be understood as the main factors for the polyimide film according to the present invention to have a low dielectric constant and a low dielectric loss rate.
  • R1, R2, and R3 can be understood as the main factors for the polyimide film according to the present invention to have a low dielectric constant and a low dielectric loss rate.
  • the aliphatic moieties derived from R1, R2, and R3 improve nonpolarity and at the same time provide the desired level of flexibility in the polyimide film to reduce defect rates in the filming process and to produce levels suitable for producing flexible metal laminates.
  • the glass transition temperature and thermal expansion coefficient of can be obtained.
  • the molecular weight of the aliphatic moiety is 5% to 20 based on the total molecular weight of one polyimide polymer chain. %, In detail, may be 6% to 17%.
  • the R1 and R2 may be an alkyl group having a non-polarity, while excluding excessive molecular weight occupancy of the aliphatic portion, in detail, each of the R1 and R2 may be a methyl group.
  • R3 may also be a substituent having a nonpolarity while excluding an excessively aliphatic molecular weight occupancy, and in detail, may be -C (CF 3 ) 2 -or -C (CH 3 ) 2- .
  • fluorine may contribute to lowering the dielectric constant and may express strong nonpolarity, which may be particularly preferable as R 3.
  • the first diamine may be 4,4'-diamino-2,2'-dimethylbiphenyl (4,4'-Diamino-2,2'-dimethylbiphenyl: m-Tolidine).
  • the second diamine is 2,2-bis [4- (4-aminophenoxyphenyl)] hexafluoropropane (2,2-Bis [4- (4-aminophenoxy phenyl)] hexafluoropropane: HFBAPP).
  • the diamine monomer may have a relatively large molecular weight.
  • the dianhydride monomer may be a monomer having a relatively small molecular weight.
  • pyromellitic dianhydride having a relatively low molecular weight of 218 may be preferred as dianhydride monomer.
  • the pyromellitic dianhydride (PMDA) may also be viewed as a dianhydride monomer having a relatively rigid structure.
  • the pyromellitic dianhydride (PMDA) is preferable in that it can impart proper elasticity to the polyimide film prepared by imidating the polyamic acid.
  • the polyimide film of this invention is obtained from the polyamic-acid solution which is a precursor of polyimide.
  • the polyamic acid solution is obtained by dissolving a monomer compound blended in such a manner that the aromatic diamine monomer and the aromatic dianhydride monomer are substantially equimolar in an organic solvent, and the obtained polyamic acid organic solvent solution is prepared under controlled temperature conditions. It is prepared by stirring until the polymerization of the monomer is completed.
  • the polyamic acid solution is usually obtained at a solid content of 5 to 35% by weight, preferably at a concentration of 10 to 30% by weight.
  • the polyamic acid solution obtains the appropriate molecular weight and solution viscosity.
  • the solvent for synthesizing the polyamic acid solution is not particularly limited, and any solvent may be used as long as it is a solvent in which the polyamic acid is dissolved, but is preferably an amide solvent.
  • the solvent may be an organic polar solvent, and in detail, may be an aprotic polar solvent, for example, N, N'-dimethylformamide (DMF), N, It may be one or more selected from the group consisting of N'-dimethylacetamide, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), Diglyme (Diglyme), but is not limited thereto. It can be used individually or in combination of 2 or more types.
  • NMP N-methyl-pyrrolidone
  • GBL gamma butyrolactone
  • Diglyme Diglyme
  • the solvent may particularly preferably be N, N-dimethylformamide and N, N-dimethylacetamide.
  • this invention provides the manufacturing method of a polyimide film.
  • all monomers may be added in one step or the monomers may be sequentially added in step (a), and in this case, partial polymerization between monomers may occur.
  • all monomers may be added in one step or the monomers may be sequentially added in step (a), and in this case, partial polymerization between monomers may occur.
  • the final polyamic acid prepared through the steps (a) to (b) has a molecular structure in which partial chains having different physical properties are connected.
  • the physical properties of the polyimide film obtained by imidating the polyamic acid by adjusting the position, length of the partial chain and the type and content of the monomer constituting the same for example, dielectric constant, dielectric loss rate, glass transition temperature, moisture absorption rate You can fine tune your back.
  • the filler may be added for the purpose of improving various properties of the film, such as sliding, thermal conductivity, conductivity, corona resistance, loop hardness.
  • the filler to be added is not particularly limited, but preferred examples thereof include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica and the like.
  • the particle size of the filler is not particularly limited and can be determined according to the film properties to be modified and the type of filler to be added.
  • the average particle diameter may be from 0.05 to 100 ⁇ m, preferably from 0.1 to 75 ⁇ m, more preferably from 0.1 to 50 ⁇ m, particularly preferably from 0.1 to 25 ⁇ m.
