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
• • 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
  • 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

• It relates to a polyimide film, a method of manufacturing the same, and a flexible metal clad laminate including the same, and more particularly, to a polyimide film having a small moisture absorption expansion coefficient, a method of manufacturing the same, and a flexible metal clad laminate including the same.
• Polyimide films have excellent mechanical and thermal dimensional stability and chemical stability, and are widely used in electric, electronic materials, space, aviation, and telecommunication fields.
• Polyimide film is a flexible printed circuit board (FPCB) material with a fine pattern due to the light and thinness of the component, such as tape automated bonding (TAB) or chip on film (COF). ), etc. It is widely used as a base film.
• a flexible circuit board generally has a structure in which a circuit including a metal foil is formed on a base film, and such a flexible circuit board is referred to as a flexible metal foil clad laminate in a broad sense.
• such polyimide has a rather high coefficient of expansion of moisture absorption. If the coefficient of expansion of moisture absorption is high, dimensional change may occur by absorbing moisture during the FPCB process, resulting in a short circuit between circuits or a distance between patterns. Changing problems can arise. Therefore, it is necessary to lower the moisture absorption and expansion coefficient of the polyimide film.
• An object of the present invention is to provide a polyimide film excellent in dimensional stability due to its low moisture absorption and expansion coefficient.
• Another object of the present invention is to provide a method of manufacturing the above-described polyimide film.
• Another object of the present invention is to provide a flexible metal foil laminate comprising the polyimide film described above.
• a polyimide film having a moisture absorption expansion coefficient of about 9ppm/%RH or less in a 25°C, 20 to 80% relative humidity section.
• the polyimide film is derived from imidization of a polyamic acid formed from the reaction of a first dianhydride, a second dianhydride, a first diamine, and a second diamine,
• the first dianhydride and the second anhydride are different from each other,
• the first diamine and the second diamine are different from each other,
• the first dianhydride includes 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, or a combination thereof,
• the first diamine includes m-phenylenediamine, p-phenylenediamine, or a combination thereof,
• a first binding ratio which is a ratio in which the first dianhydride and the first diamine are bonded, may be about 40 to about 70%.
• the polyamic acid may be formed by sequentially reacting the second anhydride and the second diamine with the pre-reactant of the first dianhydride and the first diamine to extend the ends of at least some of the pre-reactant.
• the second dianhydride may include pyromellitic dianhydride.
• the second diamine may include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, or a combination thereof.
• the first dianhydride is contained in an amount of about 40 to about 70 mol% based on the total number of moles of the first dianhydride and the second dianhydride, and the second dianhydride is It may be included in about 30 to about 60 mol%.
• the first diamine is contained in an amount of about 70 to about 98 mol%, and the second diamine is about 2 to It may be included in about 30 mol%.
• the first diamine is contained in an amount of about 80 to about 98 mol%, and the second diamine is 2 to 20 It is included in mole percent,
• the polyimide film may have a moisture absorption expansion coefficient of less than or equal to about 8 ppm/%RH in a range of 25° C. and 20 to 80% relative humidity.
• the polyimide film may have a moisture absorption expansion coefficient of about 9ppm/%RH or less in a range of 25°C and 3 to 90% relative humidity.
• It is a method for producing a polyimide film comprising; imidizing the polyamic acid,
• the first dianhydride and the second anhydride are different from each other,
• the first diamine and the second diamine are different from each other,
• the polyimide film is provided with a method of manufacturing a polyimide film having a moisture absorption expansion coefficient of about 9 ppm/% RH or less in a 25° C., 20 to 80% relative humidity range.
• the first dianhydride is 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, or a combination thereof Including,
• the first diamine includes m-phenylenediamine, p-phenylenediamine, or a combination thereof,
• a first binding ratio which is a ratio in which the first dianhydride and the first diamine are bonded, may be about 40 to about 70%.
• the second dianhydride may include pyromellitic dianhydride.
• the second diamine may include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, or a combination thereof.
