WO2020054912A1 - Film de polyimide ayant une qualité de surface améliorée et son procédé de fabrication - Google Patents

Film de polyimide ayant une qualité de surface améliorée et son procédé de fabrication Download PDF

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WO2020054912A1
WO2020054912A1 PCT/KR2018/014615 KR2018014615W WO2020054912A1 WO 2020054912 A1 WO2020054912 A1 WO 2020054912A1 KR 2018014615 W KR2018014615 W KR 2018014615W WO 2020054912 A1 WO2020054912 A1 WO 2020054912A1
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dianhydride
diamine
polyimide film
film
mol
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PCT/KR2018/014615
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English (en)
Korean (ko)
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김동영
원동영
최정열
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에스케이씨코오롱피아이 주식회사
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Priority to CN201880070343.1A priority Critical patent/CN111295411B/zh
Publication of WO2020054912A1 publication Critical patent/WO2020054912A1/fr

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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
    • 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
    • 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
    • C08G73/1075—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
    • H05K1/03—Use of materials for the substrate
    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N

Definitions

  • the present invention relates to a polyimide film having improved surface quality and a method for manufacturing 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 with excellent chemical stability along with a rigid aromatic backbone It is material. Accordingly, polyimide has been spotlighted as an insulating material for microelectronic components in which the aforementioned properties are strongly required.
  • microelectronic component examples include a thin circuit board having high circuit density and being flexible so that it can cope with the reduction in weight and size of electronic products, and the polyimide is widely used as an insulating film for thin circuit boards.
  • the thin circuit board has a structure in which a circuit including a metal foil is formed on an insulating film, and the thin circuit board is referred to as a flexible metal foil clad laminate in a broad sense and refers to a thin copper plate with a metal foil. When used, it is also referred to as a flexible copper clad laminate (FCCL) in a narrower sense.
  • FCCL flexible copper clad laminate
  • a method of manufacturing a flexible metal foil-clad laminate for example, (i) casting or imposing a polyamic acid, a precursor of polyimide, on a metal foil, followed by imidization, and (ii) sputtering.
  • a metallization method in which a metal layer is directly provided on a polyimide film
  • a lamination method in which a polyimide film and a metal foil are bonded by heat and pressure through a thermoplastic polyimide.
  • the double metallization method for example, by sputtering a metal such as copper on a polyimide film having a thickness of 20 to 38 ⁇ m, sequentially depositing a tie layer and a seed layer to form a flexible metal thin-layer laminate. It is a method of producing, and has an advantage in forming an ultra-fine circuit having a pitch of a circuit pattern of 35 ⁇ m or less, and is widely used to manufacture a flexible metal foil laminate for COF (chip on film).
  • the adhesion and adhesion with the metal plate can be greatly improved depending on the surface condition of the polyimide film.
  • surface defects such as nubs, wrinkles, and protrusions formed on the surface of the polyimide film may act as factors that reduce adhesion and adhesion to the metal deposited by sputtering, and conversely, when the surface of the polyimide film is smooth, The degree of adhesion and adhesion with the metal may be excellent at a desired level.
  • the surface defect is a major reason that gels or bubbles formed in the process of converting polyamic acid, a precursor of polyimide, into polyimide remain in the polyimide film after conversion is completed. You can.
  • these gels and bubbles may also act as one factor causing cracks in the polyimide film.
  • the main object of the present invention is to provide a polyimide film having a smooth surface and suitable for manufacturing a flexible metal foil laminate.
  • the present invention uses a specific monomer for the implementation of the polyimide film and implements its content range according to a specific embodiment of the present invention, so that there is substantially no generation of gels and bubbles, and no surface defects derived therefrom. It is possible to implement a polyimide film having surface properties.
  • the polyimide film may have an appropriate level of glass transition temperature and coefficient of thermal expansion that can be used as an insulating film for a flexible metal foil-clad laminate.
  • the present invention has a practical purpose to provide a specific embodiment thereof.