  • the modifying effect is less likely to appear. If the particle size is larger than this range, the surface properties may be largely impaired, or the mechanical properties may be greatly reduced.
  • the addition amount of the filler is not particularly limited, and can be determined by the film characteristics to be modified, the particle size of the filler, and the like.
  • the addition amount of the filler may be 0.01 to 100 parts by weight, preferably 0.01 to 90 parts by weight, more preferably 0.02 to 80 parts by weight based on 100 parts by weight of polyimide.
  • the amount of filler added is less than this range, the effect of modification by the filler is less likely to appear, and if it exceeds this range, mechanical properties of the film may be largely impaired.
  • the addition method of a filler is not specifically limited, Any known method can also be used.
  • thermal imidation method the chemical imidation method, or the composite imidation method which used the thermal imidation method and the chemical imidation method together is mentioned.
  • the thermal imidization method is a method of imidizing a polyamic acid solution by heating only without using a catalyst such as a dehydrating agent. After forming a polyamic acid on a support, it is 40 to 400 degreeC, Preferably it is 40 to 300 degreeC It is a method of obtaining a polyimide film in which the polyamic acid is imidated by gradually increasing the temperature in the temperature range of 1 to 8 hours.
  • the chemical imidation method is a method of promoting imidization of a polyamic acid solution using a catalyst such as a dehydrating agent and / or an imidizing agent.
  • a dehydrating agent and an imidization catalyst are added to a polyamic acid solution to form a film on a support, and then heated at 80 to 200 ° C, preferably 100 to 180 ° C, partially cured and dried, and then at 200 to 400 ° C.
  • the polyimide film can be obtained by heating for 5 to 400 seconds.
  • dehydrating agents are, for example, aliphatic acid anhydride, aromatic acid anhydride, N, N'-dialkylcarbodiimide, halogenated lower aliphatic, halogenated lower fatty acid anhydride, arylphosphonic acid dihalide, and thionyl halide, or And mixtures of two or more thereof.
  • aliphatic acid anhydrides such as acetic anhydride, propionic anhydride, and lactic anhydride, or a mixture of two or more thereof can be preferably used in view of ease of availability and cost.
  • an imidation agent an aliphatic tertiary amine, an aromatic tertiary amine, a heterocyclic tertiary amine, etc. are used, for example.
  • heterocyclic tertiary amines are particularly preferably used in view of reactivity as a catalyst.
  • quinoline isoquinoline, ⁇ -picolin, pyridine and the like are preferably used.
  • the imidization step is performed by applying the film forming composition containing the polyamic acid solution on a support, and heat treating the film to a temperature range of 40 ° C. to 300 ° C. on the support. And a step of peeling the gel film from the support and further heating the gel film to imidize and dry the remaining amic acid (hereinafter also referred to as "firing process").
  • a dehydrating agent and / or an imidating agent are mixed in a polyamic-acid solution at low temperature, and a composition for film forming is obtained.
  • the said dehydrating agent and the imidating agent are not specifically limited, The compound illustrated above can be selected and used.
  • the said gel film manufacturing process it can also mix in a polyamic-acid solution using the hardening
  • the chemical imidation may be insufficient, and may break during firing or the mechanical strength may decrease.
  • the film forming composition is then cast in a film form on a support such as a glass plate, an aluminum foil, an endless stainless belt, or a stainless drum.
  • the film forming composition is heated on a support in a temperature range of 80 ° C to 200 ° C, preferably 100 ° C to 180 ° C.
  • the dehydrating agent and the imidizing agent are activated, and partially hardening and / or drying occurs, thereby forming a gel film.
  • the gel film is in the intermediate stage of curing from polyamic acid to polyimide and is self supporting.
  • This invention provides the flexible metal foil laminated board containing the polyimide film mentioned above and an electrically conductive metal foil.
  • metal foil When using the flexible metal foil laminated board of this invention for an electronic device or an electrical device use, it is copper or a copper alloy, stainless steel or its alloys, nickel or a nickel alloy (alloy 42, for example). And metal foil including aluminum or an aluminum alloy.
  • copper foil such as a rolled copper foil and an electrolytic copper foil
  • a rolled copper foil and an electrolytic copper foil is used abundantly, and can also be used suitably also in this invention.
  • the antirust layer, a heat resistant layer, or an adhesive layer may be apply
  • a metal foil is laminated on one surface of the polyimide film, or an adhesive layer containing thermoplastic polyimide is added to one surface of the polyimide film, and the metal foil is attached to the adhesive layer. It may be a laminated structure.
  • the present invention also provides an electronic component comprising the flexible metal laminate sheet as an electrical signal transmission circuit.