• the first dianhydride is contained in an amount of about 40 to about 70 mol% based on the total number of moles of the first dianhydride and the second dianhydride, and the second dianhydride is It may be included in about 30 to about 60 mol%.
• the first diamine is contained in an amount of about 70 to about 98 mol%, and the second diamine is about 2 to It may be included in about 30 mol%.
• the first diamine is contained in an amount of about 80 to about 98 mol%, and the second diamine is about 2 to It is contained in about 20 mol%,
• the polyimide film may have a moisture absorption expansion coefficient of less than or equal to about 8 ppm/%RH in a range of 25° C. and 20 to 80% relative humidity.
• the polyimide film may have a moisture absorption expansion coefficient of less than or equal to about 9 ppm/%RH at 25° C. and 3 to 90% relative humidity.
• a flexible metal foil laminated plate comprising a metal foil formed on the polyimide film is provided.
• the present invention has an effect of providing a polyimide film having a small moisture absorption expansion coefficient and excellent dimensional stability, a method of manufacturing the same, and a flexible metal clad laminate including the same.
• first bonding ratio refers to the first dianhydride and the first dianhydride among the polyimide films prepared from imidization of a polyamic acid formed from the reaction of a first dianhydride, a second dianhydride, a first diamine, and a second diamine.
• the first diamine may mean a bonded ratio
• the "second bonding ratio” may mean a bonded ratio of the second dianhydride and the first diamine
• the second bonding ratio may be determined according to the first bonding ratio.
• 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 equal moles, and the molar ratio of the first dianhydride based on the total number of moles of the first dianhydride and the second dianhydride.
• a polyimide film has a moisture absorption expansion coefficient of about 9 ppm/% RH or less in the 25° C., 20 to 80% relative humidity section (eg, about 0, about 0.5, about 1, about 1.5, about 2, about 2.5, About 3, about 3.5, about 4, about 4.5, about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, about 8, about 8.5 or about 9 ppm/%RH).
• dimensional stability may be excellent.
• the lower limit of the moisture absorption expansion coefficient of the polyimide film in the range of 25° C.
• the moisture absorption expansion coefficient of the polyimide film in the range of 25° C.
• the polyimide film may be derived from imidization of a polyamic acid formed from a reaction of a first dianhydride, a second dianhydride, a first diamine, and a second diamine.
• a polyamic acid formed from a reaction of a first dianhydride, a second dianhydride, a first diamine, and a second diamine for example, in the polyimide film, from the imidization of a polyamic acid formed by sequentially reacting a second dianhydride and a second diamine with a pre-reactant of a first dianhydride and a first diamine to extend at least some of the ends of the pre-reactant. It may be induced, but is not limited thereto.
• the first dianhydride and the second anhydride may be different from each other, and the first diamine and the second diamine may be different from each other.
• the first dianhydride may include 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, or a combination thereof. have.
• the first dianhydride may be 3,3',4,4'-biphenyltetracarboxylic dianhydride, but is not limited thereto.
• the type of the second anhydride is not particularly limited as long as it is different from the first anhydride.
• the second anhydride may include pyromellitic dianhydride, but is not limited thereto.
• the first diamine may include m-phenylenediamine, p-phenylenediamine, or a combination thereof.
• the first diamine may be p-phenylenediamine, but is not limited thereto.
• the type of the second diamine is not particularly limited as long as it is different from the first diamine.
• the second diamine may include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, or a combination thereof.
• the second diamine may be 4,4'-diaminodiphenyl ether, but is not limited thereto.
• the first binding ratio which is the ratio of the first dianhydride and the first diamine in the polyimide film, is about 40 to about 70% (e.g., about 40, about 41, about 42, about 43, About 44, about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, about 57, about 58, about 59, about 60 , About 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69 or about 70%).
• the moisture absorption expansion coefficient of the polyimide film is small, so that dimensional stability may be excellent.
• the first binding ratio is, for example, about 45 to about 70%, another such as about 50 to about 70%, another such as about 40 to about 60%, another such as about 45 to about 55%. Can be According to one embodiment, the first binding ratio may be about 50 to about 70%. According to another embodiment, the first binding ratio may be about 45 to about 55%, but is not limited thereto.