  • the present invention provides a method of making the polyimide film.
  • the present invention provides a flexible metal foil laminate comprising the polyimide film and an electronic device including the same.
  • dianhydride dianhydride
  • dianhydride is intended to include its precursors or derivatives, which may not technically be dianhydrides, but will nevertheless react with diamines to form polyamic acids. And this polyamic acid can be converted back to polyimide.
  • Diamine as used herein is intended to include precursors or derivatives thereof, which may not technically be diamines, but will nevertheless react with dianhydrides to form polyamic acids, which are polyamic The acid can be converted back to polyimide.
  • any upper limit of any pair of any pair regardless of whether the ranges are disclosed separately or It should be understood that the specific values and any lower range limits or all ranges that can be formed with the desired values are specifically disclosed.
  • a range of numerical values is referred to herein, unless stated otherwise, eg, unless there is a limiting term such as greater than, less than, the range is intended to include the endpoint and all integers and fractions within the range. It is intended that the scope of the invention not be limited to the specific values recited when defining a range.
  • the first dianhydride is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) and 2,3,3', 4'-biphenyltetracarboxylic dianhydride Ride (a-BPDA) is at least one member selected from the group consisting of,
  • the first diamine is at least one member selected from the group consisting of paraphenylenediamine (PPD) and metaphenylenediamine (MPD),
  • the second dianhydride includes at least one dianhydride different from the first dianhydride
  • the second diamine includes at least one diamine different from the first diamine
  • imidization refers to a phenomenon, process, or method in which the amic acid group is converted to an imide group by inducing a ring-closure and dehydration reaction of an amic acid group forming a polyamic acid through heat and / or a catalyst.
  • the imidization proceeds excessively quickly, some of the bulk of the polyamic acid solution (or gel film) may show a deviation from the level of the imidization progress of the other.
  • imidization proceeds relatively slowly at a core (center) portion of the polyamic acid solution (or gel film) in the applied state and a portion adjacent thereto, and vice versa.
  • the imidization may proceed relatively quickly in a region in contact with or exposed to the outside.
  • the amic acid group may form a gel with the polymer chain converted to the imide group remaining moisture or a solvent, and the gel formed as such is normally formed by imidization. It can be isolated by a portion of the polyimide and present inside the polyimide film.
  • the gel film can be understood as a film intermediate having self-supporting properties in an intermediate step for conversion from polyamic acid to polyimide.
  • gas is generated inside the polyamic acid solution (or gel film) due to evaporation of moisture and solvent, and the gas may generate bubbles in the polyamic acid solution (or gel film).
  • the polyamic acid solution gradually solidifies in the form of a polyimide film through a gel film.
  • gas is slowly generated and the exhaust rate of the gas is delayed.
  • the finally obtained polyimide film may include empty spaces due to the bubbles.
  • the imidization process is performed at an appropriate level to suppress the formation of gels and bubbles.
  • Controlling the progress of imidization may include, but is not limited to, a number of factors, such as the temperature, time, catalyst added to the imidization, its content and type, etc., and may be determined by such attachment means.
  • the present invention has been found that the type, content and ratio of diamine and dianhydride constituting polyamic acid and further polyimide may also affect at least part of the progress of imidation.
  • PPD and / or MPD which are the first diamines, may have a property of inducing that the dehydration reaction of the ring by imidization proceeds relatively rapidly, despite the secondary means.
  • the BPDA-based material which is the first dianhydride
  • the BPDA-based material may have a property that induces the ring-closed dehydration reaction by imidation to proceed relatively slowly. Therefore, when the first diamine and the first dianhydride are combined in a predetermined ratio, imidization may proceed to an appropriate level.
  • the molar ratio of the first diamine to the first dianhydride is greater than 1 to less than 2, specifically 1.6 to 1.9, more detailed It may be 1.7 to 1.8, in particular 1.72.
  • the appropriate level may be, for example, a level in which gels and bubbles are less produced without controlling the secondary means.