  • the electrical signal transmission circuit may be an electronic component that transmits a signal at a high frequency of at least 2 GHz, specifically at a high frequency of at least 5 GHz, and more particularly 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 aerospace, but is not limited thereto.
  • the imidation promoter including acetic anhydride / isoquinoline / DMF (46% / 13% / 41% by weight) was added to the polyamic acid solution thus obtained at 50 parts by weight based on 100 parts by weight of the polyamic acid solution, and the obtained mixture was made of stainless steel. After application to the plate was cast using a 400 ⁇ m gap using a doctor blade and dried for 4 minutes with hot air in a 120 °C oven to prepare a gel film.
  • the gel film thus prepared was peeled off from the stainless steel plate and fixed with a frame pin. After heat-treating the frame on which the gel film was fixed at 400 ° C. for 7 minutes, the film was removed to obtain a polyimide film having an average thickness of 15 ⁇ m.
  • a polyimide film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that the molar ratio of m-tolidine and HFBAPP was changed as in Table 1.
  • a polyimide film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that the molar ratio of m-tolidine and HFBAPP was changed as in Table 1.
  • a polyimide film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that the molar ratio of m-tolidine and HFBAPP was changed as in Table 1.
  • a polyimide film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that the molar ratio of m-tolidine and HFBAPP was changed as in Table 1.
  • a polyimide film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that the molar ratio of m-tolidine and HFBAPP was changed as in Table 1.
  • a polyimide film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that ODA was added in the molar ratio shown in Table 1 instead of m-tolidine and HFBAPP.
  • a polyimide film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that ODA and PPD were added in the molar ratio shown in Table 1 instead of m-tolidine and HFBAPP.
  • a polyimide film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that PMDA and BPDA were added in the molar ratio shown in Table 1 instead of adding PMDA alone.
  • a polyimide film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that BPDA was added in the molar ratio shown in Table 1 instead of PMDA.
  • Example 1 100 - 70 30 - - Example 2 100 - 80 20 - - Example 3 100 - 50 50 - - Comparative Example 1 100 - 30 70 - - Comparative Example 2 100 - 90 10 - - Comparative Example 3 100 - 40 60 - - Comparative Example 4 100 - - - - 100 Comparative Example 5 100 - - - 25 75 Comparative Example 6 50 50 70 30 - - Comparative Example 7 - 100 70 30 - - -
  • the glass transition temperature and the moisture absorption rate of the polyimide film obtained as described above were measured in the following manner.
  • the loss modulus and storage modulus of each film were calculated using DMA, and the inflection point was measured by the glass transition temperature in the tangent graph.
  • a polyimide film was cut into squares having a size of 5 cm ⁇ 5 cm to prepare specimens. After soaking in water at 23 ° C. for 24 hours, the weight was again measured, and the moisture absorption rate was measured by expressing the difference in weight obtained as%.
  • Dielectric constant and dielectric loss rate were measured by using a ohmmeter Agilent 4294A for 72 hours.
  • the polyimide film prepared according to the embodiment of the present invention can be confirmed that not only the moisture absorption rate, dielectric constant and dielectric loss rate is significantly lower, but also the desired glass transition temperature, as described above. Likewise, all of the following conditions are satisfied.
  • the dielectric loss factor (Df) is 0.005 or less
  • Glass transition temperature (Tg) is 320 degreeC or more.
  • Comparative Examples 1 to 3 in which the content of the diamine monomer is out of the range according to the present invention can be seen that at least one of the moisture absorption rate, dielectric constant and dielectric loss rate, and glass transition temperature is significantly reduced.
  • Comparative Examples 4 and 5 having different diamine monomers from the Examples also had significant differences in dielectric constant, dielectric loss rate, and moisture absorption rate compared with the Examples.
  • Comparative Examples 4 and 5 show a significantly higher dielectric constant and dielectric loss rate compared to the examples, which can be expected to be difficult to use in electronic components in which signal transmission is performed at a high frequency in units of gigabytes.
  • Comparative Examples 4 and 5 greatly exceeds the preferred range disclosed in the present invention, which has already been described as being able to work very disadvantageously in the processing of the polyimide film.
  • the present invention has a relatively low hygroscopicity with a desired glass transition temperature due to the combination of specific dianhydride monomers, diamine monomers and their specific blending ratio, and the dielectric constant according to moisture absorption. And it can provide the polyimide film by which the dielectric loss rate raise was suppressed.
  • the present invention can also provide a flexible metal laminate that can be utilized as an electrical transmission circuit capable of high frequency communication of 2 GHz or more, including the polyimide film as described above.