• the first binding ratio which is the ratio of the first dianhydride and the first diamine in the polyimide film
• the second dianhydride is about 20 to about 50% (e.g., about 20, about 21, about 22, about 23, about 24, about 25, about 26, about 27, about 28, about 29, about 30, about 31, about 32, about 33, about 34, about 35, about 36, about 37, about 38, about 39, about 40, about 41, about 42, about 43, about 44, About 45, about 46, about 47, about 48, about 49 or about 50%).
• the polyimide film has a small coefficient of moisture absorption and excellent dimensional stability, as well as a predetermined physical property, for example, a predetermined coefficient of thermal expansion (CTE) (e.g., about 2 to about 5 ⁇ m/(m)). ⁇ °C), so when manufacturing a flexible metal foil laminate using this, the adhesion between the polyimide film and the metal foil can be excellent.
• CTE coefficient of thermal expansion
• the first dianhydride is about 40 to about 70 mol% based on the total moles of the first dianhydride and the second dianhydride (e.g., about 40, about 41, about 42, about 43, about 44, about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, about 57, about 58, about 59, about 60, About 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69 or about 70 mol%), and the second dianhydride is about 30 to about 60 mol% ( For example, about 30, about 31, about 32, about 33, about 34, about 35, about 36, about 37, about 38, about 39, about 40, about 41, about 42, about 43, about 44, about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, about 57
• the first dianhydride is, for example, about 45 to about 70 mol%, another example, about 50 to about 70 mol%, another example
• the second dianhydride is, for example, about 30 to about 55 mol%, and for another example, about 30 to about 30 to about 55 mol%. It may be included in about 50 mol%, another example about 40 to about 60 mol%, another example about 45 to about 55 mol%, but is not limited thereto.
• the first diamine is about 70 to about 98 mol% (e.g., about 70, about 71, about 72, about 73, about 74, based on the total number of moles of the first diamine and the second diamine) About 75, about 76, about 77, about 78, about 79, about 80, about 81, about 82, about 83, about 84, about 85, about 86, about 87, about 88, about 89, about 90, about 91 , About 92, about 93, about 94, about 95, about 96, about 97, or about 98 mol%), and the second diamine is about 2 to about 30 mol% (e.g., about 2, about 3 , About 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19, about 20, about 21, about 22, about 23, about 24, about 25, about 26, about 27, about 28, about 29, or about 30 mole%).
• the second diamine is about 2 to about 30 mol%
• the first diamine is, for example, about 70 to about 92 mol%, another example, about 70 to about 90 mol%, another example About 70 to about 88 mole%, another example about 80 to about 98 mole%, another example about 80 to about 92 mole%, another example about 80 to about 90 mole%, another example
• the second diamine is, for example, about 8 to about 30 mol%, for example, about 10 to about 30 mol%, and another example, about 12 to about 30 mol%, another such as about 2 to about 20 mol%, another such as about 8 to about 20 mol%, another such as about 10 to about 20 mol%, another such as about 12 To about 20 mol%, but is not limited thereto.
• the polyimide film has a moisture absorption expansion coefficient of about 9 ppm/%RH or less (eg, about 0, about 0.5, about 1, about 1.5, About 2, about 2.5, about 3, about 3.5, about 4, about 4.5, about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, about 8, about 8.5 or about 9 ppm/%RH) have. In the above range, dimensional stability may be excellent.
• the lower limit of the moisture absorption expansion coefficient of the polyimide film in the range of 25°C and 3 to 90% relative humidity is, for example, greater than 0, about 1, about 2, about 3, about 4, about 5, about 6, about 7 or About 9, about 8.9, about 8.8, about 8.7, about 8.6, about 8.5, about 8.4, about 8.3 or about 8.2 ppm/%RH
• the upper limit can be about ppm/%RH
• the upper limit can be about 9, about 8.9, about 8.8, about 8.7, about 8.6, about 8.5, about 8.4, about 8.3 or about 8.2 ppm/%RH, wherein
• the lower limit and the upper limit may be combined with each other, but are not limited thereto.