  • the level of low generation of gels and / or bubbles can be quantified, for example, by the number of surface defects per area of 10 cm * 10 cm of the polyimide film, and the polyimide film according to the present invention has an area of 10 cm * 10 cm
  • the number of sugar surface defects is 1 or less, specifically 0, and has very smooth surface properties.
  • the molar ratio is satisfied, when the first dianhydride has an excessively small number of moles based on the total number of moles of the polyamic acid, chemical resistance of the polyimide film may be lowered. Conversely, when the number of moles of the first dianhydride is large, it may cause a decrease in the glass transition temperature of the polyimide film and an excessive increase in the coefficient of thermal expansion.
  • the thermal expansion coefficient of the polyimide film may be significantly lowered.
  • the glass transition temperature can be lowered.
  • the first diamine and the first dianhydride are included in a predetermined content.
  • the content of the first dianhydride may be 40 to 50 mol% based on the total number of moles of the first dianhydride and the second dianhydride, and the second dianhydride The content of may be 50 to 60 mol%.
  • the first diamine may be 80 to 92 mol% based on the total number of moles of the first diamine and the second diamine, and the second diamine may be 8 to 20 mol%.
  • the second diamine may include one or more selected from the group consisting of 4,4'-diaminodiphenyl ether (oxydianiline, ODA) and 3,4'-diaminodiphenyl ether.
  • Such a second diamine can preferably act to improve the transparency of the polyimide film.
  • the second diamine since the second diamine has a relatively flexible structure by containing two benzene rings in a molecular structure, it may also be preferable in that it can impart an appropriate linear expansion coefficient to the polyimide film.
  • the first dianhydride, the second dianhydride, the first diamine, and the second diamine are 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and fatigue, respectively. It may be melic dianhydride, paraphenylenediamine and 4,4'-diaminodiphenyl ether.
  • the polyimide film derived from the combination of the diamine and the dianhydride may have a desirable level of thermal expansion coefficient and glass transition temperature applicable to a flexible metal foil laminate while having smooth surface characteristics as described above.
  • the polyimide film has a coefficient of thermal expansion of 2 to 7 ⁇ m / m * ° C, specifically 2 to 5 ⁇ m / m * ° C, and a glass transition temperature of 370 ° C or higher, and specifically 380 ° C or higher. You can.
  • the flexible metal foil-clad plate has a metal foil thereof, typically having a thermal expansion coefficient of 16 ⁇ m / m * ° C to 17 ⁇ m / m * ° C, and when forming a metal foil by sputtering on a polyimide film, the polyimide film It may be desirable to have a lower coefficient of thermal expansion than the metal foil, specifically, it is preferable that the polyimide film has a coefficient of thermal expansion of 2 to 7 ⁇ m / m * ° C, and more specifically 2 to 5 ⁇ m / m * ° C. You can. Therefore, since the polyimide film according to the present invention may have a coefficient of thermal expansion within the above-described preferred range, there is an advantage in implementing a flexible metal foil-clad laminate.
  • the glass transition temperature is lower than the above temperature, it is not preferable from the viewpoint of heat resistance. However, it is also undesirable that the glass transition temperature is too high.
  • the polyimide film has an excessively high glass transition temperature, an extremely low thermal expansion coefficient of less than 0.1 ⁇ m / m * ° C may be exhibited, or a negative thermal expansion coefficient may be expressed.
  • the thermal expansion coefficient between the polyimide film and the metal foil is considerably different, which may lead to a decrease in adhesion between the two and defects such as cracks.
  • the polyimide film may be more advantageous for the production of a flexible metal foil laminate when the glass transition temperature is 370 ° C to 400 ° C, and specifically 380 ° C to 400 ° C.
  • Step (a) is,
  • step (a-2) The second dianhydride and the second diamine are additionally added, or the first diamine, the second dianhydride and the second diamine are additionally added, from step (a-1). It may include the step of extending the end of at least a portion of the prepared polymer.