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)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne un film de polyimide préparé par imidisation d'un acide polyamique issu de la polymérisation : d'un monomère diamine comprenant une première diamine représentée par la formule chimique (1) et une seconde diamine représentée par la formule chimique (2) ; et d'un dianhydride pyromellitique (PMDA). La constante diélectrique (Dk) est inférieure ou égale à 3,4, et le coefficient de perte diélectrique (Df) est inférieur ou égal à 0,005.
PCT/KR2018/014616 2018-04-05 2018-11-26 Film de polyimide permettant de préparer un stratifié plaqué d'une feuille métallique souple et stratifié plaqué d'une feuille métallique souple comprenant celui-ci WO2019194386A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201880091990.0A CN111918907B (zh) 2018-04-05 2018-11-26 用于制备柔性金属箔层压板的聚酰亚胺薄膜以及包含其的柔性金属箔层压板

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2018-0039692 2018-04-05
KR1020180039692A KR102141893B1 (ko) 2018-04-05 2018-04-05 연성금속박적층판 제조용 폴리이미드 필름 및 이를 포함하는 연성금속박적층판

Publications (1)

Publication Number Publication Date
WO2019194386A1 true WO2019194386A1 (fr) 2019-10-10

Family

ID=68101047

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/014616 WO2019194386A1 (fr) 2018-04-05 2018-11-26 Film de polyimide permettant de préparer un stratifié plaqué d'une feuille métallique souple et stratifié plaqué d'une feuille métallique souple comprenant celui-ci

Country Status (4)