• the thickness of the polyimide film may be appropriately selected in consideration of the use, environment, and physical properties of the polyimide film.
• the thickness of the polyimide film is about 10 to about 500 ⁇ m (e.g., about 10, about 50, about 100, about 150, about 200, about 250, about 300, about 350, about 400, about 450 Or about 500 ⁇ m), for example about 25 to about 50 ⁇ m, for another example, about 35 to about 50 ⁇ m, for another example, about 25 to about 35 ⁇ m, but is not limited thereto.
• the coefficient of thermal expansion of the polyimide film may be appropriately selected in consideration of the use, environment of use, and physical properties of the polyimide film.
• the coefficient of thermal expansion of the polyimide film may be lower than that of the metal foil.
• the metal foil is about 16 to about 17 ⁇ m/m ⁇ ° C. (e.g., about 16, about 16.1, about 16.2, about 16.3, about 16.4, about 16.5, about 16.6, about 16.7, about 16.8, about 16.9, or It has a coefficient of thermal expansion of about 17 ⁇ m/m ⁇ ° C.), and the polyimide film has a coefficient of thermal expansion of about 2 to about 7 ⁇ m/m ⁇ ° C.
• the coefficient of thermal expansion of the polyimide film was heated from room temperature (25°C) to 420°C at a rate of 10°C/min under a load of 0.01 to 0.05N and nitrogen atmosphere using TA's TMA (thermal mechanical apparatus) Q400. It can be obtained, but is not limited thereto.
• the glass transition temperature of the polyimide film may be appropriately selected in consideration of the use, environment, and physical properties of the polyimide film.
• the polyimide film is about 370°C or higher (e.g., about 370, about 380, about 390, about 400, about 410 or about 420°C, other examples
• it may have a glass transition temperature of about 370 to about 420°C, another example of about 380°C or more, another example of about 380 to about 420°C).
• the glass transition temperature of the polyimide film can be obtained by heating at a rate of 5°C/min from room temperature (25°C) to 550°C in a nitrogen atmosphere using TA's DMA (dynamic mechanical analysis) Q800, but is limited thereto. It does not become.
• TA's DMA dynamic mechanical analysis
• a method of manufacturing a polyimide film includes mixing and reacting a first dianhydride and a first diamine in a solvent, and then adding and reacting a second dianhydride and a second diamine to form a polyamic acid solution, and imidizing the polyamic acid.
• the first dianhydride and the second anhydride are different from each other
• the first diamine and the second diamine are different from each other
• the polyimide film is 25° C., 20 to 80% relative humidity.
• the moisture absorption expansion coefficient in the section is about 9ppm/%RH or less (e.g., about 0, about 0.5, about 1, about 1.5, about 2, about 2.5, about 3, about 3.5, about 4, about 4.5, about 5 , About 5.5, about 6, about 6.5, about 7, about 7.5, about 8, about 8.5 or about 9 ppm/%RH).
• the polyimide film prepared by the above method may have excellent dimensional stability.
• a first dianhydride and a first diamine are mixed and reacted in a solvent, and then a second dianhydride and a second diamine are added and reacted to form a polyamic acid solution.
• the second dianhydride is added and reacted, and then the second diamine is added and reacted to form a polyamic acid solution.
• the second dianhydride and the second diamine may be added together and reacted to form a polyamic acid solution.
• the first dianhydride and the first diamine are mixed and reacted.
• the prereactant of the dianhydride and the first diamine and the second dianhydride may react first, and then the second diamine may react.
• the first dianhydride may include, for example, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, or a combination thereof. have.
• the first dianhydride may be 3,3',4,4'-biphenyltetracarboxylic dianhydride, but is not limited thereto.
• the type of the second anhydride is not particularly limited as long as it is different from the first anhydride.
• the second anhydride may include pyromellitic dianhydride, but is not limited thereto.