  • the total number of moles of the first dianhydride and the second dianhydride and the total number of moles of the first diamine and the second diamine are substantially equimolar, in detail
  • the second dianhydride may be further added to polymerize to a molar ratio of 0.997 to 0.999, and more specifically 0.998.
  • an organic solvent may be mixed with dianhydride and diamine.
  • the organic solvent is not particularly limited as long as it is a solvent in which polyamic acid can be dissolved, but as an example, the organic solvent may be an aprotic polar solvent.
  • Non-limiting examples of the aprotic polar solvent include amide solvents such as N, N'-dimethylformamide (DMF) and N, N'-dimethylacetamide (DMAc), p-chlorophenol, and o-chloro And phenol-based solvents such as phenol, N-methyl-pyrrolidone (NMP), gamma brotirolactone (GBL) and digrime, and these may be used alone or in combination of two or more.
  • amide solvents such as N, N'-dimethylformamide (DMF) and N, N'-dimethylacetamide (DMAc), p-chlorophenol, and o-chloro And phenol-based solvents such as phenol, N-methyl-pyrrolidone (NMP), gamma brotirolactone (GBL) and digrime, and these may be used alone or in combination of two or more.
  • the solubility of the polyamic acid may be controlled by using auxiliary solvents such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water.
  • auxiliary solvents such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water.
  • the organic solvent that can be particularly preferably used in the production of the polyamic acid of the present invention may be amide solvents N, N'-dimethylformamide and N, N'-dimethylacetamide.
  • the polyamic acid prepared as described above may have a weight average molecular weight of 150,000 g / mole or more to 1,000,000 g / mole or less, specifically 260,000 g / mole or more to 700,000 g / mole or less, and more specifically 280,000 g / mole It may be greater than or equal to 500,000 g / mole or less.
  • Polyamic acid having such a weight average molecular weight may be preferable for the production of a polyimide film having better heat resistance and mechanical properties.
  • the weight average molecular weight of the polyamic acid may be proportional to the viscosity of the precursor composition containing the polyamic acid and the organic solvent, and the viscosity may be adjusted to control the weight average molecular weight of the polyamic acid to the above range.
  • the viscosity of the precursor composition is proportional to the content of the polyamic acid solid content, specifically, the total amount of the dianhydride monomer and the diamine monomer used in the polymerization reaction.
  • the weight average molecular weight does not represent a linear proportional relationship of one dimension to the viscosity, but is proportional to the form of a logarithmic function.
  • the precursor composition of the present invention may include 15% to 20% by weight of a polyamic acid solid content and 80% to 85% by weight of an organic solvent, and in this case, a viscosity of 90,000 cP or more to 300,000 cP or less, in detail It may be 100,000 cP or more to 250,000 cP. Within this viscosity range, the weight average molecular weight of the polyamic acid may fall within the above range, and the precursor composition may not cause problems in the film forming process described above.
  • a filler may be added during the production of the polyamic acid for the purpose of improving various properties of the film such as sliding property, thermal conductivity, conductivity, corona resistance, and loop hardness of the polyimide film.
  • the filler to be added is not particularly limited, and preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.
  • the average particle diameter of the filler is not particularly limited, and can be determined according to the characteristics of the polyimide film to be modified and the type of filler to be added.
  • the average particle diameter of the filler may be 0.05 ⁇ m to 100 ⁇ m, specifically 0.1 ⁇ m to 75 ⁇ m, more preferably 0.1 ⁇ m to 50 ⁇ m, and particularly specifically 0.1 ⁇ m to 25 ⁇ m.
  • the filler may significantly impair the surface properties of the polyimide film or cause mechanical properties of the film to deteriorate.
  • the addition amount of the filler is not particularly limited, and can be determined by the characteristics of the polyimide film to be modified, the particle size of the filler, and the like.
  • the amount of the filler added is 0.01 to 100 parts by weight, preferably 0.01 to 90 parts by weight, and more preferably 0.02 to 80 parts by weight based on 100 parts by weight of the precursor composition.