Country Link
KR (1) KR102141893B1 (fr)
CN (1) CN111918907B (fr)
TW (1) TWI705988B (fr)
WO (1) WO2019194386A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102345722B1 (ko) * 2019-11-07 2022-01-03 피아이첨단소재 주식회사 고내열 저유전 폴리이미드 필름 및 이의 제조방법
KR102347633B1 (ko) * 2019-11-07 2022-01-10 피아이첨단소재 주식회사 유전특성이 개선된 폴리이미드 필름 및 그 제조방법
KR102347588B1 (ko) 2019-11-07 2022-01-10 피아이첨단소재 주식회사 고내열 저유전 폴리이미드 필름 및 이의 제조방법
KR102347634B1 (ko) * 2019-11-13 2022-01-10 피아이첨단소재 주식회사 고접착 저유전 폴리이미드 필름 및 이의 제조방법
KR102347632B1 (ko) * 2019-11-13 2022-01-10 피아이첨단소재 주식회사 저유전 폴리이미드 필름 및 이의 제조방법
KR102437830B1 (ko) * 2020-11-17 2022-08-31 피아이첨단소재 주식회사 치수안정성이 개선된 저유전 폴리이미드 필름 및 그 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002363283A (ja) * 2001-06-06 2002-12-18 Nitto Denko Corp ポリアミド酸とそれより得られるポリイミド樹脂とそれらの回路基板への利用
JP2014195947A (ja) * 2013-03-29 2014-10-16 新日鉄住金化学株式会社 両面フレキシブル金属張積層板の製造方法
KR20150058835A (ko) * 2013-11-21 2015-05-29 주식회사 엘지화학 다층 폴리이미드 필름의 층 분리방법, 그 모노머 조성 분석방법 및 분석시스템
JP2016188298A (ja) * 2015-03-30 2016-11-04 新日鉄住金化学株式会社 ポリイミド、樹脂フィルム、金属張積層体及び回路基板
JP2017025214A (ja) * 2015-07-23 2017-02-02 大日本印刷株式会社 ポリイミド樹脂および積層体

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5310863A (en) * 1993-01-08 1994-05-10 International Business Machines Corporation Polyimide materials with improved physico-chemical properties
US20070292701A1 (en) * 2004-09-24 2007-12-20 Takashi Kikuchi Novel Polyimide Film Improved in Adhesion
JP5185535B2 (ja) * 2005-01-18 2013-04-17 株式会社カネカ 接着性の改良された新規なポリイミドフィルム
KR101338328B1 (ko) * 2011-12-28 2013-12-09 웅진케미칼 주식회사 폴리아믹산 조성물의 제조방법, 폴리아믹산 조성물, 이를 이용한 폴리이미드 필름 및 디스플레이 소자용 기판
KR101493595B1 (ko) 2013-05-22 2015-02-13 에스케이씨코오롱피아이 주식회사 폴리이미드 필름
KR102239605B1 (ko) * 2014-12-23 2021-04-12 주식회사 두산 양면 연성 금속 적층판 및 그 제조방법
KR102531268B1 (ko) * 2015-12-31 2023-05-12 주식회사 동진쎄미켐 폴리이미드 필름 제조용 조성물, 이의 제조 방법 및 이를 이용한 폴리이미드 필름의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002363283A (ja) * 2001-06-06 2002-12-18 Nitto Denko Corp ポリアミド酸とそれより得られるポリイミド樹脂とそれらの回路基板への利用
JP2014195947A (ja) * 2013-03-29 2014-10-16 新日鉄住金化学株式会社 両面フレキシブル金属張積層板の製造方法
KR20150058835A (ko) * 2013-11-21 2015-05-29 주식회사 엘지화학 다층 폴리이미드 필름의 층 분리방법, 그 모노머 조성 분석방법 및 분석시스템
JP2016188298A (ja) * 2015-03-30 2016-11-04 新日鉄住金化学株式会社 ポリイミド、樹脂フィルム、金属張積層体及び回路基板
JP2017025214A (ja) * 2015-07-23 2017-02-02 大日本印刷株式会社 ポリイミド樹脂および積層体