• the first diamine may include, for example, m-phenylenediamine, p-phenylenediamine, or a combination thereof. According to one embodiment, the first diamine may be p-phenylenediamine, but is not limited thereto.
• the type of the second diamine is not particularly limited as long as it is different from the first diamine.
• the second diamine may include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, or a combination thereof.
• the second diamine may be 4,4'-diaminodiphenyl ether, but is not limited thereto.
• the first dianhydride is about 40 to about 70 mol% based on the total moles of the first dianhydride and the second dianhydride (e.g., about 40, about 41, about 42, about 43, about 44, about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, about 57, about 58, about 59, about 60, About 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69 or about 70%), and the second dianhydride is about 30 to about 60 mol% (e.g.
• the first dianhydride is, for example, about 45 to about 70 mol%, another example, about 50 to about 70 mol%, another example For example, about 40 to about 60 mol%, and for another example, about 45 to about 55 mol%
• the second dianhydride is, for example, about 30 to about 55 mol%, and for another example, about 30 to about 30 to about 55 mol%. It may be included in about 50 mol%, another example about 40 to about 60 mol%, another example about 45 to about 55 mol%, but is not limited thereto.
• the first diamine is about 70 to about 98 mol% (e.g., about 70, about 71, about 72, about 73, about 74, based on the total number of moles of the first diamine and the second diamine) About 75, about 76, about 77, about 78, about 79, about 80, about 81, about 82, about 83, about 84, about 85, about 86, about 87, about 88, about 89, about 90, about 91 , About 92, about 93, about 94, about 95, about 96, about 97, or about 98 mol%), and the second diamine is about 2 to about 30 mol% (e.g., about 2, about 3 , About 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19, about 20, about 21, about 22, about 23, about 24, about 25, about 26, about 27, about 28, about 29, or about 30 mole%).
• the second diamine is about 2 to about 30 mol%
• the first diamine is, for example, about 70 to about 92 mol%, another example, about 70 to about 90 mol%, another example About 70 to about 88 mole%, another example about 80 to about 98 mole%, another example about 80 to about 92 mole%, another example about 80 to about 90 mole%, another example
• the second diamine is, for example, about 8 to about 30 mol%, for example, about 10 to about 30 mol%, and another example, about 12 to about 30 mol%, another such as about 2 to about 20 mol%, another such as about 8 to about 20 mol%, another such as about 10 to about 20 mol%, another such as about 12 To about 20 mol%, but is not limited thereto.
• the type of the solvent is not particularly limited as long as it is a solvent capable of dissolving the polyamic acid.
• the solvent may be an aprotic polar solvent among organic solvents, such as amide solvents such as N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc), phenolic solvents such as p-chlorophenol and o-chlorophenol, N-methyl-pyrrolidone (NMP), ⁇ -butyrolactone (GBL), and Diglyme, and these may be used alone or It can be used in combination of two or more.
• amide solvents such as N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc)
• phenolic solvents such as p-chlorophenol and o-chlorophenol, N-methyl-pyrrolidone (NMP), ⁇ -butyrolactone (GBL), and Diglyme, and these may be used
• an auxiliary solvent such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water may be used to adjust the solubility of the polyamic acid.
• the polyamic acid solution is about 10 to about 20% by weight (e.g., about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19 or about 20%) polyamic acid solids and about 80 to about 90% (e.g., about 80, about 81, about 82, about 83, about 84, about 85, about 86, about 87, about 88 , About 89 or about 90% by weight) of a solvent.
• the polyamic acid solution may contain about 13 to about 17 weight percent (e.g., about 15 weight percent) polyamic acid solids and about 83 to about 87 weight percent (e.g., about 85 weight percent) solvent. It may include, but is not limited thereto.
• the polyamic acid solution is about 90,000 to about 300,000 cP (e.g., about 90,000, about 100,000, about 110,000, about 120,000, about 130,000, about 140,000, about 150,000, about 160,000, about 170,000, about 180,000 , About 190,000, about 200,000, about 210,000, about 220,000, about 230,000, about 240,000, about 250,000, about 260,000, about 270,000, about 280,000, about 290,000 or about 300,000 cP).