  • the method for adding the filler is not particularly limited, and any known method can be used.
  • the dehydrating agent is added with respect to 1 mole of the amic acid group in the polyamic acid, from 3.5 mole to 6.0 mole, specifically from 4.0 mole to 5.5 mole, and the imidizing agent is added from 0.7 mole to 1.2 mole, specifically 0.8 mole to 1.0 mole Can be.
  • the term “dehydrating agent” refers to a substance that promotes a cyclization reaction through dehydration of a polyamic acid, and includes, without limitation, aliphatic acid anhydrides, aromatic acid anhydrides, N, N'- Dialkyl carbodiimide, halogenated lower aliphatic, halogenated lower patty acid anhydride, aryl phosphonic dihalide, thionyl halide, and the like.
  • aliphatic acid anhydrides may be preferred from the viewpoint of ease of availability and cost, and non-limiting examples thereof include acetic anhydride (AA), propion acid anhydride, and lactic acid anhydride. Etc. are mentioned, These can be used individually or in mixture of 2 or more types.
  • imide agent means a substance having an effect of promoting a ring-closure reaction to a polyamic acid, for example, an imine-based component such as an aliphatic tertiary amine, an aromatic tertiary amine, and a heterocyclic tertiary amine. You can. Of these, heterocyclic tertiary amines may be preferable from the viewpoint of reactivity as a catalyst. Non-limiting examples of heterocyclic tertiary amines include quinoline, isoquinoline, ⁇ -picoline (BP), pyridine and the like, and these can be used alone or in combination of two or more.
  • an imine-based component such as an aliphatic tertiary amine, an aromatic tertiary amine, and a heterocyclic tertiary amine.
  • heterocyclic tertiary amines may be preferable from the viewpoint of reactivity as a catalyst.
  • a film-forming composition containing a dehydrating agent and / or an imidizing agent is cast in a film form on a support such as a glass plate, aluminum foil, endless stainless belt, or stainless drum, and then on the support.
  • the film-forming composition is first heat-treated at a variable temperature in the range of 50 ° C to 200 ° C, specifically 50 ° C to 150 ° C.
  • a dehydrating agent and / or an imidizing agent acts as a catalyst so that the amic acid group can be quickly converted to an imide group.
  • the gel film is stretched.
  • the process may be performed, and stretching may be performed in at least one of a machine transport direction (MD) and a transverse direction (TD) with respect to the machine transport direction.
  • MD machine transport direction
  • TD transverse direction
  • the gel film thus obtained is fixed to a tenter and then subjected to a second heat treatment at a variable temperature in the range of 50 ° C to 650 ° C, specifically 200 ° C to 600 ° C to remove water, catalyst, residual solvent, and the like remaining in the gel film. Then, almost all the remaining amic acid groups are imidized to obtain the polyimide film of the present invention.
  • a dehydrating agent and / or an imidizing agent acts as a catalyst, so that the amic acid group can be rapidly converted to an imide group, thereby realizing a high imidization rate.
  • the polyimide film obtained as described above may be heated to a temperature of 400 ° C. to 650 ° C. for 5 seconds to 400 seconds to further harden the polyimide film, and may remain inside the obtained polyimide film. It can also be done under a given tension to relieve stress.
  • Example 1 is a photograph of the surface of the polyimide film according to Example 1.
  • first PMDA as the second dianhydride and ODA as the second diamine were added at a molar ratio shown in Table 1 and stirred for 1 hour to perform polymerization.
  • the second PMDA was added in the molar ratio shown in Table 1, so that the total number of moles of the first dianhydride, the second dianhydride, and the first diamine and the second diamine was substantially equimolar. And stirred for 1 hour, the polymerization was terminated when the viscosity reached 1100 to 1300 poise (poise) to prepare a final polyamic acid.