Also Published As

Publication number Publication date
CN111918907A (zh) 2020-11-10
TWI705988B (zh) 2020-10-01
TW201943764A (zh) 2019-11-16
CN111918907B (zh) 2023-04-04
KR102141893B1 (ko) 2020-08-07
KR20190116725A (ko) 2019-10-15

Similar Documents

Publication Publication Date Title
WO2019194389A1 (fr) Film de polyimide permettant de préparer un stratifié plaqué d'une feuille métallique souple et stratifié plaqué d'une feuille métallique souple comprenant celui-ci
WO2019194386A1 (fr) Film de polyimide permettant de préparer un stratifié plaqué d'une feuille métallique souple et stratifié plaqué d'une feuille métallique souple comprenant celui-ci
WO2015183056A1 (fr) Liquide à base de polyimide et film à base de polyimide produit en l'utilisant
WO2020105888A1 (fr) Film de polyimide ayant une faible constante diélectrique et une faible hygrocospicité et son procédé de fabrication
WO2019164068A1 (fr) Film de polyimide en feuille de graphite comprenant une charge à base de pi sphérique, son procédé de fabrication et feuille de graphite fabriquée à l'aide de celui-ci
WO2016108491A1 (fr) Film de polyimide multicouche de fusion thermique utilisant de l'acide de polyamide thermoplastique hydrosoluble réticulé, et son procédé de préparation
WO2020105889A1 (fr) Film de polyimide faiblement hygroscopique, et stratifié plaqué de feuille métallique flexible le comprenant
WO2020096363A1 (fr) Film composite de polyimide ayant d'excellentes caractéristiques diélectriques et son procédé de formation
WO2021091011A1 (fr) Film de polyimide hautement résistant à la chaleur et à faible constante diélectrique et son procédé de production
WO2021095975A1 (fr) Film polyimide faiblement diélectrique et son procédé de production
WO2020091432A1 (fr) Composition de précurseur de polyimide pour améliorer l'adhésivité d'un film de polyimide et film de polyimide fabriqué à partir de celle-ci
WO2021091014A1 (fr) Film de polyimide ayant des propriétés diélectriques améliorées, et procédé de fabrication associé
WO2018080222A2 (fr) Composition de formation de film polyimide et film polyimide ainsi produit
WO2020111399A1 (fr) Film de polyimide comprenant deux charges ou plus présentant des diamètres différents de particule et appareil électronique le comprenant
WO2020040356A1 (fr) Vernis polyimide comprenant un acide carboxylique aromatique pour le revêtement de conducteurs et son procédé de fabrication
WO2016108490A1 (fr) Acide de polyamide thermoplastique hydrosoluble réticulé et son procédé de fabrication
WO2020091147A1 (fr) Vernis polyimide pour revêtement conducteur permettant d'améliorer la résistance à la chaleur d'un produit revêtu de polyimide, et produit revêtu de polyimide fabriqué à partir de ce dernier
WO2021091013A1 (fr) Film de polyimide présentant une résistance élevée à la chaleur et de faibles propriétés diélectriques et son procédé de fabrication
WO2022065804A1 (fr) Film de polyimide à faible constante diélectrique et son procédé de fabrication
WO2020241983A1 (fr) Film polyimide hautement élastique et stratifié revêtu d'une feuille métallique flexible le comprenant
WO2022108296A1 (fr) Acide polyamique faiblement diélectrique comprenant une poudre de cristaux liquides, film de polyimide, et procédé de production associé
WO2022098042A1 (fr) Film de polyimide ayant une stabilité dimensionnelle élevée, et son procédé de fabrication
WO2020209555A1 (fr) Film de polyimide multicouches ayant une excellente stabilité dimensionnelle et une excellente adhésivité, et son procédé de production
WO2019221343A1 (fr) Film de polyimide ayant une faible constante diélectrique et une faible hydrocospicité et son procédé de fabrication
WO2023090969A1 (fr) Composition de précurseur de polyimide et film de polyimide la comprenant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18913217

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18913217

Country of ref document: EP

Kind code of ref document: A1