• processability may be excellent in manufacturing the polyimide film.
• the viscosity of the polyamic acid can be obtained as an average value measured twice at 50 rpm through 7 scandals at 25° C. using a Brookfield viscometer (RVDV-II+P), but is not limited thereto.
• the viscosity of the polyamic acid solution may be about 100,000 to about 250,000 cP, but is not limited thereto.
• the polyamic acid is about 150,000 to about 1,000,000 (e.g., about 150,000, about 200,000, about 250,000, about 300,000, about 350,000, about 400,000, about 450,000, about 500,000, about 550,000, about 600,000, about 650,000, about 700,000, about 750,000, about 800,000, about 850,000, about 900,000, about 950,000, or about 1,000,000).
• the weight average molecular weight may mean a weight average molecular weight in terms of polystyrene measured using gel permeation chromatography (GPC).
• the weight average molecular weight of the polyamic acid may be about 260,000 to about 700,000, for example, about 280,000 to about 500,000, but is not limited thereto.
• the reaction may be performed at a temperature of about 0 to about 80° C. for about 10 minutes to about 30 hours, and the polymerization reaction may be controlled by adding a small amount of an end sealant before polymerization, but is limited thereto. It does not become.
• additives may be added when preparing polyamic acid for the purpose of improving various properties of the film such as sliding properties, thermal conductivity, conductivity, corona resistance, and loop hardness of the polyimide film.
• additives include fillers, and examples of such fillers include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and the like, but are not limited thereto.
• the content of the additive may be appropriately selected within a range that does not impair the object of the present invention.
• the polyamic acid in the solution can be imidized.
• a dehydrating agent and an imidizing agent may be added to the polyamic acid.
• the dehydrating agent is not particularly limited as long as it can accelerate the ring closure reaction through the dehydration action of the polyamic acid, and examples of the dehydrating agent include acetic anhydride.
• the imidizing agent is not particularly limited as long as it can accelerate the ring closure reaction to the polyamic acid, and examples of the imidizing agent include tertiary amines such as quinoline, isoquinoline, ⁇ -picoline, pyridine, and the like. .
• the contents of the dehydrating agent and the imidizing agent are not particularly limited, but for example, the dehydrating agent is about 2.5 to about 5.0 molar ratio (e.g., about 2.5, about 2.6, about 2.7, about 2.8) to 1 mol of the amic acid group in the polyamic acid.
• the step of imidizing the polyamic acid may include preparing a composition for a polyimide film by mixing a dehydrating agent and an imidizing agent with the polyamic acid; And forming the composition.
• polyamic acid is applied in the form of a film on a substrate (for example, a glass plate, aluminum foil, an endless stainless belt, or a stainless drum, etc.), and then about 30 to about 200°C (for example, about 50 to After the first heat treatment at a temperature of about 150° C. for about 15 seconds to about 30 minutes to prepare a gel film, the gel film from which the substrate was removed is prepared at a temperature of about 50 to about 650° C. (for example, about 20 to about 600° C.).
• the amic acid group can be rapidly converted to an imide group by the first heat treatment, and the amic acid group can be quickly converted to an imide group by the second heat treatment, and the solvent, dehydrating agent, imidizing agent, etc. remaining in the gel film can be removed. .
• the gel film may be selectively stretched to control the thickness of the polyimide film and improve orientation, but is not limited thereto.
• the polyimide film may be further cured by heating the second heat-treated polyimide film at a temperature of about 400 to about 650° C. for a third heat treatment for about 5 to about 400 seconds, and the third heat treatment is In order to alleviate the internal stress that may remain in the polyimide film, it may be performed under a predetermined tension.