  • the gel film thus prepared was removed from the stainless steel plate, fixed with a frame pin, and then heat-treated at 400 ° C. for 7 minutes for a frame on which the gel film was fixed to remove the film 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 ratios of the first diamine and the second diamine were changed as shown 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 ratios of the first diamine and the second diamine were changed as shown 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 ratios of the first dianhydride, the second dianhydride, the first diamine, and the second diamine were changed as shown 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 ratios of the first dianhydride, the second dianhydride, the first diamine, and the second diamine were changed as shown 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 ratios of the first dianhydride, the second dianhydride, the first diamine, and the second diamine were changed as shown 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 ratios of the first diamine and the second diamine were changed as shown 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 ratios of the first diamine and the second diamine were changed as shown 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 ratios of the first diamine and the second diamine were changed as shown in Table 1.
  • Grade S 0 surface defects; Grade A: surface defects: 5 or less; No more than 10 grade B surface defects; > 10 grade C surface defects
  • the molar ratio of the first dianhydride and the first diamine and the number of moles of the first and second dianhydride and the mole number of the first and second diamine are examples in which the surface defects are within the scope of the present invention. No, it can be seen that it has a smooth surface property.
  • FIG. 1 shows a photograph of the surface of the polyimide film prepared in Example 1, and referring to this, it can be seen that the polyimide film has no protrusions on the surface and the surface is smooth.
  • FIG. 2 shows a photograph of the surface of the polyimide film prepared in Comparative Example 1
  • FIG. 3 shows a photograph of the surface of the polyimide film prepared in Comparative Example 2.
  • FIGS. 4 and 5 show photographs of the surfaces of the polyimide films prepared in Comparative Examples 3 and 4, respectively.
  • Comparative Examples 3 and 4 are examples in which the polyimide film was prepared using a relatively large or small amount of the first diamine because the molar ratio of the first dianhydride and the first diamine is outside the scope of the present invention.
  • the gel was formed, and as a result, a number of protrusions derived from the gel were induced on the surface of the polyimide, which was completed as shown in FIGS. 4 and 5.
  • comparative examples in which the molar ratio of the first dianhydride and the first diamine and the number of moles of the first and second dianhydride and the mole number of the first and second diamine are outside the scope of the present invention are glass transition temperatures. It can be seen that at least one of the and thermal expansion coefficient is excessive, from which it can be expected that it will be disadvantageous for the implementation of the flexible circuit board. On the contrary, it can be seen that the embodiment has an advantage in implementing a flexible circuit board, as it has an appropriate level of glass transition temperature and a desirable coefficient of thermal expansion.
  • the present invention provides a polyimide film having smooth surface properties, without defects due to gels and / or bubbles, due to the combination of specific dianhydride monomers and diamine monomers and their specific blending ratio. can do.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne un film de polyimide fabriqué par imidisation d'un acide polyamique dans lequel un premier dianhydride, un second dianhydride, une première diamine et une seconde diamine sont polymérisés.
PCT/KR2018/014615 2018-09-12 2018-11-26 Film de polyimide ayant une qualité de surface améliorée et son procédé de fabrication WO2020054912A1 (fr)

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KR1020180108921A KR102171061B1 (ko) 2018-09-12 2018-09-12 표면 품질이 개선된 폴리이미드 필름 및 이의 제조방법

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KR102472532B1 (ko) * 2020-11-19 2022-12-01 피아이첨단소재 주식회사 폴리아믹산 조성물 및 이를 포함하는 폴리이미드
KR102451825B1 (ko) * 2020-11-19 2022-10-07 피아이첨단소재 주식회사 폴리아믹산 조성물 및 이를 포함하는 폴리이미드
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KR102472537B1 (ko) * 2020-11-19 2022-12-01 피아이첨단소재 주식회사 폴리아믹산 조성물 및 이를 포함하는 폴리이미드
KR102445910B1 (ko) * 2020-11-24 2022-09-22 피아이첨단소재 주식회사 높은 치수 안정성을 가지는 폴리이미드 필름 및 그 제조방법

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KR102171061B1 (ko) 2020-10-28
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CN111295411B (zh) 2023-06-13

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