• the polyimide film prepared by the above-described manufacturing method has a moisture absorption expansion coefficient of about 9 ppm/% RH or less in the range of 25° C. and 20 to 80% relative humidity (eg, about 0, about 0.5, about 1, about 1.5, About 2, about 2.5, about 3, about 3.5, about 4, about 4.5, about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, about 8, about 8.5 or about 9 ppm/%RH) have.
• dimensional stability may be excellent.
• the lower limit of the moisture absorption expansion coefficient of the polyimide film in the range of 25° C.
• the moisture absorption expansion coefficient of the polyimide film in the range of 25° C.
• the polyimide film prepared by the above-described manufacturing method has a first binding ratio of about 40 to about 70% (for example, a ratio of the first dianhydride and the first diamine bonded to each other in the polyimide film).
• 40 about 41, about 42, about 43, about 44, about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, About 57, about 58, about 59, about 60, about 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69 or about 70%).
• the first binding ratio is, for example, about 45 to about 70%, another such as about 50 to about 70%, another such as about 40 to about 60%, another such as about 45 to about 55%. Can be According to one embodiment, the first binding ratio may be about 50 to about 70%. According to another embodiment, the first binding ratio may be about 45 to about 55%, but is not limited thereto.
• the polyimide film prepared by the above-described manufacturing method has a first binding ratio of about 40 to about 70% (for example, a ratio of the first dianhydride and the first diamine bonded to each other in the polyimide film). 50 to about 70%), and the second binding ratio, which is the ratio of the second dianhydride and the first diamine, is about 20 to about 50% (e.g., about 20, about 21, about 22, about 23, about 24 , About 25, about 26, about 27, about 28, about 29, about 30, about 31, about 32, about 33, about 34, about 35, about 36, about 37, about 38, about 39, about 40, about 41, about 42, about 43, about 44, about 45, about 46, about 47, about 48, about 49 or about 50%).
• the second binding ratio which is the ratio of the second dianhydride and the first diamine
• the polyimide film has a small coefficient of moisture absorption and excellent dimensional stability, as well as a predetermined physical property, for example, a predetermined coefficient of thermal expansion (CTE) (e.g., about 2 to about 5 ⁇ m/(m)). ⁇ °C), so when manufacturing a flexible metal foil laminate using this, the adhesion between the polyimide film and the metal foil can be excellent.
• CTE coefficient of thermal expansion
• the polyimide film manufactured by the above-described manufacturing method has a moisture absorption expansion coefficient of about 9 ppm/%RH or less (for example, about 0, about 0.5, About 1, about 1.5, about 2, about 2.5, about 3, about 3.5, about 4, about 4.5, about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, about 8, about 8.5 or about 9 ppm /%RH).
• dimensional stability may be excellent.
• the lower limit of the moisture absorption expansion coefficient of the polyimide film in the range of 25°C and 3 to 90% relative humidity is, for example, greater than 0, about 1, about 2, about 3, about 4, about 5, about 6, about 7, About 8 or about 8.2 ppm/%RH, with an upper limit of about 9, about 8.9, about 8.8, about 8.7, about 8.6, about 8.5, about 8.4, about 8.3 or about 8.2 ppm/%RH
• the lower limit and the upper limit may be combined with each other, but are not limited thereto.
• the thickness of the polyimide film manufactured by the above-described manufacturing method may be appropriately selected in consideration of the use, environment, and physical properties of the polyimide film.
• the thickness of the polyimide film is about 10 to about 500 ⁇ m (e.g., about 10, about 50, about 100, about 150, about 200, about 250, about 300, about 350, about 400, about 450 Or about 500 ⁇ m), for example about 25 to about 50 ⁇ m, for another example, about 35 to about 50 ⁇ m, for another example, about 25 to about 35 ⁇ m, but is not limited thereto.
• the coefficient of thermal expansion of the polyimide film manufactured by the above-described manufacturing method may be appropriately selected in consideration of the use, environment, and physical properties of the polyimide film.
• the coefficient of thermal expansion of the polyimide film may be lower than that of the metal foil.
• the metal foil is about 16 to about 17 ⁇ m/m ⁇ ° C.
• the polyimide film has a coefficient of thermal expansion of about 2 to about 7 ⁇ m/m ⁇ ° C. (for example, about 2, about 3, about 4, about 5, about 6 or about 7 ⁇ m/m ⁇ °C, for example, about 2 to about 5 ⁇ m/m ⁇ °C), but is not limited thereto.
• the glass transition temperature of the polyimide film manufactured by the above-described manufacturing method may be appropriately selected in consideration of the use, environment, and physical properties of the polyimide film.
• the polyimide film when a polyimide film is used for a flexible metal foil laminate, the polyimide film is about 370°C or higher (e.g., about 370, about 380, about 390, about 400, about 410 or about 420°C, other examples
• it may have a glass transition temperature of about 370 to about 420°C, another example of about 380°C or more, another example of about 380 to about 420°C).
• a flexible metal foil laminated plate including the polyimide film described above is provided.
• a flexible metal foil laminate may be formed of a metal foil on one side or both sides of a polyimide film.
• the flexible metal foil laminate may include the above-described polyimide film or a polyimide film manufactured by the above-described manufacturing method; And a metal foil formed on the polyimide film.
• the flexible metal foil laminate can be manufactured by various methods commonly used in the art.
• the flexible metal foil laminate is (i) a casting method in which a polyamic acid solution is cast on a metal foil and then imidized, (ii) a metallization method in which a metal layer is directly formed on a polyimide film by sputtering, (iii) It can be produced by a method such as a lamination method in which a polyimide film and a metal foil are bonded by heat and pressure.
• the flexible metal foil laminate of the present invention has a low coefficient of moisture absorption and expansion of the polyimide film, and may have excellent dimensional stability even in a high-temperature processing process.
• DMF Dimethylformamide
• 3,3',4,4'-biphenyltetracarboxylic dianhydride as the first dianhydride and p-phenylenediamine as the first diamine were added in a molar ratio of 7:9. After the addition, it was reacted at 25° C. for 2 hours.
• pyromellitic dianhydride as a second dianhydride and 4,4'-diaminodiphenyl ether as a second diamine were added in a molar ratio of 3:1 and reacted at 30° C. for 2 hours to obtain a solid content of polyamic acid.
• a polyamic acid solution having a content of 15% by weight was prepared. At this time, 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 were substantially equimolar.
• composition for preparing a polyimide film To the thus prepared polyamic acid solution, 3.5 molar ratio of acetic anhydride and 1.1 molar ratio of isoquinoline per 1 mol of amic acid group were added to obtain a composition for preparing a polyimide film.
• the composition was cast on a SUS plate (100SA, Sandvik) using a doctor blade, and dried at 90° C. for 4 minutes to prepare a gel film. After separating the gel film from the SUS plate, heat treatment was performed at 250 to 380° C. for 14 minutes to prepare a polyimide film having an average thickness of 30 ⁇ m.
• a polyimide film was prepared using the same method as in Example 1, except that the content of each component was changed as described in Table 1.
• Example 1 70 30 90 10 70% 6.5
• Example 2 50 50 96.2 3.8 50% 6.9
• Example 3 50 50 75 25 50% 8.3
• Example 4 50 50 87 13 50% 6.2 Comparative Example 1
• 30 70 60 40 30% 12.9 Comparative Example 2
• 30 70 90 10 30% 11.7
• the polyimide films of Examples 1 to 4 of the present invention have a low coefficient of thermal expansion of 9 ppm/%RH or less in the 25°C, 20 to 80% relative humidity section, but not In the case of Comparative Examples 1 and 2, it can be seen that the coefficients of thermal expansion are as high as 12.9 and 11.7 ppm/% RH, respectively.
• the polyimide film prepared in Example 4 was cut into 25 mm ⁇ 130 mm, and then fastened to CHEmeter (BMA) to measure the dimensional change from 3% to 90% relative humidity at 25°C. As a result, it was confirmed that the moisture absorption expansion coefficient at 25° C. and 3 to 90% relative humidity was as low as 8.2 ppm/% RH.